Inorganics

23 pages, 3440 KiB

Open AccessEditor’s ChoiceReview

The Importance of Being Casiopeina as Polypharmacologycal Profile (Mixed Chelate–Copper (II) Complexes and Their In Vitro and In Vivo Activities)

by Zenayda Aguilar-Jiménez, Adrián Espinoza-Guillén, Karen Resendiz-Acevedo, Inés Fuentes-Noriega, Carmen Mejía and Lena Ruiz-Azuara

Inorganics 2023, 11(10), 394; https://doi.org/10.3390/inorganics11100394 - 7 Oct 2023

Cited by 16 | Viewed by 3163

Abstract

In this review, we present a timeline that shows the origin of mixed chelate copper (II) complexes, registered as Mark Title Casiopeínas^®, as the first copper (II) compounds proposed as anticancer drugs in 1988 and 1992. In the late twentieth century, [...] Read more.

In this review, we present a timeline that shows the origin of mixed chelate copper (II) complexes, registered as Mark Title Casiopeínas^®, as the first copper (II) compounds proposed as anticancer drugs in 1988 and 1992. In the late twentieth century, the use of essential metals as anticancer agents was not even considered, except for their antifungal or antibacterial effects; also, copper, as gold salts, was used for arthritis problems. The use of essential metals as anticancer drugs to diminish the secondary toxic effects of Cisplatin was our driving force: to find less toxic and even more economical compounds under the rational design of metal chelate complexes. Due to their chemical properties, copper compounds were the choice to continue anticancer drug development. In this order of ideas, the rational designs of mixed chelate–copper (II) complexes (Casiopeínas, (Cas) homoleptic or heteroleptic, depending on the nature of the secondary ligand) were synthesized and fully characterized. In the search for new, more effective, and less toxic drugs, Casiopeína^® (Cas) emerged as a family of approximately 100 compounds synthesized from coordinated Cu(II) complexes with proven antineoplastic potential through cytotoxic action. The Cas have the general formula [Cu(N–N)(N–O)]NO₃ and [Cu(N–N)(O–O)]NO₃, where N–N is an aromatic substituted diimine (1,10-phenanthroline or 2,2′-bipyridine), and the oxygen donor (O–O) is acetylacetonate or salicylaldehyde. Lately, some similar compounds have been developed by other research groups considering a similar hypothesis after Casiopeína’s discoveries had been published, as described herein. As an example of translational medicine criteria, we have covered each step of the established normative process for drug development, and consequently, one of the molecules (Casiopeína III ia (CasIIIia)) has reached the clinical phase I. For these copper compounds, other activities, such as antibacterial, antiparasitic and antiviral, have been discovered. Full article

(This article belongs to the Special Issue Editorial Board Members’ Collection Series in “Bioinorganic Chemistry of Copper”)

► Show Figures

Graphical abstract

15 pages, 3317 KiB

Open AccessEditor’s ChoiceArticle

Sn(IV)porphyrin-Anchored TiO₂ Nanoparticles via Axial-Ligand Coordination for Enhancement of Visible Light-Activated Photocatalytic Degradation

by Nirmal Kumar Shee and Hee-Joon Kim

Inorganics 2023, 11(8), 336; https://doi.org/10.3390/inorganics11080336 - 15 Aug 2023

Cited by 12 | Viewed by 1982

Abstract

A visible-light-active photocatalyst, SnP/AA@TiO₂, was fabricated by utilizing the coordination chemistry between the axial hydroxo-ligand in the (trans-dihydroxo)(5,10,15,20-tetraphenylporphyrinato)Sn(IV) complex (SnP) and adipic acid (AA) on the surface of TiO₂ nanoparticles. The SnP center was strongly bonded to the [...] Read more.

A visible-light-active photocatalyst, SnP/AA@TiO₂, was fabricated by utilizing the coordination chemistry between the axial hydroxo-ligand in the (trans-dihydroxo)(5,10,15,20-tetraphenylporphyrinato)Sn(IV) complex (SnP) and adipic acid (AA) on the surface of TiO₂ nanoparticles. The SnP center was strongly bonded to the surface of the TiO₂ nanoparticles via the adipic acid linkage in SnP/AA@TiO₂, as confirmed by various instrumental techniques. SnP/AA@TiO₂ exhibited remarkably enhanced photocatalytic activity toward the degradation of rhodamine B dye (RhB) in aqueous solution under visible-light irradiation. The RhB degradation efficiency of SnP/AA@TiO₂ was 95% within 80 min, with a rate constant of 0.0366 min⁻¹. The high degradation efficiency, low catalyst loading and high reusability make SnP-anchored photocatalysts more efficient than other photocatalysts, such as TiO₂ and SnP@TiO₂. Full article

(This article belongs to the Special Issue Nanocomposites for Photocatalysis)

► Show Figures

Graphical abstract

13 pages, 1153 KiB

Open AccessFeature PaperEditor’s ChoiceArticle

Redox Targets for Phosphine–Boranes

by Yonatan Morocz, Rachel E. Greben and Leonard A. Levin

Inorganics 2023, 11(7), 310; https://doi.org/10.3390/inorganics11070310 - 22 Jul 2023

Cited by 1 | Viewed by 1533

Abstract

Understanding the complex mechanisms underlying redox-mediated biological processes is a fundamental pillar of cellular biology. We describe the identification and quantification of disulfide formation and reduction in response to phosphine–borane complexes. We illustrate the specific cysteine reduction effects of the novel phosphine–borane complex [...] Read more.

Understanding the complex mechanisms underlying redox-mediated biological processes is a fundamental pillar of cellular biology. We describe the identification and quantification of disulfide formation and reduction in response to phosphine–borane complexes. We illustrate the specific cysteine reduction effects of the novel phosphine–borane complex bis(3-propionic acid methyl ester) phenylphosphine–borane complex (PB1) on cultured 661W cells. A total of 1073 unique protein fragments from 628 unique proteins were identified and quantified, of which 13 were found to be statistically significant in comparison to control cells. Among the 13 identified proteins were Notch1, HDAC1, UBA1, USP7, and subunits L4 and L7 of the 60S ribosomal subunit, all of which are involved in redox or cell death-associated pathways. Leveraging the ability of tandem mass tagging mass spectrometry to provide quantitative data in an exploratory manner provides insight into the effect PB1 and other phosphine–borane compounds may have on the cysteine redoxome. Full article

(This article belongs to the Special Issue Synthesis and Innovative Biological Activity of Boron-Containing Compounds)

► Show Figures

Figure 1

20 pages, 2848 KiB

Open AccessEditor’s ChoiceReview

Carbon Quantum Dots: The Role of Surface Functional Groups and Proposed Mechanisms for Metal Ion Sensing

by Hasan Shabbir, Edit Csapó and Marek Wojnicki

Inorganics 2023, 11(6), 262; https://doi.org/10.3390/inorganics11060262 - 20 Jun 2023

Cited by 47 | Viewed by 7270

Abstract

Carbon dots (CDs) are zero-dimensional nanomaterials composed of carbon and surface groups attached to their surface. CDs have a size smaller than 10 nm and have potential applications in different fields such as metal ion detection, photodegradation of pollutants, and bio-imaging, in this [...] Read more.

Carbon dots (CDs) are zero-dimensional nanomaterials composed of carbon and surface groups attached to their surface. CDs have a size smaller than 10 nm and have potential applications in different fields such as metal ion detection, photodegradation of pollutants, and bio-imaging, in this review, the capabilities of CDs in metal ion detection will be described. Quantum confinement is generally viewed as the key factor contributing to the uniqueness of CDs characteristics due to their small size and the lack of attention on the surface functional groups and their roles is given, however, in this review paper, the focus will be on the functional group and the composition of CDs. The surface functional groups depend on two parameters: (i) the oxidation of precursors and (ii) their composition. The mechanism of metal ion detection is still being studied and is not fully understood. This review article emphasizes the current development and progress of CDs, focusing on metal ion detection based on a new perspective. Full article

(This article belongs to the Special Issue 10th Anniversary of Inorganics: Organometallic Chemistry)

► Show Figures

Graphical abstract

12 pages, 3812 KiB

Open AccessFeature PaperEditor’s ChoiceArticle

Improved Oxide Ion Conductivity of Hexagonal Perovskite-Related Oxides Ba₃W_1+xV_1−xO_8.5+x/2

by Yugo Kikuchi, Yuta Yasui, James R. Hester and Masatomo Yashima

Inorganics 2023, 11(6), 238; https://doi.org/10.3390/inorganics11060238 - 29 May 2023

Cited by 4 | Viewed by 1700

Abstract

Hexagonal perovskite-related oxides such as Ba₃WVO_8.5 have attracted much attention due to their unique crystal structures and significant oxide ion conduction. However, the oxide ion conductivity of Ba₃WVO_8.5 is not very high. Herein, we report new hexagonal [...] Read more.

Hexagonal perovskite-related oxides such as Ba₃WVO_8.5 have attracted much attention due to their unique crystal structures and significant oxide ion conduction. However, the oxide ion conductivity of Ba₃WVO_8.5 is not very high. Herein, we report new hexagonal perovskite-related oxides Ba₃W_1+xV_1−xO_8.5+x/2 (x = −0.1, −0.05, 0.05, 0.1, 0.25, 0.4, 0.5, 0.6, and 0.75). The bulk conductivity of Ba₃W_1.6V_0.4O_8.8 was found to be 21 times higher than that of the mother material Ba₃WVO_8.5 at 500 °C. Maximum entropy method (MEM) neutron scattering length density (NSLD) analyses of neutron diffraction data at 800 °C experimentally visualized the oxide ion diffusion pathways through the octahedral O2 and tetrahedral O3 sites in intrinsically oxygen-deficient layers. By increasing the excess W content x in Ba₃W_1+xV_1−xO_8.5+x/2, the excess oxygen content x/2 increases, which leads to more oxygen atoms at the O2 and O3 oxygen sites, a higher minimum NSLD on the O2–O3 path, and a higher level of conductivity. Another reason for the increased conductivity of Ba₃W_1.6V_0.4O_8.8 is the lower activation energy for oxide ion conduction, which can be ascribed to the longer (W/V)–O2 and (W/V)–O3 distances due to the substitution of V atoms with large-sized W species. The present findings open new avenues in the science and technology of oxide ion conductors. Full article

(This article belongs to the Special Issue Layered Perovskites: Synthesis, Properties and Structures)

► Show Figures

Graphical abstract

17 pages, 5497 KiB

Open AccessFeature PaperEditor’s ChoiceArticle

Chalcogen Bonds, Halogen Bonds and Halogen···Halogen Contacts in Di- and Tri-iododiorganyltellurium(IV) Derivatives

by Sergi Burguera, Rosa M. Gomila, Antonio Bauzá and Antonio Frontera

Inorganics 2023, 11(5), 209; https://doi.org/10.3390/inorganics11050209 - 12 May 2023

Cited by 4 | Viewed by 1839

Abstract

In this manuscript, we have examined the CSD (Cambridge Structural Database) to investigate the relative ability of Te and I (in practice, the heaviest chalcogen and halogen atoms) in di- and tri-iododiorganyltellurium(IV) derivatives to establish σ-hole interactions. The geometry around the Te(IV) in [...] Read more.

In this manuscript, we have examined the CSD (Cambridge Structural Database) to investigate the relative ability of Te and I (in practice, the heaviest chalcogen and halogen atoms) in di- and tri-iododiorganyltellurium(IV) derivatives to establish σ-hole interactions. The geometry around the Te(IV) in this type of compound is trigonal bipyramidal where the stereoactive lone pair at Te(IV) occupies one of the equatorial positions. In the solid state, Te(IV) tends to form pseudo-octahedral coordination by establishing strong noncovalent interactions opposite to the two covalent bonds of the equatorial plane. Such contacts can also be classified as chalcogen bonds following the recommendation of the International Union of Pure and Applied Chemistry (IUPAC). Such contacts have been analyzed energetically in this work using density functional theory (DFT) calculations, rationalized using molecular electrostatic potential (MEP) surface analysis and characterized using a combination of the quantum theory of atoms in molecules (QTAIM) and noncovalent interaction plot (NCIplot) computational tools. Finally, the observation of halogen bonds and type I halogen···halogen contacts is also emphasized and compared to the chalcogen bonds. Energy decomposition analysis has also been performed to compare the physical nature of chalcogen, halogen and type I interactions. Full article

► Show Figures

Graphical abstract

15 pages, 9033 KiB

Open AccessEditor’s ChoiceArticle

Crystal Structure and XPS Study of Titanium-Substituted M-Type Hexaferrite BaFe_12−xTi_xO₁₉

by Kim-Isabelle Mehnert, Manuel Häßner, Yanina Mariella Dreer, Indro Biswas and Rainer Niewa

Inorganics 2023, 11(5), 207; https://doi.org/10.3390/inorganics11050207 - 10 May 2023

Cited by 7 | Viewed by 2130

Abstract

The M-type barium hexaferrite substituted with titanium, BaFe

_{12 - x}

Ti

_{x}

O

_{19}

, was synthesized from sodium carbonate flux and the obtained single crystals with a maximum degree of substitution of up to about x = 0.9 were characterized. XPS [...] Read more.

The M-type barium hexaferrite substituted with titanium, BaFe

_{12 - x}

Ti

_{x}

O

_{19}

, was synthesized from sodium carbonate flux and the obtained single crystals with a maximum degree of substitution of up to about x = 0.9 were characterized. XPS measurements were carried out for the identification of side products and in particular in order to assign the valence states of the transition-metal constituents. Due to the aliovalent exchange of iron(III) with titanium(IV), an additional charge balance needs to occur. No titanium(III) was detected, while the amount of iron(II) increased in the same order of magnitude as the amount of titanium(IV); thus, the major charge balancing is attributed to the reduction of iron(III) to iron(II). According to the XPS data, the amount of titanium(IV) typically is slightly higher than that of iron(II). This is in line with a tendency to a minor formation of vacancies on the transition-metal sites becoming more important at higher substitution levels according to PXRD and WDS measurements, completing the picture of the charge-balance mechanism. XRD taken on single crystals indicates the distribution of titanium and vacancies over three of the five transition-metal sites. Full article

(This article belongs to the Special Issue 10th Anniversary of Inorganics: Inorganic Solid State Chemistry)

► Show Figures

Figure 1

23 pages, 11040 KiB

Open AccessEditor’s ChoiceReview

Co(III) Intermediates in Cobalt-Catalyzed, Bidentate Chelation Assisted C(sp²)-H Functionalizations

by Aleksandrs Cizikovs and Liene Grigorjeva

Inorganics 2023, 11(5), 194; https://doi.org/10.3390/inorganics11050194 - 29 Apr 2023

Cited by 8 | Viewed by 2368

Abstract

The C-H bond activation and functionalization is a powerful tool that provides efficient access to various organic molecules. The cobalt-catalyzed oxidative C-H bond activation and functionalization has earned enormous interest over the past two decades. Since then, a wide diversity of synthetic protocols [...] Read more.

The C-H bond activation and functionalization is a powerful tool that provides efficient access to various organic molecules. The cobalt-catalyzed oxidative C-H bond activation and functionalization has earned enormous interest over the past two decades. Since then, a wide diversity of synthetic protocols have been published for C-C, C-Het, and C-Hal bond formation reactions. To gain some insights into the reaction mechanism, the authors performed a series of experiments and collected evidence. Several groups have successfully isolated reactive Co(III) intermediates to elucidate the reaction mechanism. In this review, we will summarize information concerning the isolated and synthesized Co(III) intermediates in cobalt-catalyzed, bidentate chelation assisted C-H bond functionalization and their reactivity based on the current knowledge about the general reaction mechanism. Full article

(This article belongs to the Special Issue Recent Highlights Using Cobalt Catalysis)

► Show Figures

Graphical abstract

13 pages, 8083 KiB

Open AccessEditor’s ChoiceArticle

First-Principles Calculations to Investigate Structural, Electronic, Optical and Magnetic Properties of Pyrochlore Oxides Eu₂Tm₂O₇ (Tm = Hf, Sn, Zr) for Energy Applications

by Zeesham Abbas, Adeela Naz, Sajjad Hussain, Shabbir Muhammad, H. Algarni, Ahsan Ali and Jongwan Jung

Inorganics 2023, 11(5), 193; https://doi.org/10.3390/inorganics11050193 - 29 Apr 2023

Cited by 18 | Viewed by 1924

Abstract

Three newly designed pyrochlore oxides, Eu₂Tm₂O₇ (Tm = Hf, Sn, Zr), are analyzed for their magnetic, optical and electronic properties using ab-initio calculations within the context of density functional theory (DFT). We can refer these compounds as direct [...] Read more.

Three newly designed pyrochlore oxides, Eu₂Tm₂O₇ (Tm = Hf, Sn, Zr), are analyzed for their magnetic, optical and electronic properties using ab-initio calculations within the context of density functional theory (DFT). We can refer these compounds as direct bandgap materials because there is a very slight difference between the height of bands at the Γ- and M-point. It is observed that bandgap engineering can be performed by replacing Hf with Sn and Zr. It is observed from total density of states (TDOS) plots that shape and height of curves is not the same in spin up and spin down channels, showing significant magnetic moment in these compounds. It is evident from magnetic properties that a major portion of total magnetic moment (

m_{t o t}

) comes from Eu-atoms. In all compounds, the magnetic moment of O, Hf, Sn and Zr atoms is negative, whereas the magnetic moment of Eu-atoms is positive, showing their antiparallel arrangement. In both spin channels, significant absorption of the incoming photons is also shown by these compounds in the ultraviolet (UV) region. We can conclude on the basis of

R (ω)

that these compounds can be utilized in applications such as anti-reflecting coatings. These compounds are potential candidates for photovoltaic applications, such as solar cells, due to efficient absorption of incoming photons in visible and UV regions. Full article

(This article belongs to the Section Inorganic Solid-State Chemistry)

► Show Figures

Figure 1

14 pages, 2933 KiB

Open AccessFeature PaperEditor’s ChoiceArticle

X-ray Absorption Spectroscopy of Phosphine-Capped Au Clusters

by Shailendra K. Sharma, Bernt Johannessen, Vladimir B. Golovko and Aaron T. Marshall

Inorganics 2023, 11(5), 191; https://doi.org/10.3390/inorganics11050191 - 28 Apr 2023

Cited by 1 | Viewed by 2200

Abstract

The structural determination of ultrasmall clusters remains a challenge due to difficulties in crystallisation. Often the atomically precise clusters undergo structural change under the influence of the environment. X-ray absorption spectroscopy (XAS) can be an attractive tool to study the electronic and geometric [...] Read more.

The structural determination of ultrasmall clusters remains a challenge due to difficulties in crystallisation. Often the atomically precise clusters undergo structural change under the influence of the environment. X-ray absorption spectroscopy (XAS) can be an attractive tool to study the electronic and geometric properties of such clusters deposited onto various supports under in situ conditions. Herein, [Au₆(dppp)₄](NO₃)₂, [Au₉(PPh₃)₈](NO₃)₃, [Au₁₃(dppe)₅Cl₂]Cl₃, and Au₁₀₁(PPPh₃)₂₁Cl₅ clusters were studied using XAS. The clusters exhibited distinct features compared to bulk gold. XANES results show a systematic increase in the absorption edge energy and white line intensity, with a decrease in cluster nuclearity. The EXAFS of clusters are sensitive to nuclearity and ligands and were fitted with their known crystal structures. This study advances the understanding of the phosphine-ligated metal clusters relevant to practical applications in catalysis and sensing. Full article

(This article belongs to the Special Issue Phosphorus Ligands for the Stabilization of Unusual and Elusive Structures in Transition Metal Complexes)

► Show Figures

Figure 1

17 pages, 1734 KiB

Open AccessEditor’s ChoiceReview

Metal Hydride Composite Structures for Improved Heat Transfer and Stability for Hydrogen Storage and Compression Applications

by Liang Liu, Alexander Ilyushechkin, Daniel Liang, Ashleigh Cousins, Wendy Tian, Cherry Chen, Jon Yin and Liezl Schoeman

Inorganics 2023, 11(5), 181; https://doi.org/10.3390/inorganics11050181 - 24 Apr 2023

Cited by 9 | Viewed by 3706

Abstract

Metal alloys and intermetallic compounds offer an attractive method for safely storing hydrogen (H₂). The metal alloys absorb H₂ into their structure, often swelling and fracturing as a result of phase transformation during hydride formation/decomposition cycles. The absorption of H [...] Read more.

Metal alloys and intermetallic compounds offer an attractive method for safely storing hydrogen (H₂). The metal alloys absorb H₂ into their structure, often swelling and fracturing as a result of phase transformation during hydride formation/decomposition cycles. The absorption of H₂ is an exothermic process, requiring the effective and efficient removal of heat. This can be challenging as heat transfer to/from powdered beds is notoriously difficult, and often limited by poor thermal conductivity. Hence, the observed reaction kinetics for absorption and desorption of H₂ is dominated by heat flow. The most common method for improving the thermal conductivity of the alloy powders is to prepare them into composite structures with other high thermal conductivity materials, such as carbons and expanded natural graphite. Such composite structures, some also combined with polymers/resins, can also mitigate safety issues related to swelling and improve cyclic durability. This paper reviews the methods that have been used to prepare such composite structures and evaluates the observed impact on thermal conductivity. Full article

(This article belongs to the Special Issue State-of-the-Art and Progress in Metal-Hydrogen Systems)

► Show Figures

Figure 1

19 pages, 2502 KiB

Open AccessFeature PaperEditor’s ChoiceArticle

C–H Metalation of Terpyridine Stereoisomers with Ni(II), Pd(II), and Pt(II)

by Leo Payen, Lukas Kletsch, Tobias Lapić, Mathias Wickleder and Axel Klein

Inorganics 2023, 11(4), 174; https://doi.org/10.3390/inorganics11040174 - 21 Apr 2023

Cited by 4 | Viewed by 2444

Abstract

Ni(II), Pd(II), and Pt(II) complexes [M(Y-terpy)X] (X = Cl or Br) containing the tridentate N^C^N-cyclometalating 2,3′:5′,2″and 2,2′:4′,2″ stereoisomers of the well-known tridentate N^N^N ligand 2,2′:6′,2″-terpyridine (terpy) were synthesised in moderate to good yields through C–H activation. For the Pt complexes, the phenyl ethynide [...] Read more.

Ni(II), Pd(II), and Pt(II) complexes [M(Y-terpy)X] (X = Cl or Br) containing the tridentate N^C^N-cyclometalating 2,3′:5′,2″and 2,2′:4′,2″ stereoisomers of the well-known tridentate N^N^N ligand 2,2′:6′,2″-terpyridine (terpy) were synthesised in moderate to good yields through C–H activation. For the Pt complexes, the phenyl ethynide derivatives [Pt(Y-terpy)(C≡CPh)] were also obtained under Sonogashira conditions. In contrast to this, C^N^N cyclometalated complexes using the 2,2′:6′,3″- and 2,2′:6′4″-terpy isomers were not obtained. Comparison of the N^C^N complexes of the cyclometalated 2,3′:5′,2″- and 2,2′:4′,2″-terpy ligands with complexes [M(dpb)Cl] of the prototypical N^C^N cyclometalating ligand dpb⁻ (Hdpb = 2,6-diphenyl-pyridine) showed higher potentials for the terpy complexes for the ligand-centred reductions in line with the superior π-accepting properties of the terpy ligands compared with dpb. Metal-centred oxidations were facilitated by the dpb ligand carrying a central σ-donating phenyl group instead of a metalated pyridine moiety. The same trends were found for the long-wavelength absorptions and the derived electrochemical and optical band gaps. The lower σ-donating capacities of the cyclometalated terpy derivatives is also confirmed by a reduced trans influence in the structure of [Ni(2,3′:5′,2″-terpy)Br_0.14/OAc_0.86]. Attempts to re-crystallise some poorly soluble Pd(II) and Pt(II) complexes of this series under solvothermal conditions (HOAc) gave two structures with N-protonated cyclometalated pyridine moieties, [Pt(2,3′:5′,2″-terpyH)Cl]^.Cl and [Pd(2,3′:5′,2″-terpyH)Cl₂]. Full article

(This article belongs to the Special Issue Revealing Reaction Mechanisms in Homogeneous Transition Metal Catalysis, 2nd Edition)

► Show Figures

Graphical abstract

12 pages, 1967 KiB

Open AccessFeature PaperEditor’s ChoiceArticle

Surface Passivation of Organic-Inorganic Hybrid Perovskites with Methylhydrazine Iodide for Enhanced Photovoltaic Device Performance

by Chongzhu Hu, Zhuangzhuang Zhang, Jun Chen and Peng Gao

Inorganics 2023, 11(4), 168; https://doi.org/10.3390/inorganics11040168 - 16 Apr 2023

Cited by 7 | Viewed by 2453

Abstract

Organic-inorganic hybrid perovskites are highly efficient in photovoltaic applications, making the commercialization of perovskite solar cells (PSCs) possible. However, the high density of defects on the surface significantly affects the performance of PSCs. To address this issue, we have demonstrated a facile post-treatment [...] Read more.

Organic-inorganic hybrid perovskites are highly efficient in photovoltaic applications, making the commercialization of perovskite solar cells (PSCs) possible. However, the high density of defects on the surface significantly affects the performance of PSCs. To address this issue, we have demonstrated a facile post-treatment strategy utilizing methylhydrazine iodide (MHyI) to passivate the surface of the perovskite film. MHyI could co-ordinate with the dangling bonds on the surface of perovskite films, effectively passivating defects in the film and suppressing carrier non-radiative recombination. As a result, PSCs with MHyI modification exhibit a champion power conversion efficiency (PCE) of 23.19% and a high open-circuit voltage (V_OC) of 1.14 V (0.43 V voltage deficit). Moreover, unencapsulated solar cells maintain their initial efficiency of 88% after 30 days of exposure to ambient air with 30% humidity, and the devices with encapsulation retained 57% of their initial efficiency after 200 h of maximum power point (MPP) loading under constant light irradiation in ambient air. Overall, our results provide a facile method for improving the performance and stability of PSCs. Full article

(This article belongs to the Section Inorganic Materials)

► Show Figures

Figure 1

23 pages, 4800 KiB

Open AccessEditor’s ChoiceArticle

Comparative Spectroscopic and Electrochemical Study of V(V)-Substituted Keggin-Type Phosphomolybdates and -Tungstates

by Jan-Christian Raabe, José Aceituno Cruz, Jakob Albert and Maximilian J. Poller

Inorganics 2023, 11(4), 138; https://doi.org/10.3390/inorganics11040138 - 23 Mar 2023

Cited by 14 | Viewed by 2417

Abstract

Vanadium-substituted Keggin-type heteropolyanions have been studied for a wide variety of applications, ranging from catalysis to antiviral/antimicrobial agents. While the V-substituted phosphomolybdates [PV_xMo_12−xO₄₀]^(3+x)− have been well investigated in this context, comparatively little is known about [...] Read more.

Vanadium-substituted Keggin-type heteropolyanions have been studied for a wide variety of applications, ranging from catalysis to antiviral/antimicrobial agents. While the V-substituted phosphomolybdates [PV_xMo_12−xO₄₀]^(3+x)− have been well investigated in this context, comparatively little is known about the corresponding phosphotungstates [PV_xW_12-xO₄₀]^(3+x)−. We have succeeded in synthesizing the sodium salts of the whole series [PV_xW_12−xO₄₀]^(3+x)−, for x = 1 to 6, and characterised them spectroscopically (FT-IR, UV-Vis, ³¹P-, and ⁵¹V-NMR) and electrochemically (CV and SWV). Thereby, direct comparisons between the vanadium-substituted phosphomolybdates and -tungstates, with substitution degrees from 1 to 6, can be established, which provides a solid basis for further investigations of potential applications. Full article

(This article belongs to the Section Coordination Chemistry)

► Show Figures

Figure 1

12 pages, 1089 KiB

Open AccessFeature PaperEditor’s ChoiceArticle

Dibromo–Isonitrile and N-acyclic Carbene Complexes of Platinum(II): Synthesis and Reactivity

by Anna Farasat, Francesca Nerli, Luca Labella, Marco Taddei and Simona Samaritani

Inorganics 2023, 11(4), 137; https://doi.org/10.3390/inorganics11040137 - 23 Mar 2023

Cited by 1 | Viewed by 1663

Abstract

A series of dibromo-N-acyclic (NAC) carbene complexes of platinum(II) were synthesized, starting from trans-[Pt(μ-Br)Br(PPh₃)]₂ and according to a protocol previously optimized for the preparation of analogous chlorinated compounds. In the first step of the synthesis, the ring opening of [...] Read more.

A series of dibromo-N-acyclic (NAC) carbene complexes of platinum(II) were synthesized, starting from trans-[Pt(μ-Br)Br(PPh₃)]₂ and according to a protocol previously optimized for the preparation of analogous chlorinated compounds. In the first step of the synthesis, the ring opening of the dinuclear precursor was carried out using suitable isonitrile ligands, while the following step consisted of the addition of N,N-diethylamine to the products obtained in the first step. The two reactions were separately investigated, and attention was given to the differences between brominated and chlorinated systems. Full article

(This article belongs to the Special Issue Phosphorus Ligands for the Stabilization of Unusual and Elusive Structures in Transition Metal Complexes)

► Show Figures

Graphical abstract

30 pages, 10177 KiB

Open AccessFeature PaperEditor’s ChoiceArticle

The Electronic Nature of Cationic Group 10 Ylidyne Complexes

by Leonard R. Maurer, Jens Rump and Alexander C. Filippou

Inorganics 2023, 11(3), 129; https://doi.org/10.3390/inorganics11030129 - 18 Mar 2023

Cited by 6 | Viewed by 2429

Abstract

We report a broad theoretical study on [(PMe₃)₃MER]⁺ complexes, with M = Ni, Pd, Pt, E = C, Si, Ge, Sn, Pb, and R = Ar^Mes, Tbb, (Ar^Mes = 2,6-dimesitylphenyl; Tbb = C₆H [...] Read more.

We report a broad theoretical study on [(PMe₃)₃MER]⁺ complexes, with M = Ni, Pd, Pt, E = C, Si, Ge, Sn, Pb, and R = Ar^Mes, Tbb, (Ar^Mes = 2,6-dimesitylphenyl; Tbb = C₆H₂-2,6-[CH(SiMe₃)₂]₂-4-^tBu). A few years ago, our group succeeded in obtaining heavier homologues of cationic group 10 carbyne complexes via halide abstraction of the tetrylidene complexes [(PMe₃)₃M=E(X)R] (X = Cl, Br) using a halide scavenger. The electronic structure and the M-E bonds of the [(PMe₃)₃MER]⁺ complexes were analyzed utilizing quantum-chemical tools, such as the Pipek–Mezey orbital localization method, the energy decomposition analysis (EDA), and the extended-transition state method with natural orbitals of chemical valence (ETS-NOCV). The carbyne, silylidyne complexes, and the germylidyne complex [(PMe₃)₃NiGeAr^Mes]⁺ are suggested to be tetrylidyne complexes featuring donor–acceptor metal tetrel triple bonds, which are composed of two strong π(M→E) and one weaker σ(E→M) interaction. In comparison, the complexes with M = Pd, Pt; E = Sn, Pb; and R = Ar^Mes are best described as metallotetrylenes and exhibit considerable M−E−C bending, a strong σ(M→E) bond, weakened M−E π-components, and lone pair density at the tetrel atoms. Furthermore, bond cleavage energy (BCE) and bond dissociation energy (BDE) reveal preferred splitting into [M(PMe₃)₃]⁺ and [ER] fragments for most complex cations in the range of 293.3–618.3 kJ·mol⁻¹ and 230.4–461.6 kJ·mol⁻¹, respectively. Finally, an extensive study of the potential energy hypersurface varying the M−E−C angle indicates the presence of isomers with M−E−C bond angles of around 95°. Interestingly, these isomers are energetically favored for M = Pd, Pt; E = Sn, Pb; and R = Ar^Mes over the less-bent structures by 13–29 kJ·mol⁻¹. Full article

(This article belongs to the Special Issue Density Functional Theory (DFT) and Semi-empirical Quantum Mechanical (SQM) Methods in Organometallic Chemistry)

► Show Figures

Graphical abstract

29 pages, 8462 KiB

Open AccessEditor’s ChoiceArticle

Structural and Biological Properties of Heteroligand Copper Complexes with Diethylnicotinamide and Various Fenamates: Preparation, Structure, Spectral Properties and Hirshfeld Surface Analysis

by Milan Piroš, Martin Schoeller, Katarína Koňariková, Jindra Valentová, Ľubomír Švorc, Ján Moncoľ, Marian Valko and Jozef Švorec

Inorganics 2023, 11(3), 108; https://doi.org/10.3390/inorganics11030108 - 6 Mar 2023

Cited by 11 | Viewed by 2726

Abstract

Herein, we discuss the synthesis, structural and spectroscopic characterization, and biological activity of five heteroligand copper(II) complexes with diethylnicotinamide and various fenamates, as follows: flufenamate (fluf), niflumate (nifl), tolfenamate (tolf), clonixinate (clon), mefenamate (mef) and N, N-diethylnicotinamide (dena). The complexes of [...] Read more.

Herein, we discuss the synthesis, structural and spectroscopic characterization, and biological activity of five heteroligand copper(II) complexes with diethylnicotinamide and various fenamates, as follows: flufenamate (fluf), niflumate (nifl), tolfenamate (tolf), clonixinate (clon), mefenamate (mef) and N, N-diethylnicotinamide (dena). The complexes of composition: [Cu(fluf)₂(dena)₂(H₂O)₂] (1), [Cu(nifl)₂(dena)₂] (2), [Cu(tolf)₂(dena)₂(H₂O)₂] (3), [Cu(clon)₂(dena)₂] (4) and [Cu(mef)₂(dena)₂(H₂O)₂] (5), were synthesized, structurally (single-crystal X-ray diffraction) and spectroscopically characterized (IR, EA, UV-Vis and EPR). The studied complexes are monomeric, forming a distorted tetragonal bipyramidal stereochemistry around the central copper ion. The crystal structures of all five complexes were determined and refined with an aspheric model using the Hirshfeld atom refinement method. Hirshfeld surface analysis and fingerprint plots were used to investigate the intermolecular interactions in the crystalline state. The redox properties of the complexes were studied and evaluated via cyclic voltammetry. The complexes exhibited good superoxide scavenging activity as determined by an NBT assay along with a copper-based redox-cycling mechanism, resulting in the formation of ROS, which, in turn, predisposed the studied complexes for their anticancer activity. The ability of complexes 1–4 to interact with calf thymus DNA was investigated using absorption titrations, viscosity measurements and an ethidium-bromide-displacement-fluorescence-based method, suggesting mainly the intercalative binding of the complexes to DNA. The affinity of complexes 1–4 for bovine serum albumin was determined via fluorescence emission spectroscopy and was quantitatively characterized with the corresponding binding constants. The cytotoxic properties of complexes 1–4 were studied using the cancer cell lines A549, MCF-7 and U-118MG, as well as healthy MRC-5 cells. Complex 4 exhibited moderate anticancer activity on the MCF-7 cancer cells with IC₅₀ = 57 μM. Full article

(This article belongs to the Special Issue Recent Progress in Coordination Chemistry)

► Show Figures

Figure 1

13 pages, 12547 KiB

Open AccessFeature PaperEditor’s ChoiceArticle

Operando CO Infrared Spectroscopy and On-Line Mass Spectrometry for Studying the Active Phase of IrO₂ in the Catalytic CO Oxidation Reaction

by Phillip Timmer, Tim Weber, Lorena Glatthaar and Herbert Over

Inorganics 2023, 11(3), 102; https://doi.org/10.3390/inorganics11030102 - 28 Feb 2023

Cited by 4 | Viewed by 2031

Abstract

We combine operando diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) with on-line mass spectrometry (MS) to study the correlation between the oxidation state of titania-supported IrO₂ catalysts (IrO₂@TiO₂) and their catalytic activity in the prototypical CO oxidation reaction. [...] Read more.

We combine operando diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) with on-line mass spectrometry (MS) to study the correlation between the oxidation state of titania-supported IrO₂ catalysts (IrO₂@TiO₂) and their catalytic activity in the prototypical CO oxidation reaction. Here, the stretching vibration of adsorbed CO_ad serves as the probe. DRIFTS provides information on both surface and gas phase species. Partially reduced IrO₂ is shown to be significantly more active than its fully oxidized counterpart, with onset and full conversion temperatures being about 50 °C lower for reduced IrO₂. By operando DRIFTS, this increase in activity is traced to a partially reduced state of the catalysts, as evidenced by a broad IR band of adsorbed CO reaching from 2080 to 1800 cm⁻¹. Full article

(This article belongs to the Special Issue Recent Advancements of Metal Oxide in Catalysis)

► Show Figures

Figure 1

27 pages, 5842 KiB

Open AccessEditor’s ChoiceReview

Green Energy by Hydrogen Production from Water Splitting, Water Oxidation Catalysis and Acceptorless Dehydrogenative Coupling

by Jesús Antonio Luque-Urrutia, Thalía Ortiz-García, Miquel Solà and Albert Poater

Inorganics 2023, 11(2), 88; https://doi.org/10.3390/inorganics11020088 - 20 Feb 2023

Cited by 13 | Viewed by 4081

Abstract

In this review, we want to explain how the burning of fossil fuels is pushing us towards green energy. Actually, for a long time, we have believed that everything is profitable, that resources are unlimited and there are no consequences. However, the reality [...] Read more.

In this review, we want to explain how the burning of fossil fuels is pushing us towards green energy. Actually, for a long time, we have believed that everything is profitable, that resources are unlimited and there are no consequences. However, the reality is often disappointing. The use of non-renewable resources, the excessive waste production and the abandonment of the task of recycling has created a fragile thread that, once broken, may never restore itself. Metaphors aside, we are talking about our planet, the Earth, and its unique ability to host life, including ourselves. Our world has its balance; when the wind erodes a mountain, a beach appears, or when a fire devastates an area, eventually new life emerges from the ashes. However, humans have been distorting this balance for decades. Our evolving way of living has increased the number of resources that each person consumes, whether food, shelter, or energy; we have overworked everything to exhaustion. Scientists worldwide have already said actively and passively that we are facing one of the biggest problems ever: climate change. This is unsustainable and we must try to revert it, or, if we are too late, slow it down as much as possible. To make this happen, there are many possible methods. In this review, we investigate catalysts for using water as an energy source, or, instead of water, alcohols. On the other hand, the recycling of gases such as CO₂ and N₂O is also addressed, but we also observe non-catalytic means of generating energy through solar cell production. Full article

(This article belongs to the Special Issue Inorganics for Catalysts: Design, Synthesis and Applications)

► Show Figures

Graphical abstract

18 pages, 3646 KiB

Open AccessEditor’s ChoiceArticle

Main Issues in the Synthesis and Testing of Thermocatalytic Ce-Doped SrFeO₃ Perovskites for Wastewater Pollutant Removal

by Davide Palma, Francesca Deganello, Leonarda Francesca Liotta, Valeria La Parola, Alessandra Bianco Prevot, Mery Malandrino, Enzo Laurenti, Vittorio Boffa and Giuliana Magnacca

Inorganics 2023, 11(2), 85; https://doi.org/10.3390/inorganics11020085 - 17 Feb 2023

Cited by 7 | Viewed by 2183

Abstract

The effect of the synthesis and processing parameters on the thermocatalytic performance of Ce-doped SrFeO₃ inorganic perovskites was investigated to improve the reproducibility and reliability of the synthetic methodology and of the testing procedure. A structural, surface and redox characterization was performed [...] Read more.

The effect of the synthesis and processing parameters on the thermocatalytic performance of Ce-doped SrFeO₃ inorganic perovskites was investigated to improve the reproducibility and reliability of the synthetic methodology and of the testing procedure. A structural, surface and redox characterization was performed to check the extent of variability in the chemical–physical properties of the prepared materials, revealing that a strict control of the synthesis parameters is indeed crucial to optimize the thermocatalytic properties of Ce-doped SrFeO₃ inorganic perovskites. The thermocatalytic tests, aimed to degrade organic pollutants in water, were performed using Orange II and Bisphenol A as target compounds, in view of a later technological application. The main issues in the synthesis and testing of Ce-doped SrFeO₃ perovskite thermocatalysts are highlighted and described, giving specific instructions for the resolution of each of them. A limited number of prepared materials showed an efficient thermocatalytic effect, indicating that a full gelification of the sol, an overstoichiometric reducer-to-oxidizer ratio, a nominal cerium content of 15 mol%, slightly higher than its solubility limit (i.e., 14 mol%), a pH of 6 and a thermal treatment at 800 °C/2 h are the best synthesis conditions to obtain an effective Ce-doped SrFeO₃ perovskite. Regarding the testing conditions, the best procedure is to follow the degradation reaction without any preconditioning with the pollutant at room temperature. The severe leaching of the active perovskite phase during tests conducted at acidic pH is discussed. Briefly, we suggest confining the application of these materials to a limited pH range. Variability between thermocatalysts prepared in two different laboratories was also checked. The issues discussed and the proposed solutions overcome some of the obstacles to achieving a successful scale up of the synthesis process. Our results were favorable in comparison to those in the literature, and our approach can be successfully extended to other perovskite catalysts. Full article

(This article belongs to the Special Issue New Advances into Nanostructured Oxides)

► Show Figures

Graphical abstract

21 pages, 1840 KiB

Open AccessEditor’s ChoiceReview

Effects of Boron-Containing Compounds on Liposoluble Hormone Functions

by Elizabeth Estevez-Fregoso, Ahmet Kilic, Diana Rodríguez-Vera, Luis E. Nicanor-Juárez, C. Elena M. Romero-Rizo, Eunice D. Farfán-García and Marvin A. Soriano-Ursúa

Inorganics 2023, 11(2), 84; https://doi.org/10.3390/inorganics11020084 - 17 Feb 2023

Cited by 13 | Viewed by 6444

Abstract

Boron-containing compounds (BCC), particularly boronic acids and derivatives, are being increasingly tested as diagnostic and therapeutic agents. Some effects of BCC involve phenomena linked to the action of steroid or thyroid hormones; among these, are the effects on muscle mass or basal metabolism. [...] Read more.

Boron-containing compounds (BCC), particularly boronic acids and derivatives, are being increasingly tested as diagnostic and therapeutic agents. Some effects of BCC involve phenomena linked to the action of steroid or thyroid hormones; among these, are the effects on muscle mass or basal metabolism. Additionally, some toxicology reports on mammals, including humans, sound an alert concerning damage to several systems, among which are the negative effects on the induction of male infertility. Systemic and local mechanisms to explain changes in metabolism and impaired fertility were collected and presented. Then, we presented the putative pharmacodynamic and pharmacokinetic mechanisms involved and demonstrated in these events. In addition, it is proposed that there are adducts of some oxygenated BCC with cis-diols in fructose, an essential source of energy for sperm–cell motility, an uncoupling of sex hormone-binding globulin (SHBG) and its ligands, and the modulation of the DNA synthetic rate. These effects share the reactivity of boron-containing compounds on the cis-diols of key molecules. Moreover, data reporting no DNA damage after BCC administration are included. Further studies are required to support the clear role of BCC through these events to disrupt metabolism or fertility in mammals. If such phenomena are confirmed and elucidated, an advance could be useful to design strategies for avoiding BCC toxicity after BCC administration, and possibly for designing metabolism regulators and contraceptive drugs, among other purposes. Boronic derivatives and carboranes have been proposed and studied in this field. Full article

(This article belongs to the Special Issue Synthesis and Innovative Biological Activity of Boron-Containing Compounds)

► Show Figures

Figure 1

22 pages, 6586 KiB

Open AccessEditor’s ChoiceReview

Carbon-Based Materials and Their Applications in Sensing by Electrochemical Voltammetry

by Trong Danh Nguyen, My Thi Ngoc Nguyen and Jun Seop Lee

Inorganics 2023, 11(2), 81; https://doi.org/10.3390/inorganics11020081 - 15 Feb 2023

Cited by 21 | Viewed by 4921

Abstract

In recent years, society has paid great attention to health care and environmental safety. Thus, research on advanced sensors for detecting substances that can harm health and the environment has been developed rapidly. Another popular target for detection techniques is disease-expressing materials that [...] Read more.

In recent years, society has paid great attention to health care and environmental safety. Thus, research on advanced sensors for detecting substances that can harm health and the environment has been developed rapidly. Another popular target for detection techniques is disease-expressing materials that can be collected from body fluids. Carbon, which has outstanding electrochemical properties, can come from a variety of sources and has many morphological shapes, is nevertheless an environmentally friendly material. While carbon nanomaterial has become one of the most common targets for high-tech development, electrochemical voltammetry has proven to be an effective measurement method. Herein, the paper proposes a currently developed carbon nanomaterial along with research on a modified carbon material. Moreover, four common voltammetry methods and related works are also introduced. Full article

(This article belongs to the Section Inorganic Materials)

► Show Figures

Figure 1

19 pages, 6775 KiB

Open AccessFeature PaperEditor’s ChoiceArticle

Coordination Chemistry of Polynitriles, Part XII—Serendipitous Synthesis of the Octacyanofulvalenediide Dianion and Study of Its Coordination Chemistry with K⁺ and Ag⁺

by Patrick Nimax, Yannick Kunzelmann and Karlheinz Sünkel

Inorganics 2023, 11(2), 71; https://doi.org/10.3390/inorganics11020071 - 2 Feb 2023

Cited by 1 | Viewed by 1565

Abstract

The reaction of diazotetracyanocyclopentadiene with copper powder in the presence of NEt₄Cl yields, unexpectedly, besides the known NEt₄[C₅H(CN)₄] (3), the NEt₄ salt of octacyanofulvalenediide (NEt₄)₂[C₁₀(CN)₈] ( [...] Read more.

The reaction of diazotetracyanocyclopentadiene with copper powder in the presence of NEt₄Cl yields, unexpectedly, besides the known NEt₄[C₅H(CN)₄] (3), the NEt₄ salt of octacyanofulvalenediide (NEt₄)₂[C₁₀(CN)₈] (5), which can be transformed via reaction with AgNO₃ to the corresponding Ag⁺ salt (4), which in turn can be reacted with KCl to yield the corresponding K⁺ salt 6. The molecular and crystal structures of 4–6 could be determined, and show a significantly twisted aromatic dianion which uses all its nitrile groups for coordination to the metals; 4 and 6 form three-dimensional coordination polymers with fourfold coordinated Ag⁺ and eightfold coordinated K⁺ cations. Full article

(This article belongs to the Special Issue Recent Progress in Coordination Chemistry)

► Show Figures

Figure 1

11 pages, 1564 KiB

Open AccessFeature PaperEditor’s ChoiceArticle

Synthesis of Novel Multifunctional bora-Ibuprofen Derivatives

by Randika T. Abeysinghe, Alexis C. Ravenscroft, Steven W. Knowlden, Novruz G. Akhmedov, Brian S. Dolinar and Brian V. Popp

Inorganics 2023, 11(2), 70; https://doi.org/10.3390/inorganics11020070 - 2 Feb 2023

Cited by 4 | Viewed by 3354

Abstract

A unique class of β-boron-functionalized non-steroidal anti-inflammatory compound (pinB-NSAID) was previously synthesized via copper-catalyzed 1,2-difunctionalization of the respective vinyl arene with CO₂ and B₂pin₂ reagents. Here, pinacolylboron-functionalized ibuprofen (pinB-ibuprofen) was used as a model substrate to develop the conditions [...] Read more.

A unique class of β-boron-functionalized non-steroidal anti-inflammatory compound (pinB-NSAID) was previously synthesized via copper-catalyzed 1,2-difunctionalization of the respective vinyl arene with CO₂ and B₂pin₂ reagents. Here, pinacolylboron-functionalized ibuprofen (pinB-ibuprofen) was used as a model substrate to develop the conditions for pinacol deprotection and subsequent boron functionalization. Initial pinacol-boronic ester deprotection was achieved by transesterification with diethanolamine (DEA) from the boralactonate organic salt. The resulting DEA boronate adopts a spirocyclic boralactonate structure rather than a diazaborocane–DABO boronate structure. The subsequent acid-mediated hydrolysis of DEA and transesterification/transamination provided a diverse scope of new boron-containing ibuprofen derivatives. Full article

(This article belongs to the Special Issue Synthesis and Innovative Biological Activity of Boron-Containing Compounds)

► Show Figures

Figure 1

18 pages, 3303 KiB

Open AccessFeature PaperEditor’s ChoiceArticle

Interactions of an Artificial Zinc Finger Protein with Cd(II) and Hg(II): Competition and Metal and DNA Binding

by Bálint Hajdu, Éva Hunyadi-Gulyás and Béla Gyurcsik

Inorganics 2023, 11(2), 64; https://doi.org/10.3390/inorganics11020064 - 29 Jan 2023

Cited by 2 | Viewed by 2670

Abstract

Cys2His2 zinc finger proteins are important for living organisms, as they—among other functions—specifically recognise DNA when Zn(II) is coordinated to the proteins, stabilising their ββα secondary structure. Therefore, competition with other metal ions may alter their original function. Toxic metal ions such as [...] Read more.

Cys2His2 zinc finger proteins are important for living organisms, as they—among other functions—specifically recognise DNA when Zn(II) is coordinated to the proteins, stabilising their ββα secondary structure. Therefore, competition with other metal ions may alter their original function. Toxic metal ions such as Cd(II) or Hg(II) might be especially dangerous because of their similar chemical properties to Zn(II). Most competition studies carried out so far have involved small zinc finger peptides. Therefore, we have investigated the interactions of toxic metal ions with a zinc finger proteins consisting of three finger units and the consequences on the DNA binding properties of the protein. Binding of one Cd(II) per finger subunit of the protein was shown by circular dichroism spectroscopy, fluorimetry and electrospray ionisation mass spectrometry. Cd(II) stabilised a similar secondary structure to that of the Zn(II)-bound protein but with a slightly lower affinity. In contrast, Hg(II) could displace Zn(II) quantitatively (logβ′ ≥ 16.7), demolishing the secondary structure, and further Hg(II) binding was also observed. Based on electrophoretic gel mobility shift assays, the Cd(II)-bound zinc finger protein could recognise the specific DNA target sequence similarly to the Zn(II)-loaded form but with a ~0.6 log units lower stability constant, while Hg(II) could destroy DNA binding completely. Full article

(This article belongs to the Special Issue Recent Progress in Coordination Chemistry)

► Show Figures

Figure 1

30 pages, 3363 KiB

Open AccessEditor’s ChoiceReview

The Role of Complexes of Biogenic Metals in Living Organisms

by Irena Kostova

Inorganics 2023, 11(2), 56; https://doi.org/10.3390/inorganics11020056 - 25 Jan 2023

Cited by 23 | Viewed by 4746

Abstract

Biogenic metals and their various inorganic, organometallic, and coordination compounds are comprehensively studied and extensively used in medical practice. Since the biogenic metals have various chemical properties corresponding to their position in the periodic table, their biological functions are different. Almost all of [...] Read more.

Biogenic metals and their various inorganic, organometallic, and coordination compounds are comprehensively studied and extensively used in medical practice. Since the biogenic metals have various chemical properties corresponding to their position in the periodic table, their biological functions are different. Almost all of the discussed biogenic elements have an ability to form coordination complexes. Furthermore, the different accessible oxidation states occupied by most of these elements enables the body to catalyze oxy-reduction interactions, depending on the biological conditions. As they are biogenic in nature, their deficiency or their excess in the body leads to numerous pathological obstructions. The application of metal-based compounds as medications is connected with the oxy-reduction properties and the capability to form coordination complexes, which are involved in many bioreactions. The usefulness of these metals as therapeutic and diagnostic agents is also pointed out. Full article

(This article belongs to the Special Issue Bioactivity of Transition Metal-Based Complexes)

► Show Figures

Figure 1

21 pages, 5621 KiB

Open AccessFeature PaperEditor’s ChoiceReview

The Applications of Metallacycles and Metallacages

by Changfeng Yin, Jiaxing Du, Bogdan Olenyuk, Peter J. Stang and Yan Sun

Inorganics 2023, 11(2), 54; https://doi.org/10.3390/inorganics11020054 - 22 Jan 2023

Cited by 9 | Viewed by 3010

Abstract

Metallacycles and metallacages constitute a class of coordination compounds composed of metal ions and organic ligands. Because of their precise stoichiometry, the flexibility and viability of design, metallacycles and metallacages have attracted considerable attention as supramolecular assemblies. Various two-dimensional polygons, three-dimensional polyhedra, and [...] Read more.

Metallacycles and metallacages constitute a class of coordination compounds composed of metal ions and organic ligands. Because of their precise stoichiometry, the flexibility and viability of design, metallacycles and metallacages have attracted considerable attention as supramolecular assemblies. Various two-dimensional polygons, three-dimensional polyhedra, and other nanoscale materials have been constructed and applied. The highly diverse structures, sizes, and shapes endow metallacycles and metallacages with unique physical and chemical properties and make them suitable for various applications such as encapsulation, separation, catalysis, and biological science. Herein, we review the recent developments in various metallacycles and metallacages in different fields. The text highlights biomedical applications involving molecular recognition and binding, antibacterial activity, and especially cancer diagnosis and treatment, including imaging, chemotherapy, PDT, and PTT. Full article

(This article belongs to the Special Issue Metallamacrocycles and Metallacages: Foundations and Applications)

► Show Figures

Graphical abstract

12 pages, 3788 KiB

Open AccessFeature PaperEditor’s ChoiceArticle

The Influence of Different Recombination Pathways on Hysteresis in Perovskite Solar Cells with Ion Migration

by Biao Li, Kun Chen, Pengjie Hang, Yuxin Yao, Chenxia Kan, Zechen Hu, Ying Wang, Yiqiang Zhang, Deren Yang and Xuegong Yu

Inorganics 2023, 11(2), 52; https://doi.org/10.3390/inorganics11020052 - 19 Jan 2023

Viewed by 2801

Abstract

The impact of hysteresis on the power conversion efficiency (PCE) of perovskite solar cells (PSCs) still faces uncertainties despite the rapid development of perovskite photovoltaics. Although ion migration in perovskites is regarded as the chief culprit for hysteresis, charge carrier recombination pathways in [...] Read more.

The impact of hysteresis on the power conversion efficiency (PCE) of perovskite solar cells (PSCs) still faces uncertainties despite the rapid development of perovskite photovoltaics. Although ion migration in perovskites is regarded as the chief culprit for hysteresis, charge carrier recombination pathways in PSCs are proposed to be necessary for the occurrence of hysteresis. Here, the impact of both bulk recombination and interface recombination on hysteresis in PSCs is investigated via drift–diffusion modeling. The simulation results demonstrate a direct correlation between recombination pathways and hysteresis in PSCs with ion migration. The simulation reveals that recombination pathways in PSCs will react to the variation in charge carrier distribution under different voltage scanning directions induced by ion migration in absorber layers, which leads to hysteresis in PSCs. Moreover, the hysteresis in normal (N-I-P) PSCs with different electron transport layers (ETLs) including sintered SnO₂, SnO₂ nano crystals and TiO₂ is experimentally explored. The results demonstrate that multiple recombination pathways coupled with ion migration can lead to obvious hysteresis in fabricated PSCs which is consistent with simulation results. This work provides great insight into hysteresis management upon composition, additive and interface engineering in PSCs. Full article

(This article belongs to the Special Issue Inorganics: 10th Anniversary)

► Show Figures

Graphical abstract

18 pages, 4081 KiB

Open AccessFeature PaperEditor’s ChoiceArticle

Latonduine-1-Amino-Hydantoin Hybrid, Triazole-Fused Latonduine Schiff Bases and Their Metal Complexes: Synthesis, X-ray and Electron Diffraction, Molecular Docking Studies and Antiproliferative Activity

by Christopher Wittmann, Tim Gruene, Alexander Prado-Roller, Sandra Aranđelović, Jóhannes Reynisson and Vladimir B. Arion

Inorganics 2023, 11(1), 30; https://doi.org/10.3390/inorganics11010030 - 3 Jan 2023

Cited by 3 | Viewed by 2381

Abstract

A series of latonduine derivatives, namely 11-nitro-indolo[2,3-d]benzazepine-7-(1-amino-hydantoin) (B), triazole-fused indolo[2,3-d]benzazepine-based Schiff bases HL¹ and HL² and metal complexes [M(p-cymene)(HL¹)Cl]Cl, where M = Ru (1), Os (2), and [...] Read more.

A series of latonduine derivatives, namely 11-nitro-indolo[2,3-d]benzazepine-7-(1-amino-hydantoin) (B), triazole-fused indolo[2,3-d]benzazepine-based Schiff bases HL¹ and HL² and metal complexes [M(p-cymene)(HL¹)Cl]Cl, where M = Ru (1), Os (2), and [Cu(HL²)Cl₂] (3) were synthesized and characterized by spectroscopic techniques (UV–vis, ¹H, ¹³C, ¹⁵N–¹H HSQC NMR) and ESI mass spectrometry. The molecular structures of B and HL¹ were confirmed by single-crystal X-ray diffraction, while that of 3 by electron diffraction of nanometer size crystalline sample. Molecular docking calculations of species B in the binding pocket of PIM-1 enzyme revealed that the 1-amino-hydantoin moiety is not involved in any hydrogen-bonding interactions, even though a good accommodation of the host molecule in the ATP binding pocket of the enzyme was found. The antiproliferative activity of organic compounds B, HL¹ and HL², as well as complexes 1–3 was investigated in lung adenocarcinoma A549, colon adenocarcinoma LS-174 and triple-negative breast adenocarcinoma MDA-MB-231 cells and normal human lung fibroblast cells MRC-5 by MTT assays; then, the results are discussed. Full article

(This article belongs to the Special Issue Inorganics: 10th Anniversary)

► Show Figures

Figure 1

20 pages, 5136 KiB

Open AccessEditor’s ChoiceArticle

Cryogels with Noble Metal Nanoparticles as Catalyst for “Green” Decomposition of Chlorophenols

by Dmitriy A. Berillo and Irina N. Savina

Inorganics 2023, 11(1), 23; https://doi.org/10.3390/inorganics11010023 - 2 Jan 2023

Cited by 6 | Viewed by 2094

Abstract

Pollution of the aquatic environment by halogen derivatives widely used as antiseptic compounds, as well as chemicals for various industrial purposes, is significant. Existing systems of bioremediation poorly solve the problem of eliminating pollution. This paper discusses the preparation of novel macroporous chitosan-based [...] Read more.

Pollution of the aquatic environment by halogen derivatives widely used as antiseptic compounds, as well as chemicals for various industrial purposes, is significant. Existing systems of bioremediation poorly solve the problem of eliminating pollution. This paper discusses the preparation of novel macroporous chitosan-based cryogels with in situ-immobilized Pd or Pt nanoparticles as a catalyst for dichlorination reactions. The formation mechanism of metal coordinated chitosan gels using Medusa software modelling and rheology (G’ and G’’) is discussed. Metal coordinated chitosan gels were subsequently converted into covalently cross-linked macroporous cryogels with in situ-immobilized Pd or Pt nanoparticles using the redox potentials difference of the reaction mixture. Noble metal nanoparticles of average size, 2.4 nm, were evenly distributed in the cryogel structure. The effectiveness of these gels as a catalyst for the decomposition of chloro-compounds o-chlorophenol, p-chlorophenol and 2,4-dichlorophenol was tested. The catalytic hydrogenation reaction was carried out using the “green reducing agent” formic acid. Increasing the excess of formic acid with heating increases the degree of conversion up to 80–90%. The CHI-GA-PdNPs cryogel at pH 6 showed better efficiency in the hydrogenation process compared to the CHI-GA-PtNPs cryogel; however, no significant difference in the degree of conversion at pH 3 was observed. The termination of a catalytic reaction in a batch mode have been studied. Several control tests were carried out to elucidate the mechanism of catalyst poisoning. The presented catalytic system may be of interest for studying reactions in a flow through mode, including the reactions for obtaining valuable chemicals. Full article

(This article belongs to the Special Issue Inorganics for Catalysts: Design, Synthesis and Applications)

► Show Figures

Graphical abstract

32 pages, 5390 KiB

Open AccessEditor’s ChoiceReview

Inorganic Finishing for Textile Fabrics: Recent Advances in Wear-Resistant, UV Protection and Antimicrobial Treatments

by Silvia Sfameni, Mariam Hadhri, Giulia Rando, Dario Drommi, Giuseppe Rosace, Valentina Trovato and Maria Rosaria Plutino

Inorganics 2023, 11(1), 19; https://doi.org/10.3390/inorganics11010019 - 1 Jan 2023

Cited by 27 | Viewed by 5807

Abstract

The surface modification of textile fabrics and therefore, the development of advanced textile materials featuring specific implemented and new properties, such as improved durability and resistance, is increasingly in demand from modern society and end-users. In this regard, the sol–gel technique has shown [...] Read more.

The surface modification of textile fabrics and therefore, the development of advanced textile materials featuring specific implemented and new properties, such as improved durability and resistance, is increasingly in demand from modern society and end-users. In this regard, the sol–gel technique has shown to be an innovative and convenient synthetic route for developing functional sol–gel coatings useful for the protection of textile materials. Compared with the conventional textile finishing process, this technique is characterized by several advantages, such as the environmentally friendly approaches based on one-step applications and low concentration of non-hazardous chemicals. The sol–gel method, starting from inorganic metal alkoxides or metal salts, leads to inorganic sols containing particles that enable a chemical or physical modification of fiber surfaces, giving rise to final multifunctional properties of treated textile fabrics. This review considered the recent developments in the synthesis of inorganic nanoparticles and nanosols by sol–gel approach for improving wear and UV resistance, as well as antibacterial or antimicrobial effects for textile applications. Full article

(This article belongs to the Special Issue New Advances into Nanostructured Oxides)

► Show Figures

Graphical abstract

16 pages, 4686 KiB

Open AccessFeature PaperEditor’s ChoiceArticle

The Crystal Structure of Carbonic Acid

by Sebastian Benz, Da Chen, Andreas Möller, Michael Hofmann, David Schnieders and Richard Dronskowski

Inorganics 2022, 10(9), 132; https://doi.org/10.3390/inorganics10090132 - 3 Sep 2022

Cited by 6 | Viewed by 9473

Abstract

Ubiquitous carbonic acid, H₂CO₃, a key molecule in biochemistry, geochemistry, and also extraterrestrial chemistry, is known from a plethora of physicochemical studies. Its crystal structure has now been determined from neutron-diffraction data on a deuterated sample in a specially [...] Read more.

Ubiquitous carbonic acid, H₂CO₃, a key molecule in biochemistry, geochemistry, and also extraterrestrial chemistry, is known from a plethora of physicochemical studies. Its crystal structure has now been determined from neutron-diffraction data on a deuterated sample in a specially built hybrid clamped cell. At 1.85 GPa, D₂CO₃ crystallizes in the monoclinic space group P2₁/c with a = 5.392(2), b = 6.661(4), c = 5.690(1) Å, β = 92.66(3)°, Z = 4, with one symmetry-inequivalent anti-anti shaped D₂CO₃ molecule forming dimers, as previously predicted. Quantum chemistry evidences π bonding within the CO₃ molecular core, very strong hydrogen bonding between the molecules, and a massive influence of the crystal field on all bonds; phonon calculations emphasize the locality of the vibrations, being rather insensitive to the extended structure. Full article

(This article belongs to the Special Issue Inorganics: 10th Anniversary)

► Show Figures

Figure 1

8 pages, 1787 KiB

Open AccessEditor’s ChoiceArticle

A Partial Anion Disorder in SrVO₂H Induced by Biaxial Tensile Strain

by Morito Namba, Hiroshi Takatsu, Wataru Yoshimune, Aurélien Daniel, Shoichi Itoh, Takahito Terashima and Hiroshi Kageyama

Inorganics 2020, 8(4), 26; https://doi.org/10.3390/inorganics8040026 - 8 Apr 2020

Cited by 13 | Viewed by 5670

Abstract

SrVO₂H, obtained by a topochemical reaction of SrVO₃ perovskite using CaH₂, is an anion-ordered phase with hydride anions exclusively at the apical site. In this study, we conducted a CaH₂ reduction of SrVO₃ thin films epitaxially [...] Read more.

SrVO₂H, obtained by a topochemical reaction of SrVO₃ perovskite using CaH₂, is an anion-ordered phase with hydride anions exclusively at the apical site. In this study, we conducted a CaH₂ reduction of SrVO₃ thin films epitaxially grown on KTaO₃ (KTO) substrates. When reacted at 530 °C for 12 h, we observed an intermediate phase characterized by a smaller tetragonality of c/a = 0.96 (vs. c/a = 0.93 for SrVO₂H), while a longer reaction of 24 h resulted in the known phase of SrVO₂H. This fact suggests that the intermediate phase is a metastable state stabilized by applying tensile strain from the KTO substrate (1.4%). In addition, secondary ion mass spectrometry (SIMS) revealed that the intermediate phase has a hydrogen content close to that of SrVO₂H, suggesting a partially disordered anion arrangement. Such kinetic trapping of an intermediate state by biaxial epitaxial strain not only helps to acquire a new state of matter but also advances our understanding of topochemical reaction processes in extended solids. Full article

(This article belongs to the Section Inorganic Solid-State Chemistry)

► Show Figures

Graphical abstract

11 pages, 5648 KiB

Open AccessEditor’s ChoiceCommunication

Magnetic Composite Submicron Carriers with Structure-Dependent MRI Contrast

by Anastasiia A. Kozlova, Sergey V. German, Vsevolod S. Atkin, Victor V. Zyev, Maxwell A. Astle, Daniil N. Bratashov, Yulia I. Svenskaya and Dmitry A. Gorin

Inorganics 2020, 8(2), 11; https://doi.org/10.3390/inorganics8020011 - 30 Jan 2020

Cited by 18 | Viewed by 3932

Abstract

Magnetic contrast agents are widely used in magnetic resonance imaging in order to significantly change the signals from the regions of interest in comparison with the surrounding tissue. Despite a high variety of single-mode T₁ or T₂ contrast agents, there is [...] Read more.

Magnetic contrast agents are widely used in magnetic resonance imaging in order to significantly change the signals from the regions of interest in comparison with the surrounding tissue. Despite a high variety of single-mode T₁ or T₂ contrast agents, there is a need for dual-mode contrast from the one agent. Here, we report on the synthesis of magnetic submicron carriers, containing Fe₃O₄ nanoparticles in their structure. We show the ability to control magnetic resonance contrast by changing not only the number of magnetite nanoparticles in one carrier or the concentration of magnetite in the suspension but also the structure of the core–shell itself. The obtained data open up the prospects for dual-mode T₁/T₂ magnetic contrast formation, as well as provides the basis for future investigations in this direction. Full article

(This article belongs to the Special Issue Smart Tools for Smart Applications: New Insights into Inorganic Magnetic Systems and Materials)

► Show Figures

Graphical abstract

59 pages, 11275 KiB

Open AccessEditor’s ChoiceReview

Magnetic Materials and Systems: Domain Structure Visualization and Other Characterization Techniques for the Application in the Materials Science and Biomedicine

by Roberto Nisticò, Federico Cesano and Francesca Garello

Inorganics 2020, 8(1), 6; https://doi.org/10.3390/inorganics8010006 - 17 Jan 2020

Cited by 54 | Viewed by 15361

Abstract

Magnetic structures have attracted a great interest due to their multiple applications, from physics to biomedicine. Several techniques are currently employed to investigate magnetic characteristics and other physicochemical properties of magnetic structures. The major objective of this review is to summarize the current [...] Read more.

Magnetic structures have attracted a great interest due to their multiple applications, from physics to biomedicine. Several techniques are currently employed to investigate magnetic characteristics and other physicochemical properties of magnetic structures. The major objective of this review is to summarize the current knowledge on the usage, advances, advantages, and disadvantages of a large number of techniques that are currently available to characterize magnetic systems. The present review, aiming at helping in the choice of the most suitable method as appropriate, is divided into three sections dedicated to characterization techniques. Firstly, the magnetism and magnetization (hysteresis) techniques are introduced. Secondly, the visualization methods of the domain structures by means of different probes are illustrated. Lastly, the characterization of magnetic nanosystems in view of possible biomedical applications is discussed, including the exploitation of magnetism in imaging for cell tracking/visualization of pathological alterations in living systems (mainly by magnetic resonance imaging, MRI). Full article

(This article belongs to the Special Issue Smart Tools for Smart Applications: New Insights into Inorganic Magnetic Systems and Materials)

► Show Figures

Graphical abstract

63 pages, 14258 KiB

Open AccessEditor’s ChoiceReview

Halogen Bonding: A Halogen-Centered Noncovalent Interaction Yet to Be Understood

by Pradeep R. Varadwaj, Arpita Varadwaj and Helder M. Marques

Inorganics 2019, 7(3), 40; https://doi.org/10.3390/inorganics7030040 - 12 Mar 2019

Cited by 122 | Viewed by 9462

Abstract

In addition to the underlying basic concepts and early recognition of halogen bonding, this paper reviews the conflicting views that consistently appear in the area of noncovalent interactions and the ability of covalently bonded halogen atoms in molecules to participate in noncovalent interactions [...] Read more.

In addition to the underlying basic concepts and early recognition of halogen bonding, this paper reviews the conflicting views that consistently appear in the area of noncovalent interactions and the ability of covalently bonded halogen atoms in molecules to participate in noncovalent interactions that contribute to packing in the solid-state. It may be relatively straightforward to identify Type-II halogen bonding between atoms using the conceptual framework of σ-hole theory, especially when the interaction is linear and is formed between the axial positive region (σ-hole) on the halogen in one monomer and a negative site on a second interacting monomer. A σ-hole is an electron density deficient region on the halogen atom X opposite to the R–X covalent bond, where R is the remainder part of the molecule. However, it is not trivial to do so when secondary interactions are involved as the directionality of the interaction is significantly affected. We show, by providing some specific examples, that halogen bonds do not always follow the strict Type-II topology, and the occurrence of Type-I and -III halogen-centered contacts in crystals is very difficult to predict. In many instances, Type-I halogen-centered contacts appear simultaneously with Type-II halogen bonds. We employed the Independent Gradient Model, a recently proposed electron density approach for probing strong and weak interactions in molecular domains, to show that this is a very useful tool in unraveling the chemistry of halogen-assisted noncovalent interactions, especially in the weak bonding regime. Wherever possible, we have attempted to connect some of these results with those reported previously. Though useful for studying interactions of reasonable strength, IUPAC’s proposed “less than the sum of the van der Waals radii” criterion should not always be assumed as a necessary and sufficient feature to reveal weakly bound interactions, since in many crystals the attractive interaction happens to occur between the midpoint of a bond, or the junction region, and a positive or negative site. Full article

(This article belongs to the Special Issue Halogen Bonding: Fundamentals and Applications)

► Show Figures

Graphical abstract

15 pages, 591 KiB

Open AccessEditor’s ChoiceReview

Designing Ruthenium Anticancer Drugs: What Have We Learnt from the Key Drug Candidates?

by James P. C. Coverdale, Thaisa Laroiya-McCarron and Isolda Romero-Canelón

Inorganics 2019, 7(3), 31; https://doi.org/10.3390/inorganics7030031 - 1 Mar 2019

Cited by 134 | Viewed by 9764

Abstract

After nearly 20 years of research on the use of ruthenium in the fight against cancer, only two Ru(III) coordination complexes have advanced to clinical trials. During this time, the field has produced excellent candidate drugs with outstanding in vivo and in vitro [...] Read more.

After nearly 20 years of research on the use of ruthenium in the fight against cancer, only two Ru(III) coordination complexes have advanced to clinical trials. During this time, the field has produced excellent candidate drugs with outstanding in vivo and in vitro activity; however, we have yet to find a ruthenium complex that would be a viable alternative to platinum drugs currently used in the clinic. We aimed to explore what we have learned from the most prominent complexes in the area, and to challenge new concepts in chemical design. Particularly relevant are studies involving NKP1339, NAMI-A, RM175, and RAPTA-C, which have paved the way for current research. We explored the development of the ruthenium anticancer field considering that the mechanism of action of complexes no longer focuses solely on DNA interactions, but explores a diverse range of cellular targets involving multiple chemical strategies. Full article

(This article belongs to the Special Issue Unconventional Anticancer Metallodrugs and Strategies to Improve their Pharmacological Profile)

► Show Figures

Figure 1

14 pages, 7701 KiB

Open AccessEditor’s ChoiceArticle

Development and Validation of Liquid Chromatography-Based Methods to Assess the Lipophilicity of Cytotoxic Platinum(IV) Complexes

by Matthias H. M. Klose, Sarah Theiner, Hristo P. Varbanov, Doris Hoefer, Verena Pichler, Mathea Sophia Galanski, Samuel M. Meier-Menches and Bernhard K. Keppler

Inorganics 2018, 6(4), 130; https://doi.org/10.3390/inorganics6040130 - 4 Dec 2018

Cited by 30 | Viewed by 7076

Abstract

Lipophilicity is a crucial parameter for drug discovery, usually determined by the logarithmic partition coefficient (Log P) between octanol and water. However, the available detection methods have restricted the widespread use of the partition coefficient in inorganic medicinal chemistry, and recent investigations have [...] Read more.

Lipophilicity is a crucial parameter for drug discovery, usually determined by the logarithmic partition coefficient (Log P) between octanol and water. However, the available detection methods have restricted the widespread use of the partition coefficient in inorganic medicinal chemistry, and recent investigations have shifted towards chromatographic lipophilicity parameters, frequently without a conversion to derive Log P. As high-performance liquid chromatography (HPLC) instruments are readily available to research groups, a HPLC-based method is presented and validated to derive the partition coefficient of a set of 19 structurally diverse and cytotoxic platinum(IV) complexes exhibiting a dynamic range of at least four orders of magnitude. The chromatographic lipophilicity parameters φ₀ and Log k_w were experimentally determined for the same set of compounds, and a correlation was obtained that allows interconversion between the two lipophilicity scales, which was applied to an additional set of 34 platinum(IV) drug candidates. Thereby, a φ₀ = 58 corresponds to Log P = 0. The same approaches were successfully evaluated to determine the distribution coefficient (Log D) of five ionisable platinum(IV) compounds to sample pH-dependent effects on the lipophilicity. This study provides straight-forward HPLC-based methods to determine the lipophilicity of cytotoxic platinum(IV) complexes in the form of Log P and φ₀ that can be interconverted and easily expanded to other metal-based compound classes. Full article

(This article belongs to the Special Issue Unconventional Anticancer Metallodrugs and Strategies to Improve their Pharmacological Profile)

► Show Figures

Graphical abstract

14 pages, 1967 KiB

Open AccessEditor’s ChoiceArticle

S–H Bond Activation in Hydrogen Sulfide by NHC-Stabilized Silyliumylidene Ions

by Amelie Porzelt, Julia I. Schweizer, Ramona Baierl, Philipp J. Altmann, Max C. Holthausen and Shigeyoshi Inoue

Inorganics 2018, 6(2), 54; https://doi.org/10.3390/inorganics6020054 - 24 May 2018

Cited by 16 | Viewed by 6037

Abstract

Reactivity studies of silyliumylidenes remain scarce with only a handful of publications to date. Herein we report the activation of S–H bonds in hydrogen sulfide by mTer-silyliumylidene ion A (mTer = 2,6-Mes₂-C₆H₃, Mes = [...] Read more.

Reactivity studies of silyliumylidenes remain scarce with only a handful of publications to date. Herein we report the activation of S–H bonds in hydrogen sulfide by mTer-silyliumylidene ion A (mTer = 2,6-Mes₂-C₆H₃, Mes = 2,4,6-Me₃-C₆H₂) to yield an NHC-stabilized thiosilaaldehyde B. The results of NBO and QTAIM analyses suggest a zwitterionic formulation of the product B as the most appropriate. Detailed mechanistic investigations are performed at the M06-L/6-311+G(d,p)(SMD: acetonitrile/benzene)//M06-L/6-311+G(d,p) level of density functional theory. Several pathways for the formation of thiosilaaldehyde B are examined. The energetically preferred route commences with a stepwise addition of H₂S to the nucleophilic silicon center. Subsequent NHC dissociation and proton abstraction yields the thiosilaaldehyde in a strongly exergonic reaction. Intermediacy of a chlorosilylene or a thiosilylene is kinetically precluded. With an overall activation barrier of 15 kcal/mol, the resulting mechanistic picture is fully in line with the experimental observation of an instantaneous reaction at sub-zero temperatures. Full article

(This article belongs to the Special Issue Coordination Chemistry of Silicon)

► Show Figures

Graphical abstract

34 pages, 10625 KiB

Open AccessEditor’s ChoiceReview

Ruthenium Complexes as Sensitizers in Dye-Sensitized Solar Cells

by Sadig Aghazada and Mohammad Khaja Nazeeruddin

Inorganics 2018, 6(2), 52; https://doi.org/10.3390/inorganics6020052 - 21 May 2018

Cited by 105 | Viewed by 11396

Abstract

In this review, we discuss the main directions in which ruthenium complexes for dye-sensitized solar cells (DSCs) were developed. We critically discuss the implemented design principles. This review might be helpful at this moment when a breakthrough is needed for DSC technology to [...] Read more.

In this review, we discuss the main directions in which ruthenium complexes for dye-sensitized solar cells (DSCs) were developed. We critically discuss the implemented design principles. This review might be helpful at this moment when a breakthrough is needed for DSC technology to prove its market value. Full article

(This article belongs to the Collection Coordination Complexes for Dye-Sensitized Solar Cells (DSCs))

► Show Figures

Graphical abstract

Journal Menu

Journal Browser

Editor’s Choice Articles

Further Information

Guidelines

MDPI Initiatives

Follow MDPI