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Keywords = Cadmium coordination polymers

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16 pages, 6437 KiB  
Article
Cd(II)-Based Coordination Polymers and Supramolecular Complexes Containing Dianiline Chromophores: Synthesis, Crystal Structures, and Photoluminescence Properties
by Nicoleta Craciun, Elena Melnic, Anatolii V. Siminel, Natalia V. Costriucova, Diana Chisca and Marina S. Fonari
Inorganics 2025, 13(3), 90; https://doi.org/10.3390/inorganics13030090 - 18 Mar 2025
Viewed by 543
Abstract
Five new coordination compounds that included three coordination polymers and two supramolecular complexes were obtained by reactions of different cadmium salts (tetrafluoroborate, nitrate, and perchlorate) with dianiline chromophores, 4,4′-diaminodiphenylmethane (ddpm), and 4,4′-diaminodiphenylethane (ddpe). The crystal structures were studied by single-crystal X-ray analysis. The [...] Read more.
Five new coordination compounds that included three coordination polymers and two supramolecular complexes were obtained by reactions of different cadmium salts (tetrafluoroborate, nitrate, and perchlorate) with dianiline chromophores, 4,4′-diaminodiphenylmethane (ddpm), and 4,4′-diaminodiphenylethane (ddpe). The crystal structures were studied by single-crystal X-ray analysis. The coordination arrays with the ddpm chromophore included {[Cd(OH)(H2O)(ddpm)2](BF4)}n (1) as a one-dimensional (1D) coordination garland chain, {[Cd(NO3)(ddpm)2](H2O)(NO3)}n (2) as a two-dimensional (2D) coordination layer, and [Cd(bpy)2(ddpm)2](ddpm)(NO3)2 (3) as a supramolecular complex. The products with the ddpe chromophore were identified as {[Cd(phen)2(ddpe)](ClO4)2}n (4) in the form of a linear coordination chain and [Cd(phen)3](ClO4)2(ddpe)0.5(CH3CN)0.5 (5) as a supramolecular complex. The extension of coordination arrays in 1, 2, and 4 was achieved via dianiline ligands as bidentate linkers and additionally via bridging of nitrate anions in 2. The diversification of products became possible due to usage of 2,2′-bipyridine (bpy) and 1,10-phenanthroline (phen) as co-ligands forming the terminal corner fragments [Cd(bpy)2]2+, [Cd(phen)2]2+, and [Cd(phen)3]2+ in 35, respectively. The assembling of coordination entities occurred via the interplay of hydrogen bonds with the participation of amino groups, water molecules, and inorganic anions. Two dianilines were powerful luminophores in the crystalline phase, while the photoluminescence in 15 was considerably weaker than in the pure ddpm and ddpe luminophores and redistributed along the spectrum. Full article
(This article belongs to the Section Coordination Chemistry)
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14 pages, 4392 KiB  
Article
Syntheses and Crystal Structures of Two Metal–Organic Frameworks Formed from Cd2+ Ions Bridged by Long, Flexible 1,7-bis(4-Pyridyl)heptane Ligands with Different Counter-Ions
by M. John Plater, Ben M. De Silva, Mark R. St J. Foreman and William T. A. Harrison
Crystals 2024, 14(12), 1105; https://doi.org/10.3390/cryst14121105 - 23 Dec 2024
Viewed by 965
Abstract
The ethanol–water layered syntheses and crystal structures of the coordination polymers [Cd(C17H22N2)2(H2O)2]·2(ClO4)·C17H22N2·C2H5OH 2 and [Cd(C17H22N [...] Read more.
The ethanol–water layered syntheses and crystal structures of the coordination polymers [Cd(C17H22N2)2(H2O)2]·2(ClO4)·C17H22N2·C2H5OH 2 and [Cd(C17H22N2)2(NO3)2] 3 are reported, where C17H22N2 is a flexible spacer, 1,7-bis(4-pyridyl)heptane. In compound 2, trans-CdO2N4 octahedral nodes are linked by pairs of bridging ligands to result in [001] looped polymeric chains. The chains stack in the [100] direction to form (010) pseudo layers. Sandwiched between them are secondary sheets of free ligands, perchlorate ions and ethanol solvent molecules. Hydrogen bonds between these species help to consolidate the structure. Compound 3 contains trans-CdO2N4 octahedral nodes as parts of regular 44 nets, which propagate in the (103) plane. Three independent nets are interpenetrated. Full article
(This article belongs to the Special Issue Celebrating the 10th Anniversary of International Crystallography)
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32 pages, 3753 KiB  
Review
An Overview of Various Applications of Cadmium Carboxylate Coordination Polymers
by Gina Vasile Scaeteanu, Catalin Maxim, Mihaela Badea and Rodica Olar
Molecules 2024, 29(16), 3874; https://doi.org/10.3390/molecules29163874 - 15 Aug 2024
Cited by 3 | Viewed by 1616
Abstract
This review highlights the most recent applications of Cd(II)-carboxylate-based coordination polymers (Cd(II)-CBCPs), such as sensors, catalysts, and storage materials, in comparison with those of Zn(II) counterparts. A wide range of species with luminescence properties were designed by using proper organic fluorophores, especially a [...] Read more.
This review highlights the most recent applications of Cd(II)-carboxylate-based coordination polymers (Cd(II)-CBCPs), such as sensors, catalysts, and storage materials, in comparison with those of Zn(II) counterparts. A wide range of species with luminescence properties were designed by using proper organic fluorophores, especially a carboxylate bridging ligand combined with an ancillary N-donor species, both with a rigid structure. These characteristics, combined with the arrangement in Cd(II)-CBCPs’ structure and the intermolecular interaction, enable the sensing behavior of a plethora of various inorganic and organic pollutants. In addition, the Lewis acid behavior of Cd(II) was investigated either in developing valuable heterogeneous catalysts in acetalization, cyanosilylation, Henry or Strecker reactions, Knoevenagel condensation, or dyes or drug elimination from wastewater through photocatalysis. Furthermore, the pores structure of such derivatives induced the ability of some species to store gases or toxic dyes. Applications such as in herbicides, antibacterials, and electronic devices are also described together with their ability to generate nano-CdO species. Full article
(This article belongs to the Special Issue Zn(II) and Cd(II) Coordination Polymers: Advances and Perspectives II)
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7 pages, 1783 KiB  
Short Note
trans-catena-Poly[[(bis-(µ-N,N′-bis[(pyridin-3-yl)methyl]ethanediamide))-diaqua-cadmium(II)] bis(nitrate) tetrahydrate)]
by Anna Caria, Enrico Podda, M. Carla Aragoni, Riccardo Lai, Anna Pintus and Massimiliano Arca
Molbank 2024, 2024(3), M1845; https://doi.org/10.3390/M1845 - 3 Jul 2024
Viewed by 1139
Abstract
The reaction between cadmium nitrate tetrahydrate and N,N′-bis(pyridin-3-ylmethyl)oxalamide (L) in a 1:3 molar ratio in a water/acetonitrile (1:6 v/v) mixture afforded single crystals of compound 1 suitable for X-ray diffraction analysis. Compound 1 consists of [...] Read more.
The reaction between cadmium nitrate tetrahydrate and N,N′-bis(pyridin-3-ylmethyl)oxalamide (L) in a 1:3 molar ratio in a water/acetonitrile (1:6 v/v) mixture afforded single crystals of compound 1 suitable for X-ray diffraction analysis. Compound 1 consists of the coordination polymer (CP) [[Cd(L)2(OH2)2](NO3)2·4H2O], in which CdII ions are bridged by neutral L antiperiplanar N-ligands in a wavy ribbon fashion developed along the c-axis. Two trans-disposed water molecules complete the pseudo-octahedral coordination geometry of the metal ion. The crystal packing of 1 revealed the interplay between π–π stacking interactions and an intricate hydrogen-bonded network involving oxalamides, nitrates, and water molecules. The donor properties of L and the intermolecular interactions in compound 1 are interpreted based on hybrid-DFT calculations. Full article
(This article belongs to the Section Structure Determination)
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20 pages, 3767 KiB  
Article
Reactions of Cadmium(II) Halides and Di-2-Pyridyl Ketone Oxime: One-Dimensional Coordination Polymers
by Christina Stamou, Pierre Dechambenoit, Zoi G. Lada, Patroula Gkolfi, Vassiliki Riga, Catherine P. Raptopoulou, Vassilis Psycharis, Konstantis F. Konidaris, Christos T. Chasapis and Spyros P. Perlepes
Molecules 2024, 29(2), 509; https://doi.org/10.3390/molecules29020509 - 19 Jan 2024
Cited by 2 | Viewed by 1926
Abstract
The coordination chemistry of 2-pyridyl ketoximes continues to attract the interest of many inorganic chemistry groups around the world for a variety of reasons. Cadmium(II) complexes of such ligands have provided models of solvent extraction of this toxic metal ion from aqueous environments [...] Read more.
The coordination chemistry of 2-pyridyl ketoximes continues to attract the interest of many inorganic chemistry groups around the world for a variety of reasons. Cadmium(II) complexes of such ligands have provided models of solvent extraction of this toxic metal ion from aqueous environments using 2-pyridyl ketoxime extractants. Di-2-pyridyl ketone oxime (dpkoxH) is a unique member of this family of ligands because its substituent on the oxime carbon bears another potential donor site, i.e., a second 2-pyridyl group. The goal of this study was to investigate the reactions of cadmium(II) halides and dpkoxH in order to assess the structural role (if any) of the halogeno ligand and compare the products with their zinc(II) analogs. The synthetic studies provided access to complexes {[CdCl2(dpkoxH)∙2H2O]}n (1∙2H2O), {[CdBr2(dpkoxH)]}n (2) and {[CdI2(dpkoxH)]}n (3) in 50–60% yields. The structures of the complexes were determined by single-crystal X-ray crystallography. The compounds consist of structurally similar 1D zigzag chains, but only 2 and 3 are strictly isomorphous. Neighboring CdII atoms are alternately doubly bridged by halogeno and dpkoxH ligands, the latter adopting the η111:μ (or 2.0111 using Harris notation) coordination mode. A terminal halogeno group completes distorted octahedral coordination at each metal ion, and the coordination sphere of the CdII atoms is {CdII1 − X)(μ − X)2(Npyridyl)2(Noxime)} (X = Cl, Br, I). The trans-donor–atom pairs in 1∙2H2O are Clterminal/Noxime and two Clbridging/Npyridyl; on the contrary, these donor–atom pairs are Xterminal/Npyridyl, Xbridging/Noxime, and Xbridging/Npyridyl (X = Br, I). There are intrachain H-bonding interactions in the structures. The packing of the chains in 1∙2H2O is achieved via π-π stacking interactions, while the 3D architecture of the isomorphous 2 and 3 is built via C-H∙∙∙Cg (Cg is the centroid of one pyridyl ring) and π-π overlaps. The molecular structures of 1∙2H2O and 2 are different compared with their [ZnX2(dpkoxH)] (X = Cl, Br) analogs. The polymeric compounds were characterized by IR and Raman spectroscopies in the solid state, and the data were interpreted in terms of the known molecular structures. The solid-state structures of the complexes are not retained in DMSO, as proven via NMR (1H, 13C, and 113Cd NMR) spectroscopy and molar conductivity data. The complexes completely release the coordinated dpkoxH molecule, and the dominant species in solution seem to be [Cd(DMSO)6]2+ in the case of the chloro and bromo complexes and [CdI2(DMSO)4]. Full article
(This article belongs to the Special Issue Zn(II) and Cd(II) Coordination Polymers: Advances and Perspectives II)
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12 pages, 2992 KiB  
Article
Fabrication, Crystal Structures, Catalytic, and Anti-Wear Performance of 3D Zinc(II) and Cadmium(II) Coordination Polymers Based on an Ether-Bridged Tetracarboxylate Ligand
by Zheng-Hua Zhao, Qin Zhang, Yu-Feng Liu, Jin-Zhong Gu and Zi-Fa Shi
Crystals 2023, 13(12), 1681; https://doi.org/10.3390/cryst13121681 - 14 Dec 2023
Cited by 2 | Viewed by 1630
Abstract
Two 3D Zn(II) and Cd(II) coordination polymers, [Zn2(µ4-dppa)(µ-dpe)(µ-H2O)]n·nH2O (1) and [Cd2(µ8-dppa)(µ-dpe)(H2O)]n ( [...] Read more.
Two 3D Zn(II) and Cd(II) coordination polymers, [Zn2(µ4-dppa)(µ-dpe)(µ-H2O)]n·nH2O (1) and [Cd2(µ8-dppa)(µ-dpe)(H2O)]n (2), have been constructed hydrothermally using 4-(3,5-dicarboxyphenoxy)phthalic acid (H4dppa), 1,2-di(4-pyridyl)ethylene (dpe), and zinc or cadmium chlorides. Both compounds feature 3D network structures. Their structure and topology, thermal stability, catalytic, and anti-wear properties were investigated. Particularly, excellent catalytic performance was displayed by zinc(II)-polymer 1 in the Knoevenagel condensation reaction at room temperature. Full article
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12 pages, 4947 KiB  
Article
A New Cd(II)-Based Coordination Polymer for Efficient Photocatalytic Removal of Organic Dyes
by Juanjuan Zhao, Zhuoyu Dang, Mohd. Muddassir, Saleem Raza, Aiguo Zhong, Xiaoxiong Wang and Juncheng Jin
Molecules 2023, 28(19), 6848; https://doi.org/10.3390/molecules28196848 - 28 Sep 2023
Cited by 178 | Viewed by 3047
Abstract
Coordination polymers (CPs) are a diverse class of multi-dimensional compounds that show promise as photocatalysts for degrading dyes in polluted water. Herein, a new 1D Cd(II)-based coordination polymer with the formula [Cd(bpyp)(nba)2] (1) (bpyp = 2,5-bis(pyrid-4-yl)pyridine and Hnba = [...] Read more.
Coordination polymers (CPs) are a diverse class of multi-dimensional compounds that show promise as photocatalysts for degrading dyes in polluted water. Herein, a new 1D Cd(II)-based coordination polymer with the formula [Cd(bpyp)(nba)2] (1) (bpyp = 2,5-bis(pyrid-4-yl)pyridine and Hnba = 4-nitrobenzoic acid) is synthesized and characterized. In 1, the two carboxyl groups of two different nba ligands show μ211 and μ111 coordination modes to connect the CdII centers and sit on either side of the chain along the b direction. The produced CP 1 was utilized as the photocatalyst in the process of the photodegradation of methyl blue (MB), methyl orange (MO), rhodamine B (RhB), and methyl violet (MV) dyes when exposed to UV light. The photocatalytic degradation activities of CP 1 were analyzed, and the results suggest that it exhibits an extraordinary efficiency in the degradation of MB, MV, MO, and RhB. RhB has a 95.52% efficiency of degradation, whereas MV has a 58.92% efficiency, MO has 35.44%, and MB has 29.24%. The photodecomposition of dyes is catalyzed mostly by •O2 and •OH, as shown by research involving the trapping of radicals. Full article
(This article belongs to the Section Inorganic Chemistry)
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12 pages, 4026 KiB  
Article
The Anion Impact on Dimensionality of Cadmium(II) Complexes with Nicotinamide
by Željka Soldin, Boris-Marko Kukovec, Milica Kovačić, Marijana Đaković and Zora Popović
Chemistry 2023, 5(2), 1357-1368; https://doi.org/10.3390/chemistry5020092 - 1 Jun 2023
Cited by 2 | Viewed by 2330
Abstract
Three novel cadmium(II) coordination compounds, the dimeric [Cd(CH3COO)2(nia)2]2 (1), the polymeric {[Cd(nia)4](ClO4)2}n (2), and the monomeric [Cd(H2O)3(nia)3](ClO4) [...] Read more.
Three novel cadmium(II) coordination compounds, the dimeric [Cd(CH3COO)2(nia)2]2 (1), the polymeric {[Cd(nia)4](ClO4)2}n (2), and the monomeric [Cd(H2O)3(nia)3](ClO4)2·nia (3), were prepared in the reactions of the nicotinamide (pyridine-3-carboxamide, nia) with the corresponding cadmium(II) salts. All prepared compounds were characterized by elemental analyses, FT-IR spectroscopy, TGA/DTA, and single crystal X-ray analysis. The impact of anions (acetate, perchlorate) and solvent used on the dimensionality of cadmium(II) complexes and the cadmium(II) coordination environment was investigated. The bridging capabilities of acetate ions enabled the formation of dimers in the crystal structure of 1. It was shown that the dimensionality of perchlorate complexes depends on the solvent used. The coordination polymer 2 is isolated from an ethanol solution, while monomeric compound 3 was obtained by using a water/ethanol mixture as a solvent. The pentagonal-bipyramidal coordination of cadmium(II) was found in the presence of chelating and bridging acetate ions in 1. In the presence of non-coordinating perchlorate anions in 2 and 3, the coordination geometry of cadmium(II) is found to be octahedral. The supramolecular amide-amide homosynthon R22(8) was preserved in the hydrogen-bonded frameworks of all three compounds. Full article
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14 pages, 2653 KiB  
Article
Polyaromatic Group Embedded Cd(II)-Coordination Polymers for Microwave-Assisted Solvent-Free Strecker-Type Cyanation of Acetals
by Anirban Karmakar, Anup Paul, Maria Fátima C. Guedes da Silva and Armando J. L. Pombeiro
Molecules 2023, 28(3), 945; https://doi.org/10.3390/molecules28030945 - 18 Jan 2023
Cited by 3 | Viewed by 2307
Abstract
In this work, two new 1D Cd(II) coordination polymers (CPs), [Cd(L1)(NMF)2]n (1) and [Cd(L2)(DMF)(H2O)2]n·n(H2O) (2), have been synthesized, characterized and employed as catalysts for the microwave-assisted solvent-free Strecker-type [...] Read more.
In this work, two new 1D Cd(II) coordination polymers (CPs), [Cd(L1)(NMF)2]n (1) and [Cd(L2)(DMF)(H2O)2]n·n(H2O) (2), have been synthesized, characterized and employed as catalysts for the microwave-assisted solvent-free Strecker-type cyanation of different acetals. Solvothermal reaction between the pro-ligand, 5-{(pyren-1-ylmethyl)amino}isophthalic acid (H2L1) or 5-{(anthracen-9-ylmethyl)amino}isophthalic acid (H2L2), and Cd(NO3)2.6H2O in the presence of NMF or DMF:THF solvent, produces the coordination polymer 1 or 2, respectively. These frameworks were characterized by single-crystal and powder X-ray diffraction analyses, ATR-FTIR, elemental and thermogravimetry analysis. Their structural analysis revealed that both CPs show one-dimensional structures, but CP 1 has a 1D double chain type structure whereas CP 2 is a simple one-dimensional network. In CP 1, the dinuclear {Cd2(COO)4} unit acts as a secondary building unit (SBU) and the assembly of dinuclear SBUs with deprotonated ligand (L12−) led to the formation of a 1D double chain framework. In contrast, no SBU was observed in CP 2. To test the catalytic effectiveness of these 1D compounds, the solvent-free Strecker-type cyanation reactions of different acetals in presence of trimethylsilyl cyanide (TMSCN) was studied with CPs 1 and 2 as heterogenous catalysts. CP 1 displays a higher activity (yield 95%) compared to CP 2 (yield 84%) after the same reaction time. This is accounted for by the strong hydrogen bonding packing network in CP 2 that hampers the accessibility of the metal centers, and the presence of the dinuclear Cd(II) SBU in CP 1 which can promote the catalytic process in comparison with the mononuclear Cd(II) center in CP 2. Moreover, the recyclability and heterogeneity of both CPs were tested, demonstrating that they can be recyclable for at least for four cycles without losing their structural integrity and catalytic activity. Full article
(This article belongs to the Topic Catalysis: Homogeneous and Heterogeneous)
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16 pages, 3694 KiB  
Article
Synthesis, Structure and Photoluminescence Properties of Cd and Cd-Ln Pentafluorobenzoates with 2,2′:6′,2′-Terpyridine Derivatives
by Maxim A. Shmelev, Julia K. Voronina, Maxim A. Evtyukhin, Fedor M. Dolgushin, Evgenia A. Varaksina, Ilya V. Taydakov, Aleksey A. Sidorov, Igor L. Eremenko and Mikhail A. Kiskin
Inorganics 2022, 10(11), 194; https://doi.org/10.3390/inorganics10110194 - 1 Nov 2022
Cited by 15 | Viewed by 2736
Abstract
Six new complexes [Cd(tpy)(pfb)2] (1, tpy = 2,2′:6′,2″-terpyridine), [Ln2Cd2(tpy)2(pfb)10] (Ln = Eu (2Eu), Tb (2Tb)), [Ln2Cd2(tbtpy)2(pfb)10]·2MeCN (Ln = Eu (3Eu [...] Read more.
Six new complexes [Cd(tpy)(pfb)2] (1, tpy = 2,2′:6′,2″-terpyridine), [Ln2Cd2(tpy)2(pfb)10] (Ln = Eu (2Eu), Tb (2Tb)), [Ln2Cd2(tbtpy)2(pfb)10]·2MeCN (Ln = Eu (3Eu), Tb (3Tb), tbtpy = 4,4′,4″-tri-tert-butyl-2,2′:6′,2″-terpyridine), [Eu2Cd2(tppz)(pfb)10]n (4, tppz = 2,3,5,6-tetra-(pyridin-2-yl)pyrazine) based on pentafluorobenzoic acid (Hpfb) have been prepared and investigated. The effect of tridentate ligands on geometry heterometallic scaffolds synthesized complexes is discussed. The supramolecular crystal structures of the new compounds are stabilized by π-π, C-F···π, C-H···O, C-H...F, F….F interactions. Non-covalent interactions have been studied using Hirschfeld surface analysis. The obtained compounds were characterized by single-crystal and powder X-ray diffraction, luminescence spectroscopy, IR spectroscopy, CHN analysis. Complexes 2Ln and 3Ln exhibit metal-centered photoluminescence, but the presence of ligand luminescence bands indicates incomplete energy transfer from the d-block to the lanthanide ion. Full article
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16 pages, 3070 KiB  
Article
Hybrid Coordination Networks for Removal of Pollutants from Wastewater
by Marko Marganovici, Bianca Maranescu, Aurelia Visa, Lavinia Lupa, Iosif Hulka, Vlad Chiriac and Gheorghe Ilia
Int. J. Mol. Sci. 2022, 23(20), 12611; https://doi.org/10.3390/ijms232012611 - 20 Oct 2022
Cited by 1 | Viewed by 2018
Abstract
The adsorption properties of two coordination polymers, resulting from the reaction of divalent metal (Ca2+ or Co2+) salts with (2-carboxyethyl)(phenyl)phosphinic acid, are presented in this paper. The structural and textural characterization before and after adsorption experiments is presented. The adsorbent [...] Read more.
The adsorption properties of two coordination polymers, resulting from the reaction of divalent metal (Ca2+ or Co2+) salts with (2-carboxyethyl)(phenyl)phosphinic acid, are presented in this paper. The structural and textural characterization before and after adsorption experiments is presented. The adsorbent materials were prepared using the hydrothermal procedure. The compound Ca[O2P(CH2CH2COOH)(C6H5)]2 (CaCEPPA) has a layered topology, with the phenyl groups oriented into the interlayer space and crystallizes in the monoclinic system. Compound Co2[(O2P(CH2CH2COO)(C6H5)(H2O)]2·2H2O (CoCEPPA) has a 1D structure composed of zig-zag chains. The adsorption performances of CaCEPPA and CoCEPPA materials were tested in the removal of cadmium and lead from aqueous solutions. The optimum pH of ions adsorption was found to be five for both adsorbent materials. Pseudo-first and second-order kinetic models were used for fitting kinetic experimental data, and Langmuir and Freundlich isotherms were used for modeling the equilibrium experimental data. The pseudo-second-order kinetic model and Langmuir isotherm best described the adsorption of Cd and Pb ions onto the studied materials, judging from the results of the error function (correlation coefficient, sum of square error, chi-square test, and average relative error) analysis. The studied materials present a higher affinity for Cd ions compared with the adsorption capacity developed for the removal of Pb ions from aqueous solutions. CoCEPPA showed the highest adsorption performance in the removal process of metal ions from aqueous solutions compared with CaCEPPA (qm = 54.9 mg Cd2+/g of CoCEPPA, qm = 36.5 mg Cd2+/g of CaCEPPA). Full article
(This article belongs to the Section Materials Science)
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18 pages, 7713 KiB  
Article
Synthesis of 3D Cadmium(II)-Carboxylate Framework Having Potential for Co-Catalyst Free CO2 Fixation to Cyclic Carbonates
by Zafar A. K. Khattak, Nazir Ahmad, Hussein A. Younus, Habib Ullah, Baoyi Yu, Khurram S. Munawar, Muhammad Ashfaq, Sher Ali, Hossain M. Shahadat and Francis Verpoort
Inorganics 2022, 10(10), 162; https://doi.org/10.3390/inorganics10100162 - 1 Oct 2022
Cited by 17 | Viewed by 3906
Abstract
Metal-organic frameworks (MOFs) are porous coordination polymers with interesting structural frameworks, properties, and a wide range of applications. A novel 3D cadmium(II)-carboxylate framework, CdMOF ([Cd2(L)(DMF)(H2O)2]n), was synthesized by the solvothermal method using a tetracarboxylic bridging [...] Read more.
Metal-organic frameworks (MOFs) are porous coordination polymers with interesting structural frameworks, properties, and a wide range of applications. A novel 3D cadmium(II)-carboxylate framework, CdMOF ([Cd2(L)(DMF)(H2O)2]n), was synthesized by the solvothermal method using a tetracarboxylic bridging linker having amide functional moieties. The CdMOF crystal structure exists in the form of a 3D layer structure. Based on the single-crystal X-ray diffraction studies, the supramolecular assembly of CdMOF is explored by Hirshfeld surface analysis. The voids and cavities analysis is performed to check the strength of the crystal packing in CdMOF. The CdMOF followed a multistage thermal degradation pattern in which the solvent molecules escaped around 200 °C and the structural framework remained stable till 230 °C. The main structural framework collapsed (>60 wt.%) into organic volatiles between 400–550 °C. The SEM morphology analyses revealed uniform wedge-shaped rectangular blocks with dimensions of 25–100 μm. The catalytic activity of CdMOF for the solvent and cocatalyst-free cycloaddition of CO2 into epichlorohydrin was successful with 100% selectivity. The current results revealed that this 3D CdMOF is more active than the previously reported CdMOFs and, more interestingly, without using a co-catalyst. The catalyst was easily recovered and reused, having the same performance. Full article
(This article belongs to the Special Issue Advances in Metal Organic Materials for Catalytic Applications)
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11 pages, 2221 KiB  
Article
The High-Temperature Soft Ferromagnetic Molecular Materials Based on [W(CN)6(bpy)]2−/− System
by Janusz Szklarzewicz, Maciej Hodorowicz, Anna Jurowska and Stanisław Baran
Molecules 2022, 27(14), 4525; https://doi.org/10.3390/molecules27144525 - 15 Jul 2022
Cited by 4 | Viewed by 1873
Abstract
The synthesis of molecular materials with magnetic properties, in particular ferromagnetic properties, has been the subject of interest in coordination chemistry for decades. In the last three decades, research has accelerated, as it has emerged that creating bridging systems based on cyanido ligands [...] Read more.
The synthesis of molecular materials with magnetic properties, in particular ferromagnetic properties, has been the subject of interest in coordination chemistry for decades. In the last three decades, research has accelerated, as it has emerged that creating bridging systems based on cyanido ligands is a good and relatively simple way to create complex polymer structures exhibiting magnetic properties. Based on many years of personal experience in the field of the synthesis of polycyanido systems, supported by comprehensive structural analysis, a simple method of transforming cyanido complexes into soft ferromagnetic materials with a Curie temperature (TC) higher than the thermal decomposition temperature, usually above 150 °C has been developed. Two soft ferromagnetic materials based on zinc and cadmium hexacyanido salts in the system with [W(CN)6(bpy)]2−/− anions are presented. The crystal structures (X-ray single crystal as well as XRD) of the precursors and the properties of the ferromagnetic materials are discussed. Most importantly, a patented method of synthesizing this type of material, based on which we obtain more than 80 soft, high-temperature ferromagnetic compounds, which proves the wide spectrum of this method, is also presented. Full article
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13 pages, 3553 KiB  
Article
Effect of Non-Covalent Interactions on the 2,4- and 3,5-Dinitrobenzoate Eu-Cd Complex Structures
by Maxim A. Shmelev, Aleksandr S. Chistyakov, Galina A. Razgonyaeva, Vladimir V. Kovalev, Julia K. Voronina, Fedor M. Dolgushin, Natalia V. Gogoleva, Mikhail A. Kiskin, Alexey A. Sidorov and Igor L. Eremenko
Crystals 2022, 12(4), 508; https://doi.org/10.3390/cryst12040508 - 6 Apr 2022
Cited by 15 | Viewed by 3123
Abstract
Heterometallic {Eu2Cd2} complexes [Eu2(NO3)2Cd2(Phen)2(2,4-Nbz)8]n·2nMeCN (I) and [Eu2(MeCN)2Cd2(Phen)2(3,5-Nbz)10] (II) with the 2,4-dinitrobenzoate (2,4-Nbz) and [...] Read more.
Heterometallic {Eu2Cd2} complexes [Eu2(NO3)2Cd2(Phen)2(2,4-Nbz)8]n·2nMeCN (I) and [Eu2(MeCN)2Cd2(Phen)2(3,5-Nbz)10] (II) with the 2,4-dinitrobenzoate (2,4-Nbz) and 3,5-dinitrobenzoate (3,5-Nbz) anions and 1,10-phenanthroline were synthesized. The compounds obtained were characterized by X-ray single-crystal analysis, powder X-ray diffraction analysis, IR spectroscopy, and elemental analysis. Moreover, the thermal stability of the complexes was also studied. Analysis of the crystal packing showed that where 1,10-phenanthroline is combined with various isomers of dinitrobenzoate anions, different arrangements of non-covalent interactions are observed in the complex structures. In the case of the compound with the 2,4-dinitrobenzoate anion, these interactions lead to a significant distortion of the metal core geometry and formation of a polymeric structure, while the complex with the 3,5-dinitrobenzoate anion has a structure that is typical of similar systems. The absence of europium metal-centered luminescence at 270 nm wavelength was shown. For all the reported compounds, a thermal stability study was carried out that showed that the compounds decomposed with a significant thermal effect. Full article
(This article belongs to the Special Issue Feature Papers in Organic Crystalline Materials)
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14 pages, 3933 KiB  
Article
A Scintillating One-Dimensional Coordination Polymer Based on Cadmium(II), N,N′-(1,4-Phenylenedicarbonyl)diglycinate, and 2,2′-Bipyridine: Crystal Structure, Hirshfeld Surface Analysis, and Luminescence Lifetime Properties
by Niels-Patrick Pook
Solids 2021, 2(4), 371-384; https://doi.org/10.3390/solids2040023 - 13 Nov 2021
Cited by 2 | Viewed by 3552
Abstract
In recent years, several coordination polymers of different dimensions and metal–organic frameworks were tested and expected to be good candidates for closing the gap between organic and plastic scintillators on the one hand side and inorganic scintillators on the other hand side. In [...] Read more.
In recent years, several coordination polymers of different dimensions and metal–organic frameworks were tested and expected to be good candidates for closing the gap between organic and plastic scintillators on the one hand side and inorganic scintillators on the other hand side. In the present work, we report the synthesis and characterization of a novel one-dimensional scintillating coordination polymer based on cadmium(II), N,N′-(1,4-phenylenedicarbonyl)di-glycinate, and 2,2′-bipyridine. Crystals could be obtained from water–methanol solutions and the structure was determined by single-crystal diffraction. The coordination polymer exhibits scintillation under X-ray excitation and laser as well as UV-light induced photoluminescence with fast decay times. Photoluminescence and X-ray excited optical luminescence (XEOL) properties and decay times were performed using a two-dimensional photon counting streak camera system with a time resolution up to 20 ps. The non-covalent interactions and supramolecular assemblies as a potential multiplier of the scintillating effect were investigated with the aid of a Hirshfeld surface analysis. The quality and phase purity of the used crystals and pellets was clarified by powder diffraction and Rietveld refinement. Full article
(This article belongs to the Special Issue Feature Papers of Solids 2021)
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