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Keywords = platinum (II) complexes

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19 pages, 1941 KiB  
Article
Structural, Quantum Chemical, and Cytotoxicity Analysis of Acetylplatinum(II) Complexes with PASO2 and DAPTA Ligands
by Stefan Richter, Dušan Dimić, Milena R. Kaluđerović, Fabian Mohr and Goran N. Kaluđerović
Inorganics 2025, 13(8), 253; https://doi.org/10.3390/inorganics13080253 - 27 Jul 2025
Viewed by 428
Abstract
The development of novel platinum-based anticancer agents remains a critical objective in medicinal inorganic chemistry, particularly in light of resistance and toxicity limitations associated with cisplatin. In this study, the synthesis, structural characterization, quantum chemical analysis, and cytotoxic evaluation of four new acetylplatinum(II) [...] Read more.
The development of novel platinum-based anticancer agents remains a critical objective in medicinal inorganic chemistry, particularly in light of resistance and toxicity limitations associated with cisplatin. In this study, the synthesis, structural characterization, quantum chemical analysis, and cytotoxic evaluation of four new acetylplatinum(II) complexes (cis-[Pt(COMe)2(PASO2)2], cis-[Pt(COMe)2(DAPTA)2], trans-[Pt(COMe)Cl(DAPTA)2], and trans-[Pt(COMe)Cl(PASO2)]: 14, respectively) bearing cage phosphine ligands PASO2 (2-thia-1,3,5-triaza-phosphaadamantane 2,2-dioxide) and DAPTA (3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) are presented. The coordination geometries and NMR spectral features of the cis/trans isomers were elucidated through multinuclear NMR and DFT calculations at the B3LYP/6-311++G(d,p)/LanL2DZ level, with strong agreement between experimental and theoretical data. Quantum Theory of Atoms in Molecules (QTAIM) analysis was applied to investigate bonding interactions and assess the covalent character of Pt–ligand bonds. Cytotoxicity was evaluated against five human cancer cell lines. The PASO2-containing complex in cis-configuration, 1, demonstrated superior activity against thyroid (8505C) and head and neck (A253) cancer cells, with potency surpassing that of cisplatin. The DAPTA complex 2 showed enhanced activity toward ovarian (A2780) cancer cells. These findings highlight the influence of ligand structure and isomerism on biological activity, supporting the rational design of phosphine-based Pt(II) anticancer drugs. Full article
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13 pages, 1631 KiB  
Article
Low-Cost Honeycomb Biomass Adsorbent for Efficient Pt Recovery from Automobile Catalyst Waste
by Rafał Olchowski, Patryk Szymczak and Ryszard Dobrowolski
Molecules 2025, 30(14), 2910; https://doi.org/10.3390/molecules30142910 - 10 Jul 2025
Viewed by 311
Abstract
Spent automobile catalysts can be an important source of platinum for industry applications. Low-cost and simple technologies for platinum recovery from this source are sought, especially involving the application of green adsorbents. Honeycomb biowaste can be an excellent candidate for this purpose; n-hexane-treated [...] Read more.
Spent automobile catalysts can be an important source of platinum for industry applications. Low-cost and simple technologies for platinum recovery from this source are sought, especially involving the application of green adsorbents. Honeycomb biowaste can be an excellent candidate for this purpose; n-hexane-treated honeycomb biowaste is therefore obtained for the first time. This material is characterized using several instrumental techniques, confirming the presence of O, N, and P heteroatoms on its surface and the complex morphology of its particles. The maximum static Pt(II)/Pt(IV) adsorption (46 mg/g and 60 mg/g, respectively) onto the n-hexane-extracted honeycomb biomass is reached at pH = 1.55 and a contact time of 50 h. The adsorption kinetics are best fitted to the pseudo-second-order model in both cases. The Langmuir model best described the Pt(II)/Pt(IV) adsorption isotherms on the studied material. Quantitative desorption of the Pt from the studied material is reached for 1 mol/L thiourea dissolved in HCl. The adsorption mechanism of Pt(IV) ions onto the obtained material is based mainly on the surface complexation reactions. The studied material is successfully applied for the first time for Pt(IV) removal from a spent automobile catalyst leachate. Full article
(This article belongs to the Special Issue Novel Adsorbents for Environmental Pollutants' Removal)
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21 pages, 2880 KiB  
Review
Italian Contribution to the Recent Growth of the Luminescent 1,3-Bis(Pyridin-2-yl)benzene Platinum(II) Complex Family
by Alessia Colombo, Claudia Dragonetti, Francesco Fagnani, Daniele Marinotto and Dominique Roberto
Inorganics 2025, 13(7), 221; https://doi.org/10.3390/inorganics13070221 - 1 Jul 2025
Viewed by 757
Abstract
The first chlorido platinum(II) complex with a cyclometallated 1,3-bis(pyridin-2-yl)benzene ligand, Pt(bpyb)Cl, was prepared in 1999. Four years later, its luminescent properties were discovered. Since then, a huge number of studies have been dedicated to the synthesis and characterization of related complexes, and to [...] Read more.
The first chlorido platinum(II) complex with a cyclometallated 1,3-bis(pyridin-2-yl)benzene ligand, Pt(bpyb)Cl, was prepared in 1999. Four years later, its luminescent properties were discovered. Since then, a huge number of studies have been dedicated to the synthesis and characterization of related complexes, and to their application in photonics, optoelectronics, bioimaging, and photodynamic therapy. The present review concerns the main results obtained in the last five years by our research group in Milan. After a brief introduction on Pt(bpyb)Cl complexes, we illustrate our recent investigations to show the Milanese contribution to the rapid growth of this platinum family. Full article
(This article belongs to the Special Issue State-of-the-Art Inorganic Chemistry in Italy)
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29 pages, 3081 KiB  
Review
“Non-Classical” Platinum Complexes: A Concise Review
by Adriana Bakalova, Nina Ruseva and Emiliya Cherneva
Int. J. Mol. Sci. 2025, 26(13), 6270; https://doi.org/10.3390/ijms26136270 - 28 Jun 2025
Viewed by 474
Abstract
The utilization of platinum complexes in medicine continues to be a prevalent treatment modality for diverse tumour types. However, it should be noted that certain platinum complexes are characterized by a high degree of toxicity. In recent years, there has been a focus [...] Read more.
The utilization of platinum complexes in medicine continues to be a prevalent treatment modality for diverse tumour types. However, it should be noted that certain platinum complexes are characterized by a high degree of toxicity. In recent years, there has been a focus among scientists on synthesizing “non-classic” platinum complexes, such as those with a trans-configuration, Pt(IV) complexes, and mixed ammine/amine platinum complexes, with the aim of reducing the toxic side effects of certain platinum complexes, including cisplatin. For instance, newly synthesized platinum complexes with a trans-configuration exhibited substantial cytotoxic activity which was comparable to that of the corresponding cis-isomers and cisplatin. This finding challenged the prevailing cis-geometry paradigm and prompted a re-evaluation of the structural activity relationships (SARs) of antitumour platinum complexes. It is widely accepted that Pt(IV) complexes act as prodrugs and release the active Pt(II) species. This property renders them promising candidates as anticancer drugs. Furthermore, it has been established that mixed ammine/amine platinum complexes are less toxic than cisplatin. In addition, compared to cisplatin, they have been observed to have equivalent or greater cytotoxic activity. Full article
(This article belongs to the Section Biochemistry)
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19 pages, 5413 KiB  
Article
A Dual-Signal Ratiometric Optical Sensor Based on Natural Pine Wood and Platinum(II) Octaethylporphyrin with High Performance for Oxygen Detection
by Zhongxing Zhang, Yujie Niu, Hongbo Mu, Jingkui Li, Jinxin Wang and Ting Liu
Sensors 2025, 25(13), 3967; https://doi.org/10.3390/s25133967 - 26 Jun 2025
Viewed by 285
Abstract
Optical oxygen sensors have attracted considerable attention owing to their high sensitivity, rapid response, and broad applicability. However, their test results may be affected by fluctuations in the pump light source and instability of the detection equipment. In this study, the intrinsic luminescence [...] Read more.
Optical oxygen sensors have attracted considerable attention owing to their high sensitivity, rapid response, and broad applicability. However, their test results may be affected by fluctuations in the pump light source and instability of the detection equipment. In this study, the intrinsic luminescence of pine wood was utilized as the reference signal, and the luminescence of platinum(II) octaethylporphyrin (PtOEP) was employed as the oxygen indication signal, to fabricate a dual-signal ratiometric oxygen sensor PtOEP/PDMS@Pine. The ratio of the luminescence of pine wood to that of PtOEP was defined as the optical parameter (OP). OP increased linearly with oxygen concentration ([O2]) in the range of 10–100 kPa, and a calibration curve was obtained. The sensor exhibits excellent anti-interference capabilities, effectively resisting fluctuations from laser sources and detection equipment. It also displays stable hydrophobicity with a contact angle of 118.3° and maintains excellent photostability under continuous illumination. The sensor exhibited long-term stability within 90 days and robust recovery performance during cyclic tests, wherein the response time and recovery time were determined to be 1.4 s and 1.7 s, respectively. Finally, the effects of temperature fluctuations and photobleaching on the sensor’s performance have been effectively corrected, enabling accurate oxygen concentration measurements in complex environments. Full article
(This article belongs to the Section Optical Sensors)
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15 pages, 1662 KiB  
Article
Peripheral Cycloalkyl Functionalized Tetradentate Platinum(II) Phosphorescent Complex: Synthesis, Optical Tuning, and OLED Applications
by Giheon Park, Seon-jin Lee, Minsoo Kang and Wan Pyo Hong
Materials 2025, 18(13), 2942; https://doi.org/10.3390/ma18132942 - 21 Jun 2025
Viewed by 716
Abstract
A tetradentate Pt(II) complex with a 5/6/6 structural backbone, Pt(PhPiPy-O-PytmCz), was synthesized by incorporating two distinct cycloalkyl groups. These structural modifications significantly enhanced the photoluminescence quantum yield and effectively increased the distance between molecules, thereby mitigating undesirable intermolecular interactions and triplet-state quenching. This [...] Read more.
A tetradentate Pt(II) complex with a 5/6/6 structural backbone, Pt(PhPiPy-O-PytmCz), was synthesized by incorporating two distinct cycloalkyl groups. These structural modifications significantly enhanced the photoluminescence quantum yield and effectively increased the distance between molecules, thereby mitigating undesirable intermolecular interactions and triplet-state quenching. This strategic molecular design resulted in an external quantum efficiency of 11.5% at a wavelength of 539 nm and significantly enhanced operational lifetimes in green phosphorescent organic light-emitting diodes (OLEDs). These findings are expected to inspire the development of new green luminescent materials and innovative strategies in OLED technology. Full article
(This article belongs to the Special Issue Advanced and Smart Materials in Photoelectric Applications)
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17 pages, 3505 KiB  
Article
Linker-Dependent Variation in the Photophysical Properties of Dinuclear 2-Phenylpyridinato(salicylaldiminato)platinum(II) Complexes Featuring NDI Units
by Soichiro Kawamorita, Tatsuya Matsuoka, Kazuki Nakamura, Bijak Riyandi Ahadito and Takeshi Naota
Molecules 2025, 30(12), 2664; https://doi.org/10.3390/molecules30122664 - 19 Jun 2025
Viewed by 350
Abstract
Through-space charge transfer (TSCT) between spatially adjacent donor and acceptor units has garnered considerable attention as a promising design principle for optoelectronic materials. While TSCT systems incorporating rigid spacers have been extensively studied to enhance through-space interactions, transition metal complexes connected by flexible [...] Read more.
Through-space charge transfer (TSCT) between spatially adjacent donor and acceptor units has garnered considerable attention as a promising design principle for optoelectronic materials. While TSCT systems incorporating rigid spacers have been extensively studied to enhance through-space interactions, transition metal complexes connected by flexible linkers remain underexplored, despite increasing interest in their potential TSCT behavior. Herein, we report the design and synthesis of a donor–acceptor–donor (D-A-D)-type complex (1), in which a central naphthalenediimide (NDI) electron acceptor is linked to 2-phenylpyridinato(salicylaldiminato)platinum(II) complexes via flexible alkyl linkers. By systematically varying the linker length (n = 3, 4, 5, 6; 1ad), we achieved precise control over the spatial arrangement between the NDI core and the platinum moieties in solution. Notably, compound 1a (n = 3) adopts an S-shaped conformation in solution, giving rise to a distinct TSCT absorption band. The structural and photophysical properties were thoroughly investigated using single-crystal X-ray diffraction, 1H NMR, NOESY analysis, and DFT calculations, which collectively support the existence of the folded conformation and associated TSCT behavior. These findings highlight that TSCT can be effectively induced in flexible molecular systems by exploiting intramolecular spatial proximity and non-covalent interactions, thereby offering new avenues for the design of responsive optoelectronic materials. Full article
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15 pages, 1744 KiB  
Article
New Conjugatable Platinum(II) Chlorins: Synthesis, Reactivity and Singlet Oxygen Generation
by José Almeida, Giampaolo Barone, Luís Cunha-Silva, Ana F. R. Cerqueira, Augusto C. Tomé, Maria Rangel and Ana M. G. Silva
Molecules 2025, 30(12), 2496; https://doi.org/10.3390/molecules30122496 - 6 Jun 2025
Viewed by 423
Abstract
An efficient protocol was developed for the microwave-mediated metallation of 5-(4-methoxycarbonylphenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (P1) with bis(benzonitrile)platinum dichloride salt and subsequent 1,3-dipolar cycloaddition of the resulting PtP1 with an azomethine ylide to give two isomeric metallochlorins: PtC1 (main isomer) and PtC3. The methyl [...] Read more.
An efficient protocol was developed for the microwave-mediated metallation of 5-(4-methoxycarbonylphenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (P1) with bis(benzonitrile)platinum dichloride salt and subsequent 1,3-dipolar cycloaddition of the resulting PtP1 with an azomethine ylide to give two isomeric metallochlorins: PtC1 (main isomer) and PtC3. The methyl ester group of metalloporphyrin PtP1 and metallochlorin PtC1 was successfully hydrolysed in an alkaline medium to yield the corresponding derivatives PtP2 and PtC2 in moderate-to-good yields. As a proof of concept of the reactivity of the carboxy group in PtP2 and PtC2, these compounds were conjugated with a hydroxylated derivative of indomethacin, a known potent non-steroidal anti-inflammatory, obtaining the conjugates PtP2-Ind and PtC2-Ind. The obtained platinum(II) porphyrins and chlorins were characterized by UV-Vis, NMR spectroscopy and mass spectrometry. The structure of PtP1 was also confirmed by X-ray crystallography. Singlet oxygen generation studies were carried out, as well as theoretical calculations, which demonstrated that the prepared Pt(II) complexes can be considered potential photosensitizers for PDT. Full article
(This article belongs to the Section Colorants)
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17 pages, 4894 KiB  
Article
Investigation of Mechanochromic and Solvatochromic Luminescence of Cyclometalated Heteroleptic Platinum(II) Complexes with Benzoylthiourea Derivatives
by Monica Iliş, Marilena Ferbinteanu, Cristina Tablet and Viorel Cîrcu
Molecules 2025, 30(11), 2415; https://doi.org/10.3390/molecules30112415 - 31 May 2025
Viewed by 554
Abstract
Two novel cyclometalated platinum(II) complexes based on 2-phenylpyridine (ppy) and 2,4-difluorophenylpyridine (dfppy) ligands in combination with a benzoylthiourea (4-(decyloxy)-N-((4-(decyloxy)phenyl)carbamothioyl)benzamide, BTU) functionalized with decyloxy alkyl chains as auxiliary ligands were synthesized and characterized for their mechanochromic and photophysical properties. Structural characterization was achieved through [...] Read more.
Two novel cyclometalated platinum(II) complexes based on 2-phenylpyridine (ppy) and 2,4-difluorophenylpyridine (dfppy) ligands in combination with a benzoylthiourea (4-(decyloxy)-N-((4-(decyloxy)phenyl)carbamothioyl)benzamide, BTU) functionalized with decyloxy alkyl chains as auxiliary ligands were synthesized and characterized for their mechanochromic and photophysical properties. Structural characterization was achieved through IR and NMR spectroscopy, single-crystal X-ray diffraction, and TD-DFT calculations. Both complexes exhibit significant photoluminescence with quantum yields up to 28.3% in a 1% PMMA film. The transitions in solution-phase spectra were assigned to mixed metal-to-ligand (MLCT) and intraligand (ILCT) charge–transfer characteristics. Temperature-dependent studies and thermal analyses confirm reversible phase transitions without mesomorphic behavior despite the presence of the two long alkyl chains. Both complexes displayed reversible mechanochromic and solvatochromic luminescence, with a change in emission color from green to red-orange emissions upon grinding and solvent treatment or heating at 80 °C. Full article
(This article belongs to the Special Issue Chemiluminescence and Photoluminescence of Advanced Compounds)
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13 pages, 2721 KiB  
Article
Unique Three-Component Supramolecular Assembly for Highly Specific Detection of Zinc Ions
by Xiaonan Geng, Lixin Zhang, Duan Xiong, Zhen Su and Qingqing Guan
Sensors 2025, 25(11), 3470; https://doi.org/10.3390/s25113470 - 30 May 2025
Viewed by 436
Abstract
The detection of zinc ions plays an essential role in protecting public health and maintaining ecological balance. However, traditional fluorescent probes for Zn2+ are limited in their specificity, especially under complex environments, due to their single-mode optical signal and inadequate recognization capacities. [...] Read more.
The detection of zinc ions plays an essential role in protecting public health and maintaining ecological balance. However, traditional fluorescent probes for Zn2+ are limited in their specificity, especially under complex environments, due to their single-mode optical signal and inadequate recognization capacities. Herein we report a dual-mode supramolecular sensing system constructed from a unique three-component assembly involving a terpyridine platinum (II) complex, oxalate, and Zn2+, enabling highly specific detection performance for Zn2+. The supramolecular sensing system exhibits excellent selectivity among various interfering substances, accompanied by ultra-low detection limit (0.199 μM) and fast response (<3 s). The high recognization capacity comes from tri-component-based supramolecular assembly, while the dual-mode response arises from the generation of intermelcular Pt-Pt and π-π interactions, which yields absorption and emission originating from low-energy metal–metal-to-ligand charge transfer (MMLCT) transitions. This work marks a pioneering demonstration for highly specific detection of Zn2+ and inspires an alternative strategy for designing cation probes. Full article
(This article belongs to the Section Chemical Sensors)
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15 pages, 2507 KiB  
Article
Selective Photothermal Therapy Using Antioxidant Nanoparticles Encapsulating Novel Near-Infrared-Absorbing Platinum(II) Complexes
by Ryota Sawamura, Hiromi Kurokawa, Atsushi Taninaka, Takuto Toriumi, Yukio Nagasaki, Hidemi Shigekawa, Hirofumi Matsui and Nobuhiko Iki
Nanomaterials 2025, 15(11), 796; https://doi.org/10.3390/nano15110796 - 25 May 2025
Viewed by 750
Abstract
Photothermal therapy (PTT) is a promising approach for cancer treatment that has minimal side effects. It locally heats tumors using agents that convert near-infrared (NIR) light energy into heat. We previously reported that the NIR-absorbing hydrophobic diradical-platinum(II) complex PtL2 (L = 3,5-dibromo-1,2-diiminobenzosemiquinonato [...] Read more.
Photothermal therapy (PTT) is a promising approach for cancer treatment that has minimal side effects. It locally heats tumors using agents that convert near-infrared (NIR) light energy into heat. We previously reported that the NIR-absorbing hydrophobic diradical-platinum(II) complex PtL2 (L = 3,5-dibromo-1,2-diiminobenzosemiquinonato radical) can kill cancer cells through its photothermal conversion ability. In this study, we developed PtL2-loading nanoparticles (PtL2@RNPs) for the delivery of the complex to tumors based on the enhanced permeability and retention effect using an amphiphilic block copolymer that can scavenge reactive oxygen species. PtL2@RNPs exhibited particle diameters of 20–30 nm, an encapsulation efficiency exceeding 90%, and loading capacities of up to 12%. Under NIR laser irradiation, PtL2@RNPs stably generated heat with almost 100% photothermal conversion efficiency. Although the particles were not modified for cancer cell targeting, their uptake by cancer cells was approximately double that by normal cells. PtL2@RNPs exhibited NIR absorption and effectively killed cancer cells at a low irradiation power (0.15 W). Normal cells treated with PtL2@RNPs remained largely undamaged under identical irradiation conditions, demonstrating a cancer-cell-specific photothermal killing effect. These findings can provide insights for future basic studies on cancer cells and the development of effective cancer treatment modalities. Full article
(This article belongs to the Section Biology and Medicines)
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12 pages, 1740 KiB  
Article
A 4-Methylbenzoylhydrazine Pt(II) Complex Inhibits the Proliferation of Breast Cancer Cells by Regulating the Cell Cycle and Inducing Apoptosis
by Huiping Wang, Xianguang Bai, Yarui Li and Kexin Chen
Inorganics 2025, 13(6), 177; https://doi.org/10.3390/inorganics13060177 - 23 May 2025
Viewed by 643
Abstract
In this study, a novel 4-methylbenzoylhydrazide·dimethyl sulfoxide·dichloro platinum(II) complex (Pt2) was synthesized and characterized, and its anti-tumor activity and action mechanism were explored. The molecular structure and spatial configuration of the complex were determined using X-ray diffraction. The results obtained using fluorescence spectroscopy [...] Read more.
In this study, a novel 4-methylbenzoylhydrazide·dimethyl sulfoxide·dichloro platinum(II) complex (Pt2) was synthesized and characterized, and its anti-tumor activity and action mechanism were explored. The molecular structure and spatial configuration of the complex were determined using X-ray diffraction. The results obtained using fluorescence spectroscopy demonstrate that this complex can effectively bind to DNA and affect its fluorescence properties. The experimental results show that Pt2 exhibited significant inhibitory effects on a variety of tumor cell lines (MCF-7, HepG-2, NCI-H460, T24, and A549), and its IC50 values were lower than those of cisplatin (DDP), indicating stronger anti-tumor activity. In addition, the complex not only significantly induced the apoptosis of MCF-7 cells but also inhibited cell cycle arrest at the G2 phase, with the proportion of G2-phase cells as high as 49.47%. In conclusion, the 4-methylbenzoylhydrazide platinum(II) complex exhibits good anti-tumor activity by inducing apoptosis and inhibiting the cell cycle, providing an important experimental basis for the development of novel platinum-based anti-tumor drugs. Full article
(This article belongs to the Special Issue Advances in Metal-Based Anticancer Drugs)
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15 pages, 2825 KiB  
Article
Metal-Involving Bifurcated Halogen Bonding with Iodide and Platinum(II) Center
by Mariya A. Kryukova, Margarita B. Kostareva, Anna M. Cheranyova, Marina A. Khazanova, Anton V. Rozhkov and Daniil M. Ivanov
Int. J. Mol. Sci. 2025, 26(10), 4555; https://doi.org/10.3390/ijms26104555 - 9 May 2025
Viewed by 529
Abstract
The cocrystallization of trans-[PtI2(NCR)2] (R = NMe21, NEt22, Ph 3, o-ClC6H44) with iodine and iodoform gave the crystalline adducts 1∙4I2, 2∙2CHI3 [...] Read more.
The cocrystallization of trans-[PtI2(NCR)2] (R = NMe21, NEt22, Ph 3, o-ClC6H44) with iodine and iodoform gave the crystalline adducts 1∙4I2, 2∙2CHI3, 3∙2CHI3, and 4∙4I2, whose structures were studied by single-crystal X-ray diffractometry (XRD). In the structures, apart from the rather predictable C–H⋯I hydrogen bonds (HBs) and I–I⋯I or C–I⋯I halogen bonds (XBs) with the iodide ligands, we identified bifurcated I–I⋯(I–Pt) and C–I⋯(I–Pt) metal-involving XBs, where the platinum center and iodide ligands function as simultaneous XB acceptors toward σ-holes of I atoms in I2 or CHI3. Appropriate density functional theory (DFT) calculations (PBE-D3/jorge-DZP-DKH with plane waves in the GAPW method) performed with periodic boundary conditions confirmed the existence of the bifurcated metal-involving I–I⋯(I–Pt) and C–I⋯(I–Pt) interactions and their noncovalent nature. Full article
(This article belongs to the Section Materials Science)
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12 pages, 781 KiB  
Article
Synthesis, Structure, and Anticancer Activity of a Dinuclear Organoplatinum(IV) Complex Stabilized by Adenine
by Alisha M. O’Brien, Kraig A. Wheeler and William A. Howard
Compounds 2025, 5(2), 16; https://doi.org/10.3390/compounds5020016 - 1 May 2025
Viewed by 566
Abstract
The dinuclear platinum(IV) compound {Pt(CH3)3}2(μ-I)2(μ-adenine) (abbreviated Pt2ad), obtained by treating cubic [PtIV(CH3)33-I)]4 with two equivalents of adenine, was isolated and structurally characterized by single [...] Read more.
The dinuclear platinum(IV) compound {Pt(CH3)3}2(μ-I)2(μ-adenine) (abbreviated Pt2ad), obtained by treating cubic [PtIV(CH3)33-I)]4 with two equivalents of adenine, was isolated and structurally characterized by single crystal X-ray diffraction. The National Cancer Institute Developmental Therapeutics Program’s in vitro sulforhodamine B assays showed Pt2ad to be particularly cytotoxic against the central nervous system cancer cell line SF-539, and the human renal carcinoma cell line RXF-393. Furthermore, Pt2ad displayed some degree of cytotoxicity against non-small cell lung cancer (NCI-H522), colon cancer (HCC-2998, HCT-116, HT29, and SW-620), melanoma (LOX-IMVI, Malme-3M, M14, MDA-MB-435, SK-MEL-28, and UACC-62), ovarian cancer (OVCAR-5), renal carcinoma (A498), and triple negative breast cancer (BT-549, MDA-MB-231, and MDA-MB-468) cells. Although anticancer studies involving some adenine platinum(II) compounds have been reported, this study marks the first assessment of the anticancer activity of an adenine platinum(IV) complex. Full article
(This article belongs to the Special Issue Organic Compounds with Biological Activity)
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20 pages, 2160 KiB  
Article
Conformational Locking of the Geometry in Photoluminescent Cyclometalated N^C^N Ni(II) Complexes
by Maryam Niazi, Iván Maisuls, Lukas A. Mai, Sascha A. Schäfer, Alex Oster, Lukas Santiago Diaz, Dirk M. Guldi, Nikos L. Doltsinis, Cristian A. Strassert and Axel Klein
Molecules 2025, 30(9), 1901; https://doi.org/10.3390/molecules30091901 - 24 Apr 2025
Viewed by 616
Abstract
In our research aimed at replacing precious transition metals like platinum with abundant base metals such as nickel for efficient triplet emitters, we synthesized and studied Ni(II) complexes [Ni(LNHR)Cl]. These complexes containing the N^C^N cyclometalating dipyridyl-phenide ligand, equipped with pending H-bonding [...] Read more.
In our research aimed at replacing precious transition metals like platinum with abundant base metals such as nickel for efficient triplet emitters, we synthesized and studied Ni(II) complexes [Ni(LNHR)Cl]. These complexes containing the N^C^N cyclometalating dipyridyl-phenide ligand, equipped with pending H-bonding amine groups (NH(C₆H₅) (LNHPh) and NH(C₆H₅CH₂), ClLNHBn). Molecular structures determined from experimental X-ray diffractometry and density functional theory (DFT) calculations in the ground state showed marked deviation of the Cl coligand (ancillary ligand) from the ideal planar coordination, with τ4 values of 0.35 and 0.33, respectively, along with hydrogen bonding interactions of the ligand NH function with the Cl coligand. The complexes exhibit long-wavelength absorption bands at approximately 425 nm in solution, with the experimental spectra being accurately reproduced through time-dependent density functional theory (TD-DFT) calculations. Vibrationally structured emission profiles and steady-state photoluminescence quantum yields of 30% for [Ni(LNHPh)Cl] and 40% for [Ni(LNHBn)Cl] (along with dual excited state lifetimes in the ns and in the ms range) were found in frozen 2-methyl-tetrahydrofuran (2MeTHF) glassy matrices at 77 K. Furthermore, within a poly(methyl methacrylate) matrix, the complexes showed emission bands centered at around 550 nm within a temperature range from 6 K to 300 K with lifetimes similar to 77 K. Based on TD-DFT potential scans along the metal–ligand (Ni–N) coordinate, we found that in a rigid environment that restricts the geometry to the Franck-Condon region, either the triplet T5 or the singlet S4 state could contribute to the photoluminescence. Full article
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