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The synthesis, structure, and circularly polarized phosphorescence (CPP) properties of axially chiral cyclometalated binuclear platinum(II) complexes were described. A series of optically pure binuclear platinum(II) complexes were synthesized in five steps from commercially available ()- or ()-1,1'-bi-2-naphthol (BINOL) as starting materials. Their three-dimensional molecular structures and square-planar coordination geometries were elucidated from X-ray diffraction and 2D NMR analysis. The complexes were found to exhibit red- to near-infrared photoluminescence in solution and in the solid state. Furthermore, dilute DMSO solutions of the enantiopure samples showed red CPP with relatively high luminescence dissymmetry factor () values. Density functional theory (DFT) calculations were conducted to examine their three-dimensional molecular conformations and photophysical properties.
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http://dx.doi.org/10.1021/acs.inorgchem.4c03675 | DOI Listing |
Angew Chem Int Ed Engl
September 2025
Department of Applied Chemistry for Environment, School of Biological and Environmental Sciences, Kwansei Gakuin University, 1 Gakuen-Uegahara, Sanda, Hyogo, 669-1330, Japan.
A series of mixed metal crystals comprising square-planar platinum(II) and palladium(II) complexes, K[M(CN)(dFppy)]·HO (M = Pt, Pd; dFppy = 2-(4,6-difluorophenyl)pyridinate), were prepared, and their unique luminescence properties-emerging upon mixing-were revealed. Seven mixed crystals with Pt/Pd ratios of 1:0.5, 1:1, 1:1.
View Article and Find Full Text PDFChembiochem
August 2025
Department of Chemistry, Royal College of Surgeons in Ireland, Dublin 2, D02 YN77, Ireland.
The development of the first Pt(II) tetrazine complex, trans-[Pt(II)Cl(dmso)(CH-Tz-Bz-NH)] (1), is reported, which exhibits good in vitro cytotoxicity against MDA-MB-231 cells and succesfully undergoes inverse electron demand Diels-Alder (IEDDA) reactions with trans-cyclooctene (TCO) and bicyclononyne (BCN) derivates in solution. We demonstrate a live-cell IEDDA reaction of 1 with a BF-azadipyrromethene fluorophore (NIR-AZA) posessing a BCN handle. A live-cell bioorthogonal reaction is established using fluorescence lifetime imaging microscopy (FLIM), through a fluorescence lifetime change of 0.
View Article and Find Full Text PDFChem Commun (Camb)
August 2025
College of Chemistry & Pharmacy, Northwest A&F University, Yangling, Shanxi 712100, P. R. China.
A platinum(II) complex (Pt-PF) with bis(imidazolyl)pyridine ligands was synthesized, and its photophysical properties were comprehensively characterized. Two distinct forms of Pt-PF (Y-Pt-PF and R-Pt-PF) exhibiting different colors and structural arrangements were identified. Modulated supramolecular Pt⋯Pt interactions and π-π stacking patterns make the yellow Y-Pt-PF to red R-Pt-PF transformation occur under mechanical grinding or exposure to CHCN or MeOH vapors demonstrating high-contrast mechanochromic and vapochromic properties.
View Article and Find Full Text PDFJ Med Chem
August 2025
Professor Rashidi Laboratory of Organometallic Chemistry, Department of Chemistry, College of Sciences, Shiraz University, Shiraz 71467-13565, Iran.
This study explores platinum(II) phototherapy using cycloplatinated compounds with bidentate 2-(4-substituted) benzoxazole ligands, [Pt()()()] (). The compounds were synthesized and fully characterized, and their photophysical, cytotoxic, and phototoxic properties were analyzed. Time-dependent Density Functional Theory (TD-DFT) calculations supported the analysis of the complexes absorption and photoluminescence, with high-energy absorption showing L'LCT/MLCT [π(Cl, Me) → π*(C^N)] contributions.
View Article and Find Full Text PDFChem Asian J
August 2025
Department of Chemistry, Gyeongsang National University (GNU), 501 Jinju-Daero, Jinju, 52828, S. Korea.
We report the self-assembling behavior of a terpyridine-based alkyne platinum(II) complex (R-L-Pt-BP) under varying composition ratios of DMSO and HO. The resulting self-assemblies exhibited distinct photoluminescence and circular dichroism (CD) properties depending on the solvent conditions. Notably, strong positive CD signals were observed for the self-assembled R-L-Pt-BP in DMSO and HO (2:8 v/v), accompanied by a red-shift in emission wavelength.
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