Metal-mediated self-assembly of isocyanides and methyl 4-aminopyrimidine-5-carboxylate leads to luminescent Pd and Pt complexes featuring C,N-cyclometalated acyclic diaminocarbene (ADC) ligands. The solid-state luminescent properties of these diaminocarbene derivatives are attributed to their triplet-state metal/metal-to-ligand charge-transfer (MMLCT) nature, which is driven by attractive intermolecular M···M interactions further reinforced by the intramolecular π-π interactions even in the structure of the Pd compound, which is the first Pd-ADC phosphor reported.
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http://dx.doi.org/10.1021/acs.inorgchem.3c03346 | DOI Listing |
Inorg Chem
December 2024
Departamento de Química Inorgánica, Facultad de Química, Universidad de Murcia, Campus de Espinardo, 19, 30100 Murcia, Spain.
Dicationic, -symmetrical, tris-chelate Pt(IV) complexes of general formula [Pt(trz)(N∧N)](OTf), bearing two cyclometalated 4-butyl-3-methyl-1-phenyl-1-1,2,3-triazol-5-ylidene (trz) ligands and one aromatic diimine [N∧N = 2,2'-bipyridine (bpy, ), 4,4'-di--butyl-2,2'-bipyridine (dbbpy, ), 4,4'-dimethoxi-2,2'-bipyridine (dMeO-bpy, ), 1,10-phenanthroline (phen, ), 4,7-diphenyl-1,10-phenanthroline (bphen, ), dipyrido[3,2-:2',3'-]phenazine (dppz, ), or 2,3-diphenylpyrazino[2,3-][1,10]phenanthroline (dpprzphen, )] are obtained through chloride abstraction from [PtCl(trz)] () using AgOTf in the presence of the corresponding diimine. Complexes show long-lived phosphorescence from LC excited states involving the diimine ligand, with quantum yields that reach 0.18 in solution and 0.
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December 2024
Institute for Organic Synthesis and Photoreactivity (ISOF), National Research Council of Italy (CNR), Via Piero Gobetti 101, 40129 Bologna, Italy.
The 4-methyl-2-(pyridin-2-yl)-2,1-borazaronaphthalene molecule Hazab-py has been successfully used, for the first time, as a ligand in a ruthenium(II) polypyridine complex A (with the formula [Ru(dtbbpy)(azab-py)], where dtbbpy = 4,4'-di--butyl-2,2'-bipyridine). This compound was characterized by NMR spectroscopy and high-resolution mass spectrometry (MS), and its electrochemical and photophysical properties were fully investigated and compared to those of its homoleptic analogue [Ru(dtbbpy)] (B), an archetypical mono-cationic cyclometalated complex C (with the formula [Ru(dtbbpy)(ppy)], where Hppy = 2-phenylpyridine), and the more structurally similar analogue [Ru(dtbbpy)(naft-py)] (D), where the B-N unit of the azaborine ligand is replaced by a standard CC one, resulting in the 2-(naphthalen-2-yl)pyridine ligand (Hnaft-py). The presence of the novel 1,2-azaborine ligand induces a 0.
View Article and Find Full Text PDFInorg Chem
December 2024
Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, Narashino, Chiba 275-8575, Japan.
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.
View Article and Find Full Text PDFInorg Chem
December 2024
The Biomedical and Environmental Sensor Technology (BEST) Research Centre, Biosensors Program, La Trobe Institute for Molecular Science (LIMS), La Trobe University, Melbourne, Victoria 3086, Australia.
A series of electrochemiluminescent (ECL) iridium(III) complexes with the general formula [Ir(CN)(pim)] (where CN = cyclometalating ligands 2-phenylpyridinato (ppy) or 2-(2,4-difluorophenyl)pyridinato (dFppy), and pim = 2-(2-pyridyl)imidazole) have been synthesized. In each case, the 2-(2-pyridyl)imidazole ancillary ligand has been modified to facilitate bioconjugation and ECL label development. All complexes exhibit blue-shifted optical and electro-generated phosphorescence relative to the archetypal complex [Ir(ppy)(bpy)] (bpy = 2,2'-bipyridine).
View Article and Find Full Text PDFInorg Chem
December 2024
Key Laboratory of Advanced Light Conversion Materials and Biophotonics, School of Chemistry and Life Resources, Renmin University of China, Beijing 100872, China.
Bidentate Pt(II) complexes with cyclometalated -heteroarene or -heterocyclic carbene (NHC) ligands have been extensively studied as phosphorescent emitters over the past two decades. Herein, we introduce a difluoromethyl group (CFH) into the wingtip of NHCs, where CFH acts as a lipophilic hydrogen bond (HB) donor. Their cyclometalated Pt(II) complexes show excellent PLQYs (up to 93%) and phosphorescence lifetimes mainly due to the rigid structure with hydrogen bonding between the CFH group and the adjacent O atom at the β-diketonate ligand.
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