Site-Selective Benzannulation of N-Heterocycles in Bidentate Ligands Leads to Blue-Shifted Emission from [(P^N)Cu]2(μ-X)2 Dimers

dc.contributor.authorMondal, Rajarshi
dc.contributor.authorLozada, Issiah
dc.contributor.authorDavis, Rebecca L
dc.contributor.authorWilliams, J A Gareth
dc.contributor.authorHerbert, David E
dc.date.accessioned2021-10-22T17:52:21Z
dc.date.available2021-10-22T17:52:21Z
dc.date.issued2018-04-12
dc.date.submitted2021-10-15T20:08:12Zen_US
dc.description.abstractBenzannulated bidentate pyridine/phosphine (P^N) ligands bearing quinoline or phenanthridine (3,4-benzoquinoline) units have been prepared, along with their halide-bridged, dimeric Cu(I) complexes of the form [(P^N)Cu]2(μ-X)2. The copper complexes are phosphorescent in the orange-red region of the spectrum in the solid-state under ambient conditions. Structural characterization in solution and the solid-state reveals a flexible conformational landscape, with both diamond-like and butterfly motifs available to the Cu2X2 cores. Comparing the photophysical properties of complexes of (quinolinyl)phosphine ligands with those of π-extended (phenanthridinyl)phosphines has revealed a counterintuitive impact of site-selective benzannulation. Contrary to conventional assumptions regarding π-extension and a bathochromic shift in the lowest energy absorption maxima, a blue shift of nearly 40 nm in the emission wavelength is observed for the complexes with larger ligand π-systems, which is assigned as phosphorescence on the basis of emission energies and lifetimes. Comparison of the ground-state and triplet excited state structures optimized from DFT and TD-DFT calculations allows attribution of this effect to a greater rigidity for the benzannulated complexes resulting in a higher energy emissive triplet state, rather than significant perturbation of orbital energies. This study reveals that ligand structure can impact photophysical properties for emissive molecules by influencing their structural rigidity, in addition to their electronic structure.en_US
dc.description.sponsorshipNatural Sciences and Engineering Research Council of Canada (RGPIN-2014-03733)en_US
dc.identifier.citationInorganic Chemistry 2018, 57(9), 4966–4978en_US
dc.identifier.doi10.1021/acs.inorgchem.7b03223
dc.identifier.other0000-0002-0679-6025
dc.identifier.other0000-0001-8190-2468
dc.identifier.urihttp://hdl.handle.net/1993/36053
dc.language.isoengen_US
dc.publisherAmerican Chemical Societyen_US
dc.rightsopen accessen_US
dc.subjectCoordination Chemistryen_US
dc.titleSite-Selective Benzannulation of N-Heterocycles in Bidentate Ligands Leads to Blue-Shifted Emission from [(P^N)Cu]2(μ-X)2 Dimersen_US
dc.typePreprinten_US
local.author.affiliationFaculty of Scienceen_US
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