Pavan Mandapati
Luminescent Platinum(II) Complexes of N^N–^N Amido Ligands with Benzannulated N-Heterocyclic Donor Arms: Quinolines Offer Unexpectedly Deeper Red Phosphorescence than Phenanthridines
Mandapati, Pavan; Braun, Jason D.; Killeen, Charles; Davis, Rebecca L.; Williams, J.A. Gareth; Herbert, David E.
Authors
Jason D. Braun
Charles Killeen
Rebecca L. Davis
Professor Gareth Williams j.a.g.williams@durham.ac.uk
Professor
David E. Herbert
Abstract
A platform for investigating the impact of π-extension in benzannulated, anionic pincer-type N^N–^N-coordinating amido ligands and their Pt(II) complexes is presented. Based on bis(8-quinolinyl)amine, symmetric and asymmetric proligands bearing quinoline or π-extended phenanthridine (3,4-benzoquinoline) units are reported, along with their red-emitting, phosphorescent Pt(II) complexes of the form (N^N–^N)PtCl. Comparing the photophysical properties of complexes of (quinolinyl)amido ligands with those of π-extended (phenanthridinyl)amido analogues revealed a counterintuitive impact of site-selective benzannulation. Contrary to conventional assumptions regarding π-extension, and in contrast to isoenergetic lowest energy absorption bands and a red shift in fluorescence from the organic proligands, a blue shift of nearly 40 nm in the emission wavelength is observed for Pt(II) complexes with more extended bis(phenanthridinyl) ligand π-systems. Comparing the ground state and triplet excited state structures optimized from density functional theory (DFT) and time-dependent-DFT calculations, we trace this effect to a greater rigidity of the benzannulated complexes, resulting in a higher energy emissive triplet state, rather than to a significant perturbation of orbital energies caused by π-extension.
Citation
Mandapati, P., Braun, J. D., Killeen, C., Davis, R. L., Williams, J. G., & Herbert, D. E. (2019). Luminescent Platinum(II) Complexes of N^N–^N Amido Ligands with Benzannulated N-Heterocyclic Donor Arms: Quinolines Offer Unexpectedly Deeper Red Phosphorescence than Phenanthridines. Inorganic Chemistry, 58(21), 14808-14817. https://doi.org/10.1021/acs.inorgchem.9b02480
Journal Article Type | Article |
---|---|
Acceptance Date | Oct 9, 2019 |
Online Publication Date | Oct 22, 2019 |
Publication Date | Nov 4, 2019 |
Deposit Date | Oct 24, 2019 |
Publicly Available Date | Oct 22, 2020 |
Journal | Inorganic Chemistry |
Print ISSN | 0020-1669 |
Electronic ISSN | 1520-510X |
Publisher | American Chemical Society |
Peer Reviewed | Peer Reviewed |
Volume | 58 |
Issue | 21 |
Pages | 14808-14817 |
DOI | https://doi.org/10.1021/acs.inorgchem.9b02480 |
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Copyright Statement
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic chemistry copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.inorgchem.9b02480
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