Luminescent Platinum(II) Complexes of N^N–^N Amido Ligands with Benzannulated N-Heterocyclic Donor Arms: Quinolines Offer Unexpectedly Deeper Red Phosphorescence than Phenanthridines
| dc.contributor.author | mandapati, pavan | |
| dc.contributor.author | Braun, Jason | |
| dc.contributor.author | Killeen, Charles | |
| dc.contributor.author | Davis, Rebecca L | |
| dc.contributor.author | Williams, J A Gareth | |
| dc.contributor.author | Herbert, David E | |
| dc.date.accessioned | 2021-10-22T17:52:35Z | |
| dc.date.available | 2021-10-22T17:52:35Z | |
| dc.date.issued | 2019-10-22 | |
| dc.date.submitted | 2021-10-15T20:14:28Z | en_US |
| dc.description.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. | en_US |
| dc.description.sponsorship | Natural Sciences and Engineering Research Council of Canada (RGPIN-2014-03733) | en_US |
| dc.identifier.citation | Inorganic Chemistry 2019, 58(21), 14808–14817 | en_US |
| dc.identifier.doi | 10.1021/acs.inorgchem.9b02480 | |
| dc.identifier.uri | http://hdl.handle.net/1993/36054 | |
| dc.language.iso | eng | en_US |
| dc.publisher | American Chemical Society | en_US |
| dc.rights | open access | en_US |
| dc.subject | Coordination Chemistry | en_US |
| dc.title | Luminescent Platinum(II) Complexes of N^N–^N Amido Ligands with Benzannulated N-Heterocyclic Donor Arms: Quinolines Offer Unexpectedly Deeper Red Phosphorescence than Phenanthridines | en_US |
| dc.type | Preprint | en_US |
| local.author.affiliation | Faculty of Science | en_US |