Publication details for Prof. J.A. Gareth WilliamsMandapati, Pavan, Braun, Jason D., Killeen, Charles, Davis, Rebecca L., Williams, J. A. Gareth & Herbert, David 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.
- Publication type: Journal Article
- ISSN/ISBN: 0020-1669 (print), 1520-510X (electronic)
- DOI: 10.1021/acs.inorgchem.9b02480
- Further publication details on publisher web site
- Durham Research Online (DRO) - may include full text
Author(s) from Durham
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.