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Strategic Modulation of the Photonic Properties of Conjugated Organometallic Pt–Ir Polymers Exhibiting Hybrid CT‐Excited States
Author(s) -
Soliman Ahmed M.,
ZysmanColman Eli,
Harvey Pierre D.
Publication year - 2015
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.201400542
Subject(s) - excited state , density functional theory , ligand (biochemistry) , materials science , absorption (acoustics) , photochemistry , emission spectrum , conjugated system , chemistry , absorption spectroscopy , metal , polymer , computational chemistry , spectral line , atomic physics , physics , optics , biochemistry , receptor , astronomy , metallurgy , composite material
Polymer 6 , ([ trans ‐Pt(PBu 3 ) 2 (CC) 2 ]‐[Ir(dFMeppy) 2 (N^N)](PF 6 )) n , (( [Pt] ‐ [Ir] (PF 6 )) n ; N^N = 5,5′‐disubstituted‐2,2′‐bipyridyl; dFMeppy = 2‐(2,4‐difluoro‐phenyl)‐5‐methylpyridine) is prepared along with model compounds. These complexes are investigated by absorption and emission spectroscopy and their photophysical and electrochemical properties are measured and compared with their corresponding non fluorinated complexes. Density functional theory (DFT) and time‐dependent DFT computations corroborate the nature of the excited state as being a hybrid between the metal‐to‐ligand charge transfer ( 1,3 MLCT) for the trans ‐Pt(PBu 3 ) 2 (CCAr) 2 unit, [Pt] and the metal‐to‐ligand/ligand‐to‐ligand′ charge transfer ( 1,3 ML′CT/LL′CT) for [Ir] with L = dFMeppy. Overall, the fluorination of the phenylpyridine group expectedly does not change the nature of the excited state but desirably induces a small blue shift of the absorption and emission bands along a slight decrease in emission quantum yields and lifetimes.