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The Role of Substituent Effects in Tuning Metallophilic Interactions and Emission Energy of Bis‐4‐(2‐pyridyl)‐1,2,3‐triazolatoplatinum(II) Complexes
Author(s) -
Prabhath M. R. Ranga,
Romanova Julia,
Curry Richard J.,
Silva S. Ravi P.,
Jarowski Peter D.
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201502390
Subject(s) - homoleptic , substituent , excited state , excimer , photochemistry , photoluminescence , density functional theory , singlet state , chemistry , monomer , time dependent density functional theory , metal , ligand (biochemistry) , fluorescence , crystallography , materials science , computational chemistry , atomic physics , stereochemistry , polymer , organic chemistry , optoelectronics , optics , biochemistry , physics , receptor
The photoluminescence spectra of a series of 5‐substituted pyridyl‐1,2,3‐triazolato Pt II homoleptic complexes show weak emission tunability (ranging from λ =397–408 nm) in dilute (10 −6 M ) ethanolic solutions at the monomer level and strong tunability in concentrated solutions (10 −4 M ) and thin films (ranging from λ =487–625 nm) from dimeric excited states (excimers). The results of density functional calculations (PBE0) attribute this “turn‐on” sensitivity and intensity in the excimer to strong Pt–Pt metallophilic interactions and a change in the excited‐state character from singlet metal‐to‐ligand charge transfer ( 1 MLCT) to singlet metal‐metal‐to‐ligand charge transfer ( 1 MMLCT) emissions in agreement with lifetime measurements.