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DFT/TDDFT studies of the ancillary ligand effects on structures and photophysical properties of rhenium (I) tricarbonyl complexes with the imidazo[4,5‐f]‐1,10‐phenanthroline ligand
Author(s) -
Yang XiaoZhu,
Zhang TingTing,
Wei Jia,
Jia JianFeng,
Wu HaiShun
Publication year - 2015
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.24951
Subject(s) - homo/lumo , time dependent density functional theory , rhenium , chemistry , density functional theory , phenanthroline , ligand (biochemistry) , ionization energy , electron affinity (data page) , computational chemistry , photochemistry , crystallography , molecule , ionization , inorganic chemistry , organic chemistry , ion , biochemistry , receptor
The seven rhenium (I) tricarbonyl complexes having a general formula fac ‐[ReBr(CO) 3 (R 1 ,R 2 ,R 3 ‐N ^ N)] (N ^ N = imidazo[4,5‐f]‐1,10‐phenanthroline; R 1 = t Bu, R 2 = R 3 = H, 1 ; R 1 = CCH, R 2 = R 3 = H, 2 ; R 1 = t Bu, R 2 = CCH, R 3 = H, 3 ; R 1 = t Bu, R 2 = R 3 = CCH, 4 ; R 1 = t Bu, R 2 = CH 3 , R 3 = H, 5 ; R 1 = t Bu, R 2 = R 3 = CH 3 , 6 ; R 1 = t Bu, R 2 = OCH 3 , R 3 = H, 7 ) have been investigated theoretically by density functional theory (DFT) and time‐dependent density functional theory (TDDFT) methods. The different substituted groups on N ^ N ligand induce changes on the electronic structures and photophysical properties for these complexes. It is found that the introduction of CC decreases the energy level of lowest unoccupied molecular orbital (LUMO) while the introduction of CH 3 or OCH 3 lead to increase the energy level of LUMO. The order of LUMO energy level rising is in line with the increasing of donating abilities of substituted groups; and the influence of R 2 position is greater than that of R 1 position on LUMO energy level. The lowest energy absorption bands have changes in the order of 7 < 6 < 5 < 1 < 2 < 3 < 4 . These results of electronic affinity (EA), ionization potential (IP), and reorganization energy ( λ ) indicate that all of these complexes can be used as electron transporting materials. Moreover, the smallest difference between λ electron and λ hole of 4 indicates that it is better to be used as an emitter in the organic light‐emitting diodes. © 2015 Wiley Periodicals, Inc.