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Nonlinear Absorbing Platinum(II) Diimine Complexes: Synthesis, Photophysics, and Reverse Saturable Absorption
Author(s) -
Liu Rui,
Zhou Dapeng,
Azenkeng Alexander,
Li Zhongjing,
Li Yuhao,
Glusac Ksenija D.,
Sun Wenfang
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201200254
Subject(s) - diimine , ultrafast laser spectroscopy , photochemistry , saturable absorption , chemistry , nanosecond , platinum , absorption (acoustics) , acetylide , singlet state , absorption spectroscopy , density functional theory , excited state , materials science , laser , computational chemistry , optics , atomic physics , organic chemistry , physics , fiber laser , fiber , composite material , catalysis
A series of platinum(II) diimine complexes with different substituents on fluorenyl acetylide ligands ( 1 a – 1 e ) were synthesized and characterized. The influence of the auxiliary substituent on the photophysics of these complexes has been systematically investigated spectroscopically and theoretically (using density functional theory (DFT) methods). All complexes exhibit ligand‐centered 1 π,π* transitions in the UV and blue spectral region, and broad, structureless 1 MLCT/ 1 LLCT ( 1 a , 1 b , 1 d and 1 e ) or 1 MLCT/ 1 LLCT/ 1 π,π* ( 1 c ) absorption bands in the visible region. All complexes are emissive in solution at room temperature, with the emitting state is tentatively assigned to mixed 3 MLCT/ 3 π,π* states. The degree of 3 π,π* and 3 MLCT mixing varies with different substituents and solvent polarities. Complexes 1 a – 1 e exhibit relatively strong singlet and triplet transient absorption from 450 to 800 nm, at which point reverse saturable absorption (RSA) could occur. Nonlinear transmission experiments at 532 nm by using nanosecond laser pulses demonstrate that 1 a – 1 e are strong reverse saturable absorbers and could potentially be used as broadband nonlinear absorbing materials.