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Phosphorescent Cationic Iridium (III) Complexes with 1,3,4-Oxadiazole Cyclometalating Ligands:Solvent-Dependent Excited-State Dynamics
Zhuoran Kuang,Xian Wang,Zhen Wang,Guiying He,Qianjin Guo,Lei He*,Andong Xia*
Author NameAffiliationE-mail
Zhuoran Kuang Beijing National Laboratory for Molecular Sciences(BNLMS), Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China;University of Chinese Academy of Sciences, Beijing 100049, China  
Xian Wang Beijing National Laboratory for Molecular Sciences(BNLMS), Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China;University of Chinese Academy of Sciences, Beijing 100049, China  
Zhen Wang College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China  
Guiying He Beijing National Laboratory for Molecular Sciences(BNLMS), Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China;University of Chinese Academy of Sciences, Beijing 100049, China  
Qianjin Guo Beijing National Laboratory for Molecular Sciences(BNLMS), Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China  
Lei He* College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China helei06@csu.edu.cn 
Andong Xia* Beijing National Laboratory for Molecular Sciences(BNLMS), Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China;University of Chinese Academy of Sciences, Beijing 100049, China andong@iccas.ac.cn 
Abstract:
To elucidate the nature of low-lying triplet states and the effect of ligand modifications on the excited-state properties of functional cationic iridium complexes,the solventdependent excited-state dynamics of two phosphorescent cationic iridium (III) complexes,namely[Ir (dph-oxd)2(bpy)]PF6(1) and[Ir (dph-oxd)2(pzpy)]PF6(2),were investigated by femtosecond and nanosecond transient absorption spectroscopy.Upon photoexcitation to the metal-to-ligand charge-transfer (MLCT) states,the excited-state dynamics shows a rapid process (τ=0.7-3 ps) for the formation of solvent stabilized 3MLCT states,which significantly depends on the solvent polarity for both 1 and 2.Sequentially,a relatively slow process assigned to the vibrational cooling/geometrical relaxation and a long-lived phosphorescent emissive state is identified.Due to the different excited-state electronic structures regulated by ancillary ligands,the solvation-induced stabilization of the 3MLCT state in 1 is faster than that in 2.The present results provide a better sight of excited-state relaxation dynamics of ligand-related iridium (III) complexes and solvation effects on triplet manifolds.
Key words:  Iridium complex  Phosphorescence  Metal-to-ligand charge transfer  Transient absorption  Solvation
FundProject:This work is supported by the National Basic Research Program of China (No.2013CB834604),the National Natural Foundation of China (No.21673252,No.21333012,No.21373232,and No.51403240) and the Strategic Priority Research Program of the Chinese Academy of Sciences (No.XDB12020200).
1,3,4-噁二唑环金属配体的磷光型铱阳离子配合物:溶剂相关的激发态动力学研究
匡卓然,王娴,王振,何桂营,郭前进,何磊*,夏安东*
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DOI:10.1063/1674-0068/30/cjcp1703058
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