NDLI: Understanding the photophysical properties of chiral dinuclear Re(I) complexes and the role of Re(I) in their complexes

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Understanding the photophysical properties of chiral dinuclear Re(I) complexes and the role of Re(I) in their complexes

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Understanding the photophysical properties of chiral dinuclear Re(I) complexes and the role of Re(I) in their complexes

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Yang, Guochun Pan, Xiumei Liu, Chunyu Si, Yanling Shi, Shaoqing
Description	Author Affiliation: Liu C ( Faculty of Chemistry, Northeast Normal University, Changchun, 130024 Jilin, China. yanggc468@nenu.edu.cn panxm460@nenu.edu.cn.)
Abstract	Chiral transition metal complexes not only have large nonlinear optical (NLO) response but also meet the non-centrosymmetric requirement of second-order NLO materials. Therefore, chiral transition metal complexes become very active in the NLO area. Recently, the second-order NLO response of chiral dinuclear Re(I) complex 2 has been found to be 1.5 times larger than that of $KH_{2}PO_{4}$ (KDP) based on experimental measurement. However, its NLO origin has not been determined and a structure–property relationship has not been established at the microscopic level, which are very important to further improve the performance. It is found that charge transfer from metal to ligand is mainly responsible for its NLO origin. Based on complex 2, the designed complexes have remarkably large second-order NLO activity. For instance, the designed complex 9 has a very large second-order NLO response value (115.81 × $10^{−30}$ esu), which is about 668 times larger than the organic molecule urea. Moreover, time-dependent density functional theory (TDDFT) calculations have been used to investigate their UV-Vis/CD spectra. The simulated circular dichroism (CD) spectra of the complex 2 are in good agreement with the experimental ones, which can be used to assign the absolute configurations (ACs) of chiral dinuclear Re(I) complexes with high confidence. The electronic absorption wavelengths, electron transition properties, and the second-order NLO responses strongly depend on the nature of substituent, different ligands (pyridine and isoquinoline) and their combinations. Based on NBO analysis, the interactions between $[Re(CO)_{3}Cl]$ fragments and ligands are of n → σ* character.
ISSN	14779226
Issue Number	17
Journal	Dalton Trans.
Volume Number	45
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2016-05-07
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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