Carborane tuning on iridium complexes: redox-switchable second-order NLO responses

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• 作者：Jiao Wang ; Wen-Yong Wang ; Xin-Yan Fang ; Yong-Qing Qiu
• 关键词：Carborane ; Iridium complexes ; Redox ; Second ; order NLO response
• 刊名：Journal of Molecular Modeling
• 出版年：2015
• 出版时间：April 2015
• 年：2015
• 卷：21
• 期：4
• 全文大小：1,108 KB
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• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Computer Applications in Chemistry
  Biomedicine
  Molecular Medicine
  Health Informatics and Administration
  Life Sciences
  Computer Application in Life Sciences
  
• 出版者：Springer Berlin / Heidelberg
• ISSN：0948-5023

文摘

Much effort has been devoted to investigating the molecular geometries, electronic structures, redox properties and nonlinear optical (NLO) properties of Ir complexes involving o-, m- or p-carborane groups by density functional theory (DFT) methods. Switchable second-order NLO properties were induced by redox processes involving these complexes, and it was found that mainly the coordination bonds of Ir complexes changed during the oxidation process. Our calculations revealed that oxidation reactions have a significant influence on the second-order NLO response owing to the change in charge transfer pattern. The β tot values of oxidized species are at least ? times larger for set I and ? times larger for set II than those of the corresponding parent complexes. Introduction of carborane groups into ppy (phenylpyridine) ligands can enhance the second-order NLO response by 1.2–-.6 times by a metal-to-ligand charge transfer (MLCT) transition between the Ir atom and carborane. The β tot of complex 2 [(ppy)2Ir(phen)]+ (phen-?phenanthroline) is 3.3 times larger than that of complex 1 (ppy)2Ir(acce) (acce-?acetylacetonate), which is caused by ligand-to-ligand charge transfer (LLCT) between ppy ligands and the ancillary ligand. Therefore, it can be concluded that the second-order NLO response can be effectively enhanced by oxidation reactions. Graphical abstract Redox-switchable second-order nonlinear optical (NLO) responses