caa a22 4500 605512620 CHVBK 20210128100656.0 cr unu---uuuuu 210128e20150401xx s 000 0 eng 10.1007/s00894-015-2650-0 doi (NATIONALLICENCE)springer-10.1007/s00894-015-2650-0 Carborane tuning on iridium complexes: redox-switchable second-order NLO responses [Elektronische Daten] [Jiao Wang, Wen-Yong Wang, Xin-Yan Fang, Yong-Qing Qiu] 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 ∼9 times larger for set I and ∼5 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- 1.6 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 Springer-Verlag Berlin Heidelberg, 2015 Carborane nationallicence Iridium complexes nationallicence Redox nationallicence Second-order NLO response nationallicence Wang Jiao Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, 130024, Changchun, Jilin, People's Republic of China aut Wang Wen-Yong Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, 130024, Changchun, Jilin, People's Republic of China aut Fang Xin-Yan Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, 130024, Changchun, Jilin, People's Republic of China aut Qiu Yong-Qing Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, 130024, Changchun, Jilin, People's Republic of China aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/4(2015-04-01), 1-10 1610-2940 21:4<1 2015 21 894 https://doi.org/10.1007/s00894-015-2650-0 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2650-0 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Wang Jiao Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, 130024, Changchun, Jilin, People's Republic of China aut NATIONALLICENCE 700 1- Wang Wen-Yong Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, 130024, Changchun, Jilin, People's Republic of China aut NATIONALLICENCE 700 1- Fang Xin-Yan Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, 130024, Changchun, Jilin, People's Republic of China aut NATIONALLICENCE 700 1- Qiu Yong-Qing Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, 130024, Changchun, Jilin, People's Republic of China aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/4(2015-04-01), 1-10 1610-2940 21:4<1 2015 21 894