Carborane Tuning on Iridium Complexes: Redox-switchable Second-order NLO Responses

Overview

Journal J Mol Model

Publisher Springer

Specialty Molecular Biology

Date 2015 Mar 21

PMID 25791353

Citations 2

Authors

Jiao Wang

Wen-Yong Wang

Xin-Yan Fang

Yong-Qing Qiu

Affiliations

Soon will be listed here.

Abstract

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.

Citing Articles

An Unprecedented Family of Luminescent Iridium(III) Complexes Bearing a Six-Membered Chelated Tridentate C^N^C Ligand.

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The influence of Sc doping on structural, electronic and optical properties of BeO, MgO and CaO nanocages: a DFT study.

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