Structure-property relationships of photofunctional diiridium(II) complexes with tetracationic charge and an unsupported Ir–Ir bond

Zheng，Fangrui1,2; Yang，Yuhong1; Wu，Siye1; Zhao，Shunan1; Zhu，Yifan1; Su，Huimin3; Dai，Jun Feng3; Yan，Zeyin1; Chung，Lung Wa1; Wong，Keith Man Chung1

2022-12-01

10.1038/s42004-022-00775-4

Communications Chemistry   Impact Factor & Quartile

2399-3669

2399-3669

In contrast to the extensively studied dirhodium(II) complexes and iridium(III) complexes, neutral or dicationic dinuclear iridium(II) complexes with an unsupported ligand are underdeveloped. Here, a series of tetracationic dinuclear iridium(II) complexes, featuring the unsupported Ir(II)–Ir(II) single bond with long bond distances (2.8942(4)–2.9731(4) Å), are synthesized and structurally characterized. Interestingly, compared to the previous unsupported neutral or dicationic diiridium(II) complexes, our DFT and high-level DLPNO-CCSD(T) results found the largest binding energy in these tetracationic complexes even with the long Ir(II)–Ir(II) bond. Our study further reveals that London dispersion interactions enhance the stability cooperatively and significantly to overcome the strong electrostatic repulsion between two half dicationic metal fragments. This class of complexes also exhibit photoluminescence in solution and solid states, which, to our knowledge, represents the first example of this unsupported dinuclear iridium(II) system. In addition, their photoreactivity involving the generation of iridium(II) radical monomer from homolytic cleavage was also explored. The experimental results of photophysical and photochemical behaviours were also correlated with computational studies.

SCI

English

First ; Corresponding

National Natural Science Foundation of China["21933003","22193020","22193023","22171126"] ; Science, Technology and Innovation Commission of Shenzhen Municipality["JCYJ20210324104609025","JCYJ20190809165411528"] ; Shenzhen Nobel Prize Scientists Laboratory Project[C17783101] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]

Chemistry

Chemistry, Multidisciplinary

WOS:000886992600001

NATURE PORTFOLIO

2-s2.0-85142412807

Scopus

1.Department of Chemistry,Southern University of Science and Technology,Shenzhen,1088 Xueyuan Blvd.,518055,China
2.Analysis and Testing Center,Shenzhen Technology University,Shenzhen,3002 Lantian Road,518118,China
3.Shenzhen Institute for Quantum Science and Engineering,Southern University of Science and Technology,International Quantum Academy (SIQA),and Shenzhen Branch,Hefei National Laboratory,Shenzhen Key Laboratory of Quantum Science and Engineering,Shenzhen,Futian District,518055,China

Zheng，Fangrui,Yang，Yuhong,Wu，Siye,等. Structure-property relationships of photofunctional diiridium(II) complexes with tetracationic charge and an unsupported Ir–Ir bond[J]. Communications Chemistry,2022,5(1).

Zheng，Fangrui.,Yang，Yuhong.,Wu，Siye.,Zhao，Shunan.,Zhu，Yifan.,...&Wong，Keith Man Chung.(2022).Structure-property relationships of photofunctional diiridium(II) complexes with tetracationic charge and an unsupported Ir–Ir bond.Communications Chemistry,5(1).

Zheng，Fangrui,et al."Structure-property relationships of photofunctional diiridium(II) complexes with tetracationic charge and an unsupported Ir–Ir bond".Communications Chemistry 5.1(2022).