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Electronic Structures and Photo-Induced Geometry Distortion of Dinuclear Platinum(II) Complexes Featuring Janus-Type N-Heterocyclic Carbenes: A Theoretical Study

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Abstract

A series of neutral and anionic platinum(II) complexes bearing Janus-type N-Heterocyclic carbenes (NHC) with different extents of π conjugation were constructed theoretically by bridging two cyclometallated platinum(II) centers using diNHC linkers. The diNHCs bind to Pt(II) in either in monodentate (neutral complex I, II) or bidentate (anionic complex III−V) fashion. Structures of all complexes were first optimized. Single point and TD-DFT calculations have been carried out using the gas-phased optimized geometries to gain insight into their electronic structures, possible electronic transitions, and to probe the influence of diNHC ligand design on the photo-responsiveness of the complexes. The response of complexes I−III is limited to UV light; however, complexes IV and V, which contain cyclometallated diNHCs, exhibit absorption bands in the visible region. Additionally, the emissive triplet excited state and the metal-center triplet excited states (3MC) were also investigated. Interestingly, the results suggest that the internal conversion triplet excited state to 3MC in I and III, which induces significant coordination geometry distortion, is energetically favorable for complexes I and III suggesting potentially photo-enhanced reactivities of these two complexes.

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Funding

This research is funded by the Vietnam National University, Hanoi (VNU) under project number QG.20.16.

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Authors and Affiliations

  1. Tran Quoc Tuan University —First Army Academy, Co Dong, Son Tay, 12700, Hanoi, Vietnam

    Kieu Thanh Canh

  2. Faculty of Chemistry, VNU University of Science, Vietnam National University, Hoan Kiem, 11021, Hanoi, Vietnam

    Phung Thi Thanh Hien & Nguyen Van Ha

  3. Hanoi National University of Education, Cau Giay, 11300, Hanoi, Vietnam

    Nguyen Thi Thanh Huyen

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  1. Kieu Thanh Canh
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Correspondence to Nguyen Van Ha.

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Canh, K., Hien, P.T., Huyen, N.T. et al. Electronic Structures and Photo-Induced Geometry Distortion of Dinuclear Platinum(II) Complexes Featuring Janus-Type N-Heterocyclic Carbenes: A Theoretical Study. Russ J Coord Chem 49, 753–764 (2023). https://doi.org/10.1134/S1070328423600043

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