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Electronic Structures of Reduced and Superreduced Ir2(1,8-diisocyanomenthane)4n+ Complexes

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J. Heyrovský Institute of Physical Chemistry, Czech Academy of Sciences, Dolejškova 3, 182 23 Prague, Czech Republic
Beckman Institute, California Institute of Technology, Pasadena, California 91125, United States
§ School of Biological and Chemical Sciences, Queen Mary University of London, Mile End Road, London E1 4NS, United Kingdom
Cite this: Inorg. Chem. 2017, 56, 5, 2874–2883
Publication Date (Web):February 20, 2017
https://doi.org/10.1021/acs.inorgchem.6b03001
Copyright © 2017 American Chemical Society

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    Abstract

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    Molecular and electronic structures of Ir2(1,8-diisocyanomenthane)4n+ (Ir(dimen)n+) complexes have been investigated by DFT for n = 2, 1, 0 (abbreviated 2+, 1+, 0). Calculations reproduced the experimental structure of 2+, ν(C≡N) IR, and visible absorption spectra of all three oxidation states, as well as the EPR spectrum of 1+. We have shown that the two reduction steps correspond to successive filling of the Ir–Ir pσ orbital. Complexes 2+ and 1+ have very similar structures with 1+ having a shorter Ir–Ir distance. The unpaired electron density in 1+ is delocalized along the Ir–Ir axis and over N atoms of the eight C≡N– ligands. The second reduction step 1+0 changes the Ir(CN−)4 coordination geometry at each Ir site from approximately planar to seesaw whereby one −N≡C–Ir–C≡N– moiety is linear and the other bent at the Ir (137°) as well as N (146°) atoms. Although complex 0 is another example of a rare (pσ)2 dimetallic species (after [Pt2(μ-P2O5(BF2)2)4]6–, J. Am. Chem. Soc.2016, 138, 5699), the redistribution of lower lying occupied molecular orbitals increases electron density predominantly at the bent C≡N– ligands whose N atoms are predicted to be nucleophilic reaction centers.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.6b03001.

    • Calculated IR and UV–vis spectra of the 3:1 orientational isomer of 2+, 1+, and 0; frontier MO compositions of both deformational isomers of 2+, 1+, and 0; figures showing 1+ spin density distribution and spectroscopically important MOs of 2+, 1+, and 0 (PDF)

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    Cited By

    This article is cited by 4 publications.

    1. Martin Pižl, Bryan M. Hunter, Igor V. Sazanovich, Michael Towrie, Harry B. Gray, Stanislav Záliš, Antonín Vlček. Excitation-Wavelength-Dependent Photophysics of d8d8 Di-isocyanide Complexes. Inorganic Chemistry 2022, 61 (6) , 2745-2759. https://doi.org/10.1021/acs.inorgchem.1c02645
    2. Martin Pižl, Bryan M. Hunter, Gregory M. Greetham, Michael Towrie, Stanislav Záliš, Harry B. Gray, Antonín Vlček. Ultrafast Wiggling and Jiggling: Ir2(1,8-diisocyanomenthane)42+. The Journal of Physical Chemistry A 2017, 121 (48) , 9275-9283. https://doi.org/10.1021/acs.jpca.7b10215
    3. Fangrui Zheng, Yuhong Yang, Siye Wu, Shunan Zhao, Yifan Zhu, Huimin Su, Jun-Feng Dai, Zeyin Yan, Lung Wa Chung, Keith Man-Chung Wong. Structure-property relationships of photofunctional diiridium(II) complexes with tetracationic charge and an unsupported Ir–Ir bond. Communications Chemistry 2022, 5 (1) https://doi.org/10.1038/s42004-022-00775-4
    4. Harry B. Gray, Stanislav Záliš, Antonín Vlček. Electronic structures and photophysics of d8-d8 complexes. Coordination Chemistry Reviews 2017, 345 , 297-317. https://doi.org/10.1016/j.ccr.2017.01.008

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