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TD-DFT computations for trigonal silicon(IV) coordination compounds of rigid bidentates

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Abstract

Computations using standard time dependent DFT (B3LYP/6-31G) can neither reproduce experimental CD spectra of optically active tris(2,4-pentanedionato)silicon(IV), [Si(acac)3]+, nor the CD of a series of similar coordination compounds of Si(IV). These compounds are characterized by exciton coupled ligand transitions which are not influenced by orbitals on the central ion. We have found that TD DFT calculations using long range functionals can indeed reproduce the measured CD satisfactorily. The detailed interpretations make use of D3 point group symmetry and symmetry adapted excited state functions allowing for the electronic coupling of the excitation of the ligands. Computations of similar problems for transition metal ions coordinated to rigid π systems are common and probably also sensitive to the choice of functional.

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Acknowledgments

We wish to thank University of Copenhagen for giving us working conditions for this project.

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Authors and Affiliations

  1. Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100, Copenhagen, Denmark

    Sven E. Harnung

  2. IGM, Faculty of Life Sciences, University of Copenhagen, Thorvaldsensvej 40, 1871, Frederiksberg, Denmark

    Erik Larsen

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  1. Sven E. Harnung
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  2. Erik Larsen
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Correspondence to Erik Larsen.

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Dedicated to Professor Leonard F. Lindoy, a pioneer of macrocyclic and supramolecular chemisttry, on the occasion of his 75th birthday.

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Harnung, S.E., Larsen, E. TD-DFT computations for trigonal silicon(IV) coordination compounds of rigid bidentates. J Incl Phenom Macrocycl Chem 71, 419–428 (2011). https://doi.org/10.1007/s10847-011-9976-8

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  • DOI: https://doi.org/10.1007/s10847-011-9976-8

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