TY - JOUR

T1 - β-Diketonate Coordination: Vibrational Properties, Electronic Structure, Molecular Topology, and Intramolecular Interactions. Beryllium(II), Copper(II), and Lead(II) as Study Cases

AU - Martynova, Svetlana

AU - Krisyuk, Vladislav

AU - Sukhikh, Aleksandr

AU - Benassi, Enrico

N1 - The authors are grateful to Dr. Irina V. Mirzaeva and Dr. Vladislav V. Komarov for their helpful and stimulating discussions. This work was supported by the Ministry of Science and Higher Education of the Russian Federation, No. 121031700314-5 and by the “5-100” program” and made possible, thanks to the computational resources kindly provided by the Siberian Supercomputing Center (SSCC) RAS SB. The authors express their gratitude to Dr. Nikolay V. Kuchin for his technical assistance.

PY - 2025

Y1 - 2025

N2 - Nine metal complexes formed by three symmetric β-diketonates (viz., acetylacetonate (acac), 1,1,1,3,3,3-hexafluoro-acetylacetonate (hfac), and 2,2,6,6-tetramethylheptane-3,5-dionate (tmhd)) and three metal ions (with three different coordination geometries, viz., BeII - tetrahedral, CuII - square planar, and PbII - “swing” square pyramidal) were investigated. The study combines structural analyses, vibrational spectroscopic techniques, and quantum chemical calculations with the aim of bridging crystal structure, electronic structure, molecular topology, and far-infrared (FIR) spectroscopic characteristics. The effect of intramolecular interactions on the structural, electronic, and spectroscopic features is the center of this study. The crystal structure of Be(tmhd)2 is also reported and discussed for the first time. A complete review of the experimental IR spectra is offered; discrepancies in the assignments of some peaks are revealed among the published works. Anharmonic effects were considered for acac complexes; however, they were negligible for the FIR modes. A systematic comparison between computed and experimentally measured data allowed us to design an inexpensive, yet efficient computational protocol to investigate large polynuclear complexes.

AB - Nine metal complexes formed by three symmetric β-diketonates (viz., acetylacetonate (acac), 1,1,1,3,3,3-hexafluoro-acetylacetonate (hfac), and 2,2,6,6-tetramethylheptane-3,5-dionate (tmhd)) and three metal ions (with three different coordination geometries, viz., BeII - tetrahedral, CuII - square planar, and PbII - “swing” square pyramidal) were investigated. The study combines structural analyses, vibrational spectroscopic techniques, and quantum chemical calculations with the aim of bridging crystal structure, electronic structure, molecular topology, and far-infrared (FIR) spectroscopic characteristics. The effect of intramolecular interactions on the structural, electronic, and spectroscopic features is the center of this study. The crystal structure of Be(tmhd)2 is also reported and discussed for the first time. A complete review of the experimental IR spectra is offered; discrepancies in the assignments of some peaks are revealed among the published works. Anharmonic effects were considered for acac complexes; however, they were negligible for the FIR modes. A systematic comparison between computed and experimentally measured data allowed us to design an inexpensive, yet efficient computational protocol to investigate large polynuclear complexes.

UR - https://www.mendeley.com/catalogue/7eecea1a-d0d6-31c4-9e8f-495b91029b5e/

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85215694224&origin=inward&txGid=744cd5726f83e76363777c4922418b58

U2 - 10.1021/acs.jpca.4c05850

DO - 10.1021/acs.jpca.4c05850

M3 - Article

C2 - 39824749

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

ER -