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Computational study of ground‐state properties of μ 2 ‐bridged group 14 porphyrinic sandwich complexes
Author(s) -
Kohn Julia,
Bursch Markus,
Hansen Andreas,
Grimme Stefan
Publication year - 2023
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.26870
Subject(s) - ground state , group (periodic table) , state (computer science) , chemistry , computational chemistry , crystallography , mathematics , atomic physics , physics , organic chemistry , algorithm
The structural properties of μ 2 ‐bridged porphyrinic double‐decker complexes are investigated and the influence of various ligands, metals, substituents, and bridging atoms on the dominant structural motif is elucidated. A variety of quantum chemical methods including semiempirical (SQM) methods and density functional theory (DFT) is assessed for the calculation of ecliptic and staggered conformational energies. Local coupled cluster (DLPNO‐CCSD(T1)) data are generated for reference. The r 2 SCAN‐3c composite scheme as well as the B2PLYP‐D4/def2‐QZVPP approach are identified as reliable methods. Energy decomposition analyses (EDA) and localized molecular orbital analyses (LMO) are used to investigate the bonding situation and the nature of the inter‐ligand interaction energy underlining the crucial role of attractive London dispersion interactions. Targeted modification of the bridging atom, e.g., by replacing O 2− by S 2− is shown to drastically change the major structural features of the investigated complexes. Further, the influence of different substituents of varying size at the phthalocyanine ligand regarding the dominant conformation is described.