Computational study of ground‐state properties of μ2‐bridged group 14 porphyrinic sandwich complexes. Issue 3 (26th April 2022)

• Record Type: Journal Article
• Authors: Kohn, Julia; Bursch, Markus; Hansen, Andreas; Grimme, Stefan
• Is Part Of: Journal of computational chemistry. Volume 44:Issue 3(2023)
• Page Start: 229
• Page End: 239
• Publication Date: 2022-04-26
• Subjects: density functional theory -- energy decomposition -- London dispersion -- phthalocyanines -- sandwich complexes; Chemistry -- Data processing -- Periodicals; 542.85
• DOI: 10.1002/jcc.26870
• Languages: English
• ISSNs: 0192-8651

Abstract

Abstract: 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. Abstract : The influences of various constitutional parameters, like metals, ligands, bridging atom, bridging angle, substituent or stacking angle, onto shape and energetic properties of μ 2 ‐bridged porphyrinic double‐decker complexes is evaluated and targeted design possibilities are proposed. With the help of high level density functional theory and semiempirical methods, the electronic nature of the stabilization of ecliptic and staggered structure motifs is explained.