Computational study of ground-state properties of μ2-bridged group 14 porphyrinic sandwich complexes,Journal of Computational Chemistry

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Computational study of ground-state properties of μ2-bridged group 14 porphyrinic sandwich complexes
Journal of Computational Chemistry ( IF 3.4 ) Pub Date : 2022-04-26 , DOI: 10.1002/jcc.26870
Julia Kohn ₁ , Markus Bursch ₂ , Andreas Hansen ₁ , Stefan Grimme ₁

Affiliation

The structural properties of μ₂-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 r²SCAN-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 O²⁻ by S²⁻ 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.

中文翻译：

μ2-桥接 14 族卟啉夹心配合物基态性质的计算研究

研究了μ ₂ -桥接卟啉双层配合物的结构特性，并阐明了各种配体、金属、取代基和桥接原子对主要结构基序的影响。评估了各种量子化学方法，包括半经验 (SQM) 方法和密度泛函理论 (DFT)，用于计算黄道和交错构象能。生成局部耦合簇 (DLPNO-CCSD(T1)) 数据以供参考。r ²SCAN-3c 复合方案以及 B2PLYP-D4/def2-QZVPP 方法被认为是可靠的方法。能量分解分析 (EDA) 和局部分子轨道分析 (LMO) 用于研究键合情况和配体间相互作用能的性质，强调了有吸引力的伦敦色散相互作用的关键作用。桥接原子的有针对性的修改，例如，通过用S ^{2−替换 O}²⁻表明可以显着改变所研究复合物的主要结构特征。此外，描述了酞菁配体上不同大小的不同取代基对主要构象的影响。

更新日期：2022-04-26

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