Computational study of ground-state properties of μ 2 -bridged group 14 porphyrinic sandwich complexes.
Julia KohnMarkus BurschAndreas HansenStefan GrimmePublished in: Journal of computational chemistry (2022)
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.
Keyphrases
- density functional theory
- molecular dynamics
- metal organic framework
- computed tomography
- molecular dynamics simulations
- photodynamic therapy
- atomic force microscopy
- single molecule
- electronic health record
- drug delivery
- magnetic resonance imaging
- big data
- machine learning
- deep learning
- heavy metals
- health risk
- mass spectrometry
- health risk assessment
- drinking water
- quantum dots
- artificial intelligence
- crystal structure
- human health