Quantum Chemical Studies of Noncovalent Interactions and Multicenter Bonds Utilizing Local Vibrational Modes
Noncovalent interactions play an important role for the design of novel drugs, better catalysts, synthesis of complex supramolecular structures, and so on. To develop new materials, a well-founded knowledge of how to control the strength of these interactions is desirable. Despite the many investigations done so far, a quantitative assessment of the intrinsic strength of most types of noncovalent interactions is still missing. Recently and for the first time, the Konkoli-Cremer local modes analysis was successfully used to probe the intrinsic strength of hydrogen and pnicogen bonds. We extended these investigations to more than 300 halogen and chalcogen bonds. A series of electronic effects was found to play a major role for the strength of these noncovalent interactions. Among these are relativistic effects, support by a hydrogen bond, charge transfer, and the formation of 3c-4e bonds. Additionally, a new type of chalcogen bonded complex was found. Based on these effects, new strategies for the design of novel material are suggested. In a subsequent project, a conformationally driven bonding mechanism for a general description of noncovalent interaction involving pnicogen, chalcogen, and halogen atoms was proposed. Apart from noncovalent interactions, we designed a general building principle to explain the stability of small gold clusters based on the σ-aromaticity of Au3 ring subunits. These studies provide an ample view on how the strength of noncovalent interactions can be tuned, serving as a starting point for the rational design of novel materials.
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Oliveira, Vytor, "Quantum Chemical Studies of Noncovalent Interactions and Multicenter Bonds Utilizing Local Vibrational Modes" (2017). Chemistry Theses and Dissertations. 1.