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- Title
Reconciling Electrostatic and n→π* Orbital Contributions in Carbonyl Interactions.
- Authors
Muchowska, Kamila B.; Pascoe, Dominic J.; Borsley, Stefan; Smolyar, Ivan V.; Mati, Ioulia K.; Adam, Catherine; Nichol, Gary S.; Ling, Kenneth B.; Cockroft, Scott L.
- Abstract
Interactions between carbonyl groups are prevalent in protein structures. Earlier investigations identified dominant electrostatic dipolar interactions, while others implicated lone pair n→π* orbital delocalisation. Here these observations are reconciled. A combined experimental and computational approach confirmed the dominance of electrostatic interactions in a new series of synthetic molecular balances, while also highlighting the distance‐dependent observation of inductive polarisation manifested by n→π* orbital delocalisation. Computational fiSAPT energy decomposition and natural bonding orbital analyses correlated with experimental data to reveal the contexts in which short‐range inductive polarisation augment electrostatic dipolar interactions. Thus, we provide a framework for reconciling the context dependency of the dominance of electrostatic interactions and the occurrence of n→π* orbital delocalisation in C=O⋅⋅⋅C=O interactions.
- Subjects
NONBONDING electron pairs; NATURAL orbitals; PROTEIN structure; CARBONYL group; COMPUTATIONAL chemistry; LIQUID-liquid equilibrium
- Publication
Angewandte Chemie, 2020, Vol 132, Issue 34, p14710
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.202005739