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Reconciling Electrostatic and n→π* Orbital Contributions in Carbonyl Interactions
Author(s) -
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.
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202005739
Subject(s) - lone pair , dipole , chemistry , electrostatics , orbital overlap , natural bond orbital , molecular orbital , non bonding orbital , context (archaeology) , computational chemistry , chemical physics , pi bond , atomic orbital , molecular physics , physics , molecule , electron , quantum mechanics , bond length , bond order , density functional theory , organic chemistry , biology , paleontology
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.