On the Stability of Cyclophane Derivates Using a Molecular Fragmentation Method

• Published in: Chemphyschem 2016-12, Vol.17 (23), p.3863-3874
• Main Authors: Meitei, Oinam Romesh, Heßelmann, Andreas
• Format: Article
• Language: English
• Subjects: cyclophane; fragmentation methods; intermolecular perturbation theory; intramolecular interactions; molecular strain
• ISSN: 1439-4235; 1439-7641
• DOI: 10.1002/cphc.201600942

A molecular fragmentation method is used to study the stability of cyclophane derivates by decomposing the molecular energy into the molecular strain and intramolecular interaction energies. The molecular strain energies obtained by utilising the fragmentation method are in good agreement with existing experimental data. The intramolecular interaction energies calculated as the difference between the supermolecular energy and the bonded fragment energies are repulsive in the cyclophanes studied. The nature of this interaction is studied for groups of systematically extended doubled layered paracyclophane systems using the random‐phase approximation (RPA), two recently developed extensions to the RPA and standard density functional theory (DFT) methods including dispersion corrections. Upon a systematic increase in conjugation the strongly repulsive intramolecular interaction energy reduces and thus leads to an increase in the stability. Finally, existing experimental and theoretical estimates of the molecular strain are compared with the results of this work. Breaking good: The molecular strain in selected cyclophane molecules is investigated by separating it from intramolecular interaction contributions of opposite ring members via a fragmentation approach.