Phenyl isocyanide has been chosen as a prototype to probe the π-πinteraction modulated by the -NC group, which has a chameleonic nature with two main resonance forms showing a triple bond and being carbenoid. The rotational spectroscopic investigation complemented with theoretical analyses indicates that the phenyl isocyanide dimer has a scissor-like configuration controlled by dispersive forces along with the formation of π-πstacking. This is the first rotational spectroscopic evidence, to the best of our knowledge, that the mono-substitution by an -NC group on benzene can activate the meta position in forming noncovalent interactions. This work also provides experimental evidence on the importance of substituent effects in modulating π-πstacked structures, as well as practical proof of a biased interaction behavior of isocyanide-substituted aromatic molecules.

Scissor-like Face to Face π-πStacking : A Surprising Preference Induced by the Isocyano Group in the Self-Assembled Dimer of Phenyl Isocyanide

Bloino J.
;
Gou Q.
;
Caminati W.;
2022

Abstract

Phenyl isocyanide has been chosen as a prototype to probe the π-πinteraction modulated by the -NC group, which has a chameleonic nature with two main resonance forms showing a triple bond and being carbenoid. The rotational spectroscopic investigation complemented with theoretical analyses indicates that the phenyl isocyanide dimer has a scissor-like configuration controlled by dispersive forces along with the formation of π-πstacking. This is the first rotational spectroscopic evidence, to the best of our knowledge, that the mono-substitution by an -NC group on benzene can activate the meta position in forming noncovalent interactions. This work also provides experimental evidence on the importance of substituent effects in modulating π-πstacked structures, as well as practical proof of a biased interaction behavior of isocyanide-substituted aromatic molecules.
2022
Settore CHIM/02 - Chimica Fisica
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11384/128973
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