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Intermolecular π ‐dimer of oxoverdazyl radicals with long‐distance multicenter (2e/8c) bonding via nitrogen atoms
Author(s) -
Rosokha Sergiy V.,
Zhang Jing,
Lu Jianjiang,
Kochi Jay K.
Publication year - 2010
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1612
Subject(s) - chemistry , dimer , intermolecular force , van der waals force , crystallography , radical , supramolecular chemistry , atomic orbital , monomer , molecule , electron , crystal structure , organic chemistry , polymer , physics , quantum mechanics
The 1,5‐dimethyl‐6‐oxoverdazyl radical's solid‐state structure shows distinct π ‐dimeric units with close interplanar separations (3.10 Å) between the head‐over‐tail cofacial moieties and several interatomic contacts shorter than the sums of the van der Waals radii. Evaluations of the frontier orbitals of monomeric oxoverdazyl and its π ‐dimer reveal that interaction of the radical SOMOs (concentrated on the nitrogen atoms) leads to the formation of the supramolecular orbital involving four equivalent bonding (N…N) segments between two oxoverdazyl moieties. As such, this π ‐dimer represents a rare example of nitrogen‐based multicenter (2e/8c) long‐distance bonding and emphasizes the universal character of this phenomenon in organic (ion‐) radical systems. Copyright © 2009 John Wiley & Sons, Ltd.