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Nonconventional Supramolecular Self‐Assemblies of Zinc(II)–Salphen Building Blocks
Author(s) -
Groizard Thomas,
Kahlal Samia,
Dorcet Vincent,
Roisnel Thierry,
Bruneau Christian,
Halet JeanFrançois,
GramageDoria Rafael
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201600866
Subject(s) - supramolecular chemistry , chemistry , hydrogen bond , molecule , natural bond orbital , intermolecular force , zinc , van der waals force , methanol , crystallography , isopropyl alcohol , photochemistry , organic chemistry
In the presence of methanol (or ethanol) and acetone molecules, a zinc(II)–salphen [salphen = N , N′ ‐bis(3,5‐di‐ tert ‐butylsalicylidene)‐1,2‐phenylenediamine] building block gives rise to discrete supramolecular dimers involving both intermolecular hydrogen bonding and unique oxygen ··· oxygen interactions, that is, the O ··· O distances are much shorter than twice the van der Waals radius of an oxygen atom. These types of unexpected self‐assembled structures have been studied thoroughly through a combination of experimental (X‐ray diffraction, IR spectroscopy, solid‐state UV/Vis absorption spectroscopy, and elemental analysis) and theoretical [DFT and natural bond orbital (NBO) calculations] studies. However, their solution structures involve different equilibrating species according to variable‐temperature 1 H NMR spectroscopy. The replacement of the methanol (or ethanol) and acetone molecules by bulkier isopropyl alcohol and 2‐butanone, respectively, leads to structures with no oxygen ··· oxygen interactions. An infinite supramolecular polymeric chain stabilized by hydrogen bonding is obtained in the presence of water. The present study highlights that even well‐explored molecules can provide extremely interesting possibilities for metallo‐supramolecular chemistry.