Nonconventional Supramolecular Self-Assemblies of Zinc(II)-Salphen Building Blocks

作者：Groizard Thomas; Kahlal Samia; Dorcet Vincent; Roisnel Thierry; Bruneau Christian; Halet Jean Francois^*; Gramage Doria Rafael^*

来源：European Journal of Inorganic Chemistry, 2016, 2016(32): 5143-5151.

DOI：10.1002/ejic.201600866

• Zinc
• Schiff bases
• Hydrogen bonds
• Self-assembly
• Supramolecular 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<bold>oxygen interactions</bold>, that is, the O<bold>O distances are much shorter than twice the van der Waals radius of an oxygen atom</bold>. 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 H-1 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<bold>oxygen interactions</bold>. 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.

• 出版日期2016-11