A new type of polytopic coordination compound: The synthesis and NMR studies of the first hybrid thiacalix[4]arenoclathrochelates

作者：Solovieva Svetlana E; Tyuftin Andrey A; Muravev Anton A; Gruner Margit; Habicher Wolf; Korobko Sergey V; Antipin Igor S; Konovalov Alexander I; Bubnov Yurii N; Voloshin Yan Z^*

来源：Polyhedron, 2013, 50(1): 90-100.

DOI：10.1016/j.poly.2012.10.028

• Calixarenes
• Clathrochelates
• Iron complexes
• Macrocyclic compounds
• Ligand reactivity
• NMR spectroscopy

Nucleophilic substitution of the reactive chlorine atoms of iron(II) dichloroclathrochelate with thiol-terminated thiacalix[4]arene nucleophiles in the 1,3-alternate conformation afforded the first hybrid calixarenoclathrochelates with both ring-closed and ring-opened structures. The 1:1, 1:2 and 1:3 condensations of tetra-O-substituted thiacalix[4]arenes with thiol-terminated spacer substituents at the lower rim of the macrocyclic platform were performed. These thiol-terminated calixarene precursors were obtained from their O-omega-bromoalkyl precursors in the 13-alternate conformation, which are the products of alkylation of the parent thiacalix[4]arene with a series of homological alpha-omega-dibromoalkanes. The complexes obtained were characterized using elemental analysis, MALDI-TOF and ESI mass spectrometry, IR, H-1, F-19, B-11 and C-13{H-1} NMR spectra; their molecular structures in solution were thoroughly studied by one- and two-dimensional NMR spectroscopy as well as by molecular mechanics calculations. The formation of the thiacalix[4]arenoclathrochelates depends on the length of their ribbed spacer substituents in the chelate alpha-dioximate fragments of the cage frameworks; those with four bridging methylene groups seem to be optimal for the synthesis of the ring-closed hybrid molecules with two metal-encapsulating macrobicycles.

• 出版日期2013-2-13