A thiophenophane ligand with endodentate coordination

A new thiophenophane has been synthesized which has encapsulated a Cu(I) io n. Endodentate coordination has been possible by a -CH2CH2- spacer between the thiophene and sulfur. Geometrical and electronic characteristics are ve ry similar to [Cu(18S6)](+). The crystal structure of [Cu(4.7,10,13,19-pent athiabicyclo[14.2.11-nonadeca-1(18),16-diene)](2)[CuCl4].H2O represents the first example of a Cu(I) complex whose charge is compensated by a Cu(II) s pecies. Although no interaction exists between the cationic and anionic cen ters in the solid, as evidenced by X-ray analysis, an interaction indeed ta kes place in solution. It has been proven that the electrochemical properti es in solution are not the sum of the individual contributions. but they ar e required to be the result of an interaction between the cationic and anio nic complexes. most probably generating new bonds. (C) 2001 Elsevier Scienc e Ltd. All rights reserved.