The solid charge-transfer complexes formed in the reaction of the electron donor 1,4,7-trimethyl-1,4,7-triazacyclononane (TMTACN) with the acceptors iodine, tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) have been isolated. These were characterized through electronic and infrared spectra as well as thermal and elemental analysis. The results show that the formed solid CT-complexes have the formulas [(TMTACN)I]I(3), [(TMTACN)(TCNE)(5)] and [(TMTACN)(TCNQ)(3)] in full agreement with the known reaction stoichiometries in solution. The chloranil Cr-solid complex cannot be isolated in pure form. (C) 2008 Elsevier B.V. All rights reserved.