Structural, magnetic, electrical and optical characterization of systems built from [M([9]aneN3)2]2+ (M = CuII or NiII) and TCNQ or TCNQF4

Three different supramolecular architectures corresponding to [M([9]aneN(3))(2)](TCNQ)(2), (M = Ni-II 1 or Cu-II 2, [9]aneN(3) = 1,4,7-triazacyclononane, TCNQ = 7,7,8,8-tetracyanoquinodimethane), [Cu([9]aneN(3))(2)](TCNQ)(3) and [Cu([9]aneN(3))(2)](TCNQF(4))(2), 4 (TCNQF(4) = 2,3,5,6-tetrafluoro-7,7,8,8,-tetracyanoquinodimethane), have been prepared and crystallographically characterized: 1, triclinic, P (1) over bar, a = 8.6488(9), b = 8.919(3), c = 11.316(2) Angstrom, alpha = 82.06(2), beta = 74.331(10), gamma = 85.71(2)degrees, Z = 1; 2, triclinic, P (1) over bar, a = 8.6806(11), b = 8.915(5), c = 11.348(2) Angstrom, alpha = 82.03(3), beta = 74.109(14), gamma = 84.95(2)degrees, Z = 1; 3, tridinic, P (1) over bar, a = 8.350(2), b = 9.884(4), c = 14.369(4) Angstrom, alpha = 74.10(2), beta = 89.01(2), gamma = 69.11(2)degrees, Z = 1; 4, triclinic, P (1) over bar, a = 15.416(5), b = 161146(4), c = 16.441(4) Angstrom, alpha = 77.15(2), beta = 78.04(3), gamma = 85.43(3)degrees, Z = 2. Compounds 1 and 2 are formed by dimeric (TCNQ)(2)(2) - units and 4 by three different dimeric (TCNQF(4))(2)(2-) units. Compound 3 is formed by isolated [Cu([9]aneN(3))(2)](2+) groups and trimeric (TCNQ)(3)(2-) units. The electrical, optical and magnetic properties of the four new compounds have been interpreted on the basis of their supramolecular architectures.