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

Abstract

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 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, P1, a=8.6488(9), b=8.919(3), c=11.316(2) Å, α=82.06(2), β=74.331(10), γ=85.71(2)°, Z=1; 2, triclinic, P1, a=8.6806(11), b=8.915(5), c=11.348(2) Å, α=82.03(3), β=74.109(14), γ=84.95(2)°, Z=1; 3, triclinic, P1, a=8.350(2), b=9.884(4), c=14.369(4) Å, α=74.10(2), β=89.01(2), γ=69.11(2)°, Z=1; 4, triclinic, P1, a=15.476(5), b=16.146(4), c=16.441(4) Å, α=77.15(2), β=78.04(3), γ=85.43(3)°, 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.