Paramagnetic transition metal complexes with a redox-active ligand: Mhfac2EDO-EDT-TTF-pyn; M CuII, n 1, 2; M MnII, n 2Electronic supplementary information (ESI) available: detailed X-ray structural data including crystallographic parameters, atomic coordinates, bond distances and angles, anisotropic thermal parameters, and H atom coordinates for L1, 2, 3and 4as CIF file; charts of cyclic voltametry for L1, 2, and 3; UV-Vis-IR spectra for L1, 2, 3; χT vs. T plots for 2and 3; ESR spectra for 2and 3. See http://dx.doi.org/10.1039/b507163a

Synthesis, crystal structures, electrochemical and physical properties of the new ligand, EDO-EDT-TTF-py L1 4,5-ethylenedioxy-4′,5′-4-pyridylethylenedithiotetrathiafulvalene, and the paramagnetic transition metal coordination complexes, Mhfac2EDO-EDT-TTF-py2; M Cuii2, Mnii3, and Cuiihfac2EDO-EDT-TTF-py 4 are reported where hfac hexafluoroacetylacetonato. Crystal data: L1 triclinic system, space group P1, a 8.40603, b 10.50933, c 11.53185 , α 64.7582, β 86.9232, γ 72.4442°, V 875.226 3, Z 2, 2and 3are isostructural data for 3are given in brackets, triclinic system, space group P1, a 7.10854 7.10139, b 11.12107 11.1112, c 16.362811 16.3463 , α 91.6822 91.6626, β 91.0143 91.0367, γ 93.5473° 93.6516°, V 1290.31 31286.33 3, Z 1, 4 triclinic system, space group P1, a 9.29371, b 15.18972, c 24.31746 , α 92.4611, β 93.0481, γ 105.4911°, V 3297.61 3, Z 4.CCDC reference numbers 275856–275859. See http://dx.doi.org/10.1039/b507163afor crystallographic data in CIF or other electronic format.In the compounds 2, 3and 4, the ligand L1is coordinated to the transition metals through the nitrogen atom of the pyridine group. In the crystal, the organic and inorganic layers are segregated. The arrangement of the organic layers is similar to the well known βphase in BEDT-TTF bisethylenedithiotetrathiafulvalene charge transfer complexes, showing that the crystal packing is mainly governed by π–π stacking of the organic molecules. L1is a TTF derivative and shows the electron donating ability with oxidation potential E1½ 0.52 V versusSCE in benzonitrile. The same oxidation potentials were observed for complexes 2and 3, indicating the negligible interactions between the ligands and the metals in solution.