Spin-gap formation and thermal structural studies in reduced hybrid layered vanadates.

Reduced layered M(C4H4N2)V4O10 ((I, M = Co; II, M = Ni; III, M = Zn); C4H4N2 = pyrazine, pyz) hybrid solids were synthesized via hydrothermal reactions at 200-230 degrees C, and their structures determined by single-crystal X-ray diffraction (Cmcm, No. 63, Z = 4; a = 14.311(2), 14.2372(4), 14.425(1) A; b = 6.997(1), 6.9008(2), 6.9702(6) A; and c = 11.4990(8), 11.5102(3), 11.479(1) A; for I, II, and III, respectively). All three solids are isostructural and contain V4O102- layers condensed from edge- and corner-shared VO5 square pyramids. A single symmetry-unique V atom is reduced by 1/2 electron (on average) and bonds via its apical oxygen atom to interlayer Mpyz2+ chains. Magnetic susceptibility measurements show a strong temperature dependence and a Curie constant that is consistent with two randomly localized spins per V4O10(2-) formula for III. Further, the unusual discovery of a remarkably well-defined transition to a singlet ground state, as well as formation of a spin gap, is found for III at 22(1) K. The temperature-dependent electrical conductivities show apparent activation energies of 0.36 (I), 0.46 (II), and 0.59 eV (III). During heating cycles in flowing N2, the samples exhibit weight losses corresponding to the removal of predominantly pyrazine, pyrazine fragments, and CO2 via reaction of pyrazine with the vanadate layer. The complete removal of pyrazine without loss of crystallinity is found for well-ground samples of I and III. The SEM images of I and II after heating at 400-500 degrees C show relatively intact crystals, but at 600 degrees C further structural collapse results in the formation of macropores at the surfaces.