文摘
Incorporation of urea molecules into the magnetic system MnII-[NbIV(CN)8] results in formation of two magnetic polymorphs {[MnII(H2O)(urea)2]2[NbIV(CN)8]}n chiral 伪 and centric 尾 crystallizing in space groups P41 and P1̅, respectively. Both polymorphs exhibit extremely similar structures and are soft ferrimagnets with critical temperatures of 43 and 42 K, respectively. The presence of coordinated urea in the noncentrosymmetric 伪 produces NLO functionality, second harmonic generation (SHG), whereas centric 尾 is just another molecular magnet. As a result of interaction of both functionalities below magnetic ordering temperature, the magnetization-induced SHG (MSHG) is observed for polymorph 伪. The observed MSHG/SHG signal ratio was the largest among molecule-based noncentrosymmetric magnets. The presence of urea molecules in both polymorphs gives also rise to their interesting topotactic reactivity. Both polymorphs can be easily transformed into a new entity {[MnII(H2O)]2[NbIV(CN)8]路2.5MeOH}n 2b with significant shift of critical temperature Tc to 70 K. Subsequent hydration of 2b leads to {[MnII(H2O)2]2[NbIV(CN)8]路4H2O}n 3 with Tc of 47 K.