Spin-Crossover Dendrimers: Generation Number-Dependent Cooperativity for Thermal Spin Transition

Poly(benzyl ether) dendrons having a focal triazole unit (Gntrz: trz = triazole; n = generation number = 0-2) were found to react with (MeSO(3))(2)Fe to form dendritic coordination polymers ([Fe(Gntrz)(3)](MeSO(3))(2).2H(2)O) that undergo the thermal spin transition. When the generation number of the dendritic unit was larger (n = 0 --> 1 --> 2), the average degree of polymerization (D(p) = 20 --> 10 --> 3) and spin-crossover temperature (T(c) = 335 --> 315 --> 300 K) of the resulting polymer were lower. However, the abruptness of the spin transition was not monotonically dependent on the generation number; (G1trz)Fe exhibited an abrupt spin transition with a temperature width of only 10 K, while the smallest and largest members of the (Gntrz)Fe family both displayed a rather broad spin-transition temperature width (30 (n = 0) and 50 K (n = 2)). X-ray diffraction and calorimetric analyses indicated the presence of a discotic columnar core-shell assembly with a crystal lattice best occupied by a C(3)(v)() symmetric array of medium-sized (G1trz)Fe.