New coordination polymers of the formula [M(btre)(2)(NCS)(2)] (btre = 1,2-bis(1,2,4-triazol-4-yl)ethane; M(II) = Fe, Co) have been synthesized, and their crystal structures have been determined at 293 K by X-ray analysis. The Fe(II) compound (C(7)H(8)FeN(7)S(2)) crystallizes in the monoclinic space group P2(1)/n, a = 12.439(5) A, b = 8.941(2) A, c = 9.321(3) A, beta = 90.88(2) degrees , V = 1036.6(6) A(3), Z = 2, 3791 reflections [I > 3sigma(I)], R(F) = 0.036, wR2 = 0.123. The Co(II) compound is isostructural to the Fe(II) compound. The crystal structure consists of a 2D sheet in which the metal ions are linked by bis monodentate (N1, N1') 1,2,4-triazole ligands. The structure is stabilized by pi-bond interactions between two adjacent sheets and by S...S interactions. Temperature-dependent SQUID, (57)Fe Mössbauer, and X-ray diffraction measurements indicate that [Fe(btre)(2)(NCS)(2)] retains a HS ground state upon cooling from 293 K down to 8 K. The surprising absence of spin-crossover behavior for this Fe(II)-1,2,4-triazole polymeric coordination compound that has been confirmed by pressure experiments up to approximately 12 kbar and by light irradiation experiments at 10 K is discussed on the basis of its structural features. Insight into the origin of the cooperative effects of the spin transition in [Fe(btr)(2)(NCS)(2)].H(2)O (btr = 4,4'-bis-1,2,4-triazole) is also given thanks to a re-evaluation of its distortion parameters in the high- and low-spin states.

[Fe(NH2trz)3]SnF6n x H2O (NH(2)trz=4-amino-1,2,4-triazole; n=1 (1), n=0.5 (2)) are new 1D spin-crossover coordination polymers. Compound 2 exhibits an incomplete spin transition centred at around 210 K with a thermal hysteresis loop approximately 16 K wide. The spin transition of 2 was detected by the Mössbauer resonance of the 119Sn atom in the SnF6 (2-) anion primarily on the basis of the evolution of its local distortion. Rapid-cooling 57Fe Mössbauer and superconducting quantum interference device experiments allow dramatic widening of the hysteresis width of 2 from 16 K up to 82 K and also shift the spin-transition curve into the room temperature region. This unusual behaviour of quenched samples on warming is attributed to activation of the molecular motion of the anions from a frozen distorted form towards a regular form at temperatures well above approximately 210 K. Potential applications of this new family of materials are discussed.