Charge-transfer phase transition and zero thermal expansion in caesium manganese hexacyanoferrates

A series of caesium manganese hexacyanoferrates is prepared; Cs(I)(1.78)Mn(II)Fe(II)(CN)6]0.78Fe(III)(CN)6](0.22) (1), Cs(I)(1.57)Mn(II)Fe(II)(CN)6]0.57Fe(III)(CN)6](0.43) (2), Cs(I)(1.51)Mn(II)Fe(II)(CN)6]0.51Fe(III)(CN)6](0.49) (3), and Cs(I)(0.94)Mn(II)Fe(II)(CN)6]0.21Fe(III)(CN)6](0.70).0.8H2O (4). 1-3 show charge-transfer phase transitions between the high-temperature (HT) and low-temperature (LT) phases with transition temperatures (T(1/2 downward arrow), T(1/2 upward arrow)) of (207 K, 225 K) (1), (190 K, 231 K) (2), and (175 K, 233 K) (3) at a cooling and warming rates of 0.5 K min(-1). Variable temperature IR spectra indicate that the valence states of the LT phases of 1-3 are Cs(I)(1.78)Mn(II)(0.78)Mn(III)(0.22)Fe(II)(CN)6], Cs(I)(1.57)Mn(II)(0.57)Mn(III)(0.43)Fe(II)(CN)6], and Cs(I)(1.51)Mn(II)(0.51)Mn(III)(0.49) Fe(II)(CN)6], respectively. The XRD measurements for 1-3 show that crystal structures of the HT and LT phases are cubic structures (Fm3combining macron]m), but the lattice constants decrease from the HT phase to the LT phase; a = 10.5446(17) --> 10.4280(7) A (1), 10.5589(17) --> 10.3421(24) A (2), and 10.5627(11) --> 10.3268(23) A (3). The magnetization vs. temperature curves and the magnetization vs. external magnetic field curves show that the LT phases are ferromagnetic with Curie temperatures of 4.3 (1), 5.0 (2), and 5.6 K (3). At a cooling rate of -0.5 K min(-1), 4 does not show the charge-transfer phase transition, but does show a behavior of zero thermal expansion with a thermal expansivity of +0.2 x 10(-6) K(-1) throughout the temperature range 300 and 20 K.