The aqueous reaction of Mn(II) and NaCN leads to the isolation of the 3-D Prussian blue analogue (PBA) Na(2)Mn[Mn(CN)(6)]·2H(2)O (1·H(2)O), which under careful dehydration forms 1. 1·H(2)O is monoclinic [P2(1)/n, a = 10.66744(32) Å, b = 7.60223(23) Å, c = 7.40713(22) Å, β = 92.4379(28)°], while 1 is rhombohedral [R ̅3, a = 6.6166(2) Å, c = 19.2585(6) Å], and both structures are atypical for PBAs, which are typically face centered cubic. Most notably, the average ∠Mn-N-C angles are 165.3(3)° and 142.4(4)° for 1·H(2)O and 1, respectively, which are significantly reduced from linearity. This is attributed to the ionic nature of high-spin Mn(II) accommodating a reduced ∠Mn-N-C to minimize void space. Both 1 and 1·H(2)O magnetically order as ferrimagnets below their ordering temperature, T(c), of 58 and 30 K, respectively, as determined from the average of several independent methods. 1 and 1·H(2)O are hard magnets with 5 K coercive fields of 15,300 and 850 Oe, and remnant magnetizations of 9075 and 102 emu·Oe/mol, respectively. These data along with previous T(c)'s reported for related materials reveal that T(c) increases as the ∠Mn-N-C deviates further from linearity. Hence, the bent cyanide bridges play a crucial role in the superexchange mechanism by increasing the coupling via shorter Mn(II)···Mn(II) separations, and perhaps an enhanced overlap.

The reaction of Mn(II) and KCN in aqueous and non-aqueous media leads to the isolation of three-dimensional (3-D) Prussian blue analogues, K(2)Mn[Mn(CN)(6)] (1a-d, 1e, respectively). Use of RbCN forms Rb(2)Mn[Mn(CN)(6)] (2). 1 and 2 are isomorphic {monoclinic, P2(1)/n: 1 [a = 10.1786(1) A, b = 7.4124(1) A, c = 6.9758(1) A, beta = 90.206(1)(o)]; 2 [a = 10.4101(1) A, b = 7.4492(1) A, c = 7.2132(1) A, beta = 90.072(1)(o)]}, with a small monoclinic distortion from the face centered cubic (fcc) structure that is typical of Prussian blue structured materials that was previously reported for K(2)Mn[Mn(CN)(6)]. Most notably the average Mn-N-C angles are 148.8 degrees and 153.3 degrees for 1 and 2, respectively, which are significantly reduced from linearity. This is attributed to the ionic nature of high spin Mn(II) accommodating a reduced M-CN-M' angle and minimizing void space. Compounds 1a,b have a sharp, strong nu(OH) band at 3628 cm(-1), while 1e lacks a nu(OH) absorption. The nu(OH) absorption in 1a,b is attributed to surface water, as use of D(2)O shifts the nu(OH) absorption to 2677 cm(-1), and that 1a-e are isostructural. Also, fcc Prussian blue-structured Cs(2)Mn[Mn(CN)(6)] (3) has been structurally [Fm3m: a = 10.6061(1) A] and magnetically characterized. The magnetic ordering temperature, T(c), increases as K(+) (41 K) > Rb(+) (34.6 K) > Cs(+) (21 K) for A(2)Mn[Mn(CN)(6)] in accord with the increasing deviation for linearity of the Mn-N-C linkages [148.8 (K(+)) > 153.3 (Rb(+)) > 180 degrees (Cs(+))], decreasing Mn(II)...Mn(II) separations [5.09 (K(+)) < 5.19 (Rb(+)) < 5.30 A (Cs(+))], and decreasing size of the cation (increasing electrostatic interactions). Hence, the bent cyanide bridges play a crucial role in the superexchange mechanism by increasing the coupling via shorter Mn(II)...Mn(II) separations, and perhaps enhanced overlap. In addition, the temperature dependent magnetic behavior of K(4)[Mn(II)(CN)(6)].3H(2)O is reported.

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The reaction of Mn(II) and [NEt(4)]CN leads to the isolation of solvated [NEt(4)]Mn(3)(CN)(7) (1) and [NEt(4)](2) Mn(3)(CN)(8) (2), which have hexagonal unit cells [1: R3m, a = 8.0738(1), c = 29.086(1) Å; 2: P3m1, a = 7.9992(3), c = 14.014(1) Å] rather than the face centered cubic lattice that is typical of Prussian blue structured materials. The formula units of both 1 and 2 are composed of one low- and two high-spin Mn(II) ions. Each low-spin, octahedral [Mn(II)(CN)(6)](4-) bonds to six high-spin tetrahedral Mn(II) ions through the N atoms, and each of the tetrahedral Mn(II) ions are bound to three low-spin octahedral [Mn(II)(CN)(6)](4-) moieties. For 2, the fourth cyanide on the tetrahedral Mn(II) site is C bound and is terminal. In contrast, it is orientationally disordered and bridges two tetrahedral Mn(II) centers for 1 forming an extended 3D network structure. The layers of octahedra are separated by 14.01 Å (c axis) for 2, and 9.70 Å (c/3) for 1. The [NEt(4)](+) cations and solvent are disordered and reside between the layers. Both 1 and 2 possess antiferromagnetic superexchange coupling between each low-spin (S = 1/2) octahedral Mn(II) site and two high-spin (S = 5/2) tetrahedral Mn(II) sites within a layer. Analogue 2 orders as a ferrimagnet at 27(±1) K with a coercive field and remanent magnetization of 1140 Oe and 22,800 emuOe mol(-1), respectively, and the magnetization approaches saturation of 49,800 emuOe mol(-1) at 90,000 Oe. In contrast, the bonding via bridging cyanides between the ferrimagnetic layers leads to antiferromagnetic coupling, and 3D structured 1 has a different magnetic behavior to 2. Thus, 1 is a Prussian blue analogue with an antiferromagnetic ground state [T(c) = 27 K from d(χT)/dT].

Thermolysis of either the 3-D, bridged-layered [NEt(4)]Mn(II)(3)(CN)(7) or 2-D, layered [NEt(4)](2)Mn(II)(3)(CN)(8) forms Mn(II)(CN)(2). Rietveld analysis of the high-resolution synchrotron powder X-ray diffraction data determined that Mn(II)(CN)(2) is cubic [a = 6.1488(3) Å] (space group = Pn3m) consisting of two independent, interpenetrating networks having the topology of the diamond lattice. Each tetrahedrally coordinated Mn(II) is bonded to four orientationally disordered cyanide ligands. Mn(II)(CN)(2) magnetically orders as an antiferromagnet with a T(c) = 73 K determined from the peak in d(χT)/dT. Exchange coupling estimated via the mean field Heisenberg model from the transition temperature (J/k(B) = -4.4 K) and low temperature magnetic susceptibility of the ordered phase (J/k(B) = -7.2 K) indicate that Mn(II)(CN)(2) experiences weak antiferromagnetic coupling. The discrepancy between those estimates is presumably due to local anisotropy at the Mn(II) sites arising from the CN orientational disorder or interactions between the interpenetrating lattices.