Photoinduced magnetization of the cyano-bridged 3d-4f heterobimetallic assembly Nd(DMF)4(H2O)3(mu-CN)Fe(CN)5.H2O (1) (DMF = N,N-dimethylformamide) is described in this paper. The chiMT values are enhanced by about 45% after UV light illumination in the temperature range of 5-50 K. We propose that UV light illumination induces a structural distortion in 1. This small structural change is propagated by molecular interactions in the inorganic network. Furthermore, the cooperativity resulting from the molecular interaction functions to increase the activation energy of the relaxation processes, which makes observation of the photoexcited state possible. The flexible network structure through the hydrogen bonds in 1 plays an essential role for the photoinduced phenomenon. This finding may open up a new domain for developing the molecule-based magnetic materials.

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Preparations, crystal structures, and spectral and magnetic properties of two new chiral one-dimensional cyano-bridged coordination polymers, [Cu(II)L2]M(II)(CN)].2H2O (M(II) = Ni(II) (1) and Pt(II) (2), L = trans-cyclohexane-(1R,2R)-diamine) have been presented. Complex 1 crystallizes in the monoclinic P2(1) space group with a = 9.864(4) A, b = 15.393(8) A, c = 7.995(4) A, beta = 110.32(3) degrees , V = 1138.4(10) A3, and Z = 2, while 2 crystallizes in the monoclinic P2(1) space group with a = 9.899(3) A, b = 15.541(4) A, c = 8.102(2) A, beta = 111.02(2) degrees , V = 1163.6(5) A3, and Z = 2. The unique zigzag cyano-bridged chains along the crystallographic b axis consist of alternate chiral [CuL(2)]2+ cations and square-planar [M(CN)4]2- anions. One side of the axial Cu-N(triple bond C) bond distances are 2.324(6) and 2.34(1) A with Cu-N[triple bond]C angles of 137.8(6) degrees and 138.2(9) degrees for 1 and 2, respectively. On the other hand, the opposite side of the axial Cu-N(triple bond C) bond distances are 3.120(8) and 3.09(1) A with significantly large bent Cu-N[triple bond]C angles of 97.9(5) degrees and 96.8(7) degrees for 1 and 2, respectively. The novel axial bonding features of extremely long semi-coordination Cu-N bonds are attributed to coexistence of pseudo-Jahn-Teller elongation and electrostatic interaction in the unique zigzag cyano-bridged chains. The characteristic bonding features with overlap between small 3d (Ni(II)) or large 5d (Pt(II)) and 3d (Cu(II)) orbitals results in larger shifts in XPS peaks of not only Cu2p(1/2) and Cu2p(3/2) but also Ni2p(1/2) and Ni2p(3/2) for 1 than those of 2, which is also consistent with weak antiferromagnetic interactions with Weiss constants of -5.31 and -5.94 K for 1 and 2, respectively. The d-d, pi-pi*, and CT bands in the electronic, CD, and MCD spectra for 1 and 2 in the solid state at room temperature are discussed from the viewpoint of magneto-optical properties.

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Photofunctional magnetic vesicles of spiropyran (SP1822) that contain iron oxide particles, which exhibit super-paramagnetic properties at room temperature, were prepared. Photoinduced aggregation of the vesicles was observed by UV illumination. As a result, we were able to increase the magnetization value by photoillumination at room temperature.