羧酸功能化自旋交叉铁(II)网格用于可调切换和混合电极制备。
Carboxylic Acid Functionalized Spin-Crossover Iron(II) Grids for Tunable Switching and Hybrid Electrode Fabrication.
机构信息
Graduate School of Pure and Applied Sciences , University of Tsukuba , Tennodai 1-1-1 , Tsukuba , Ibaraki 305-8571 , Japan.
Photon Factory and Condensed Matter Research Center, Institute of Materials Structure Science , High Energy Accelerator Research Organization , Oho 1-1 , Tsukuba , Ibaraki 305-0801 , Japan.
出版信息
Inorg Chem. 2018 Nov 19;57(22):14013-14017. doi: 10.1021/acs.inorgchem.8b01856. Epub 2018 Oct 31.
Two carboxyl-substituted iron(II) grids, one protonated, Fe(HL)·4MeCN·AcOEt (1), and the other deprotonated, [Fe(L)]·DMSO·EtOH (2), where HL = 4-{4,5-bis[6-(3,5-dimethylpyrazol-1-yl)pyrid-2-yl]-1 H-imidazol-2-yl}benzoic acid, were synthesized. Single-crystal X-ray structure analyses reveal that both complexes have a tetranuclear [2 × 2] grid structure. 1 formed one-dimensional chains through intermolecular hydrogen bonds between the carboxylic acid units of neighboring grids, while 2 formed two-dimensional layers stabilized by π-π-stacking interactions. 1 showed spin transition between the 3HS-1LS and 1.5HS-2.5LS states around 200 K, while 2 showed spin-crossover between the 4LS and 2LS-2HS states above 300 K. A modified indium-tin oxide (ITO) electrode was fabricated by soaking the ITO in a solution of 1. The resultant electrode showed reversible redox waves attributed to the original redox processes of iron(II)/iron(III).
两个羧酸取代的铁(II)网格，一个质子化的Fe(HL)·4MeCN·AcOEt(1)，另一个去质子化的[Fe(L)]·DMSO·EtOH(2)，其中 HL = 4-{4,5-双[6-(3,5-二甲基吡唑-1-基)吡啶-2-基]-1 H-咪唑-2-基}苯甲酸，被合成。单晶 X 射线结构分析表明，这两个配合物都具有四核[2×2]网格结构。1 通过相邻网格的羧酸单元之间的分子间氢键形成一维链，而 2 通过π-π堆积相互作用形成二维层。1 在 200 K 左右表现出 3HS-1LS 和 1.5HS-2.5LS 态之间的自旋跃迁，而 2 在 300 K 以上表现出 4LS 和 2LS-2HS 态之间的自旋交叉。通过将 ITO 浸泡在 1 的溶液中制备了改性的铟锡氧化物(ITO)电极。所得电极显示出归因于铁(II)/铁(III)原始氧化还原过程的可逆氧化还原波。
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