Achieving white light emission and increased magnetic anisotropy by transition metal substitution in functional materials based on dinuclear DyIII(4-pyridone)[MIII(CN)6]3− (M = Co, Rh) molecules
Achieving white light emission and increased magnetic anisotropy by transition metal substitution in functional materials based on dinuclear DyIII(4-pyridone)[MIII(CN)6]3− (M = Co, Rh) molecules
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DOI：
10.1039/c7tc03963h
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发表时间：
2018-01
影响因子：
6.4
通讯作者：
Junhao Wang;S. Chorazy;K. Nakabayashi;B. Sieklucka;S. Ohkoshi
中科院分区：
文献类型：
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作者：
Junhao Wang;S. Chorazy;K. Nakabayashi;B. Sieklucka;S. Ohkoshi
构建块方法导致了两个独特的双功能磁致发光分子材料的构建，{[DyIII(4-吡啶酮)4(H2O)2][MIII(CN)6]}·nH2O(M=Co，n=2，1；M=Rh，n=4，2)，结合氰桥联的双核分子{DyIIICoIII}(1)或{DyIIIRhIII}(2)，在具有吸引力的非中心对称Cmc21空间群的超分子网络中结晶。这两种化合物都表现出颜色可调的光致发光和磁化强度慢弛豫的双重物理性质。在激发波长可调的情况下，1表现出从黄色到蓝色的多色光致发光，而2在室温下的336 nm激发下还表现出近白光发射。1和2表现出4f金属中心的强磁各向异性，表现为单分子磁体行为，其各向异性势垒分别为187(6)K和214(4)K。我们已经证明和讨论了在{[DyIII(4-吡啶酮)4(H2O)2][MIII(CN)6]}·2H2O晶体材料中用较重的[Rh III(CN)6]3−取代[CoIII(CN)6]3−是获得由增强磁各向异性的单分子磁体组成的白光固态矩阵的有效途径。这种非同寻常的光致发光分子基磁体可以成为未来应用于双功能光学和磁性器件的良好前提。
A building block approach has led to the construction of two unique bifunctional magneto-luminescent molecular materials, {[DyIII(4-pyridone)4(H2O)2][MIII(CN)6]}·nH2O (M = Co, n = 2, 1; M = Rh, n = 4, 2), incorporating the cyanido-bridged dinuclear {DyIIICoIII} (1) or {DyIIIRhIII} (2) molecules, that crystallize within the supramolecular network in the attractive non-centrosymmetric Cmc21 space group. Both compounds reveal dual physical properties of colour-tunable photoluminescence and slow relaxation of magnetization. While 1 exhibits multi-coloured photoluminescence ranging from yellow to blue, tuned by the excitation wavelength, 2 additionally reveals nearly white light emission under 336 nm excitation at room temperature. 1 and 2 show 4f-metal-centered strong magnetic anisotropy presenting Single-Molecule Magnet (SMM) behaviour with the large anisotropic energy barriers of 187(6) K for 1, and 214(4) K for 2. We have shown and discussed that the replacement of [CoIII(CN)6]3− by the heavier [RhIII(CN)6]3− analogue in {[DyIII(4-pyridone)4(H2O)2][MIII(CN)6]}·2H2O crystalline materials is an efficient route towards white light emissive solid state matrices composed of Single-Molecule Magnets with enhanced magnetic anisotropy. Such extraordinary photoluminescent molecule-based magnets can become good prerequisites for future application in bifunctional optical and magnetic devices.