Convenient Preparation of Lanthanide Aryloxides from Lanthanide Nitrate Polyether Complexes and the Crystal Structure of [La(OC6H3Me2-2,6)3(MeO(CH2CH2O)4Me)]
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Abstract:
Anhydrous lanthanide chlorides, which can be tedious to prepare, are the usual starting materials for the synthesis of lanthanide aryloxides. Here we report on the use of easily prepared lanthanide nitrate polyether complexes in the synthesis of lanthanide 2,6-dimethylphenoxides. The crystal structure of 8-coordinate [La(OC6H3Me2-2,6)3(tetraglyme)] is reported.Keywords:
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Isostructural lanthanide metal–organic frameworks (MOFs) are synthesized through the spontaneous self-assembly of H3BTPCA (1,1′,1″-(benzene-1,3,5-triyl)tripiperidine-4-carboxylic acid) ligands and lanthanide ions (we term these MOFs Ln-BTPCA, Ln = La3+, Tb3+, Sm3+, etc.). Prompted by the observation that the different lanthanide ions have identical coordination environment in these MOFs, we explored and succeeded in the preparation of mixed-lanthanide analogues of the single-lanthanide MOFs by way of in situ doping using a mixture of lanthanide salts. With careful adjustment of the relative concentration of the lanthanide ions, the color of the luminescence can be modulated, and white light-emission can indeed be achieved. The mechanisms possibly responsible for the observed photophysical properties of these mixed-lanthanide MOFs are also discussed.
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三价的 lanthanide 离子显示迷人的光性质。相应元素和他们的第一工业使用的发现亲密地被连接到他们的光性质。这种关系被使活着直到什么时候的今天象节省精力的灯光的设备，显示，光纤维和放大器，激光，为生物医学的分析并且在察觉到的 celluio 的应答的光污点和成像那样的包含 lanthanide 材料的许多高科技应用，重重地依靠 lanthanide 离子的灿烂、纯颜色的排放。在这评论，我们首先在 f-f 转变，促进感受性机制，和对包含 lanthanide 的光效率的评价上与强调构画出 lanthanide 光的基础放射性的分子的大厦。强调然后被放在 lanthanide 光的二个快发展中方面上：为电信和轻射出二极管的材料，和生物医学的成像并且察觉到。在为塑料放大器和波导的射出 NIR 材料的最近的进展被描述，和最小化激动的状态的非放射的释放的研究人员带的主要答案。在 1999 那耳 tris (8-hydroxyquinolinate ) 的示范显示了合适的明亮绿的排出物因为射出二极管(OLED ) 的器官的光被认识到在 OLED， 25% 刺激精力导致汗衫状态， 75% 说到三位字节跟随。因为 lanthanide 离子是好三位字节，熄灭 ers，他们现在也在这些灯光的设备的发展起一个关键作用。生物分子的光分析在知道的最敏感的分析技术之中。lanthanide 的长一生使状态激动允许解决时间的光谱学被过去常，压制样品汽车荧光并且到达很低的察觉限制。可见 lanthanide 传感器现在无所不在地不仅在医药诊断并且在房间成像被规定，而且使用象 Yb (III ) 那样的离子的 NIR 排放的可行性现在是因为更深的穿入，在生物纸巾被测试。
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In this paper a new and facile method for preparation of anhydrous lanthanidetrichlorides is reported. Pure LnCl3·nTHF were obtained in high yields by the reaction of lanthanide oxides with chlorotrimethylsilane and methanol in tetrahydrofuran under mild condition.
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Electronegativity
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Lanthanide contraction
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The preparation of anhydrous lanthanide bromides by chemical vapor transport method is reported. A mixture of LnBr_3 and Al_2O_3 is formed when Ln_2O_3 react directly with Al powder and Br_2. AlBr_3 is also formed with excess amount of Al and Br_2. Vapor Al_2Br_6 forms at high temperature. It reacts further with LnBr_3 to become complex LnAl_3Br_(12) and the complex decomposes at low temperature. LnBr_3 was separated from other solids by means of chemical vapor transport at a temperature gradient from 753K to 453K. The purity of products was more than (99.5%.)
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