High proton conduction behavior in 12-connected 3D porous lanthanide–organic frameworks and their polymer composites
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Abstract:
Two novel 12-connected 3D porous lanthanide–organic frameworks have been synthesized by the reaction of bipyridine-carboxylate ligand bpydbH2 and lanthanide metal ions. Both of them show a high proton conduction behavior as well as their composite membranes.Keywords:
Carboxylate
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.
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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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We demonstrate the conceptual advantage of using metal-organic frameworks (MOFs) for the creation of a polymetallic material that contains several different near-IR-emitting lanthanide cations and operates as a barcode material with unique luminescence properties. By choosing the ratio of lanthanide salts used during the synthesis, we can control the ratio of lanthanide cations present in the resulting material. We have demonstrated that the emission intensity of each of the different lanthanide cations is proportional to its amount in the MOF crystal, resulting in unique spectroscopic barcodes that depend on the lanthanide cation ratios and compositions.
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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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A series of new lanthanoid selenidoantimonates(V) [Ln(en)(tepa)SbSe4] (Ln = La (Ia), Ce (Ib), Pr (Ic); en = ethylenediamine, tepa = tetraethylenepentamine) and [Ln2(tepa)2(μ-OH)2Cl2]-{[Ln(tepa)]2(μ-OH)2(SbSe4)2} (Ln = Y (IIa), Sm (IIb), Gd (IIc), Tb (IId), Dy (IIe), and Tm (IIf)) were solvothermally synthesized and structurally characterized. The structures of Ia-c consist of neutral molecules [Ln(en)(tepa)SbSe4], where the tetrahedral [SbSe4](3-) anion acts as a ligand to chelate the [Ln(en)(tepa)](3+) cation. The structures of IIa-f contain isolated dinuclear [Ln2(tepa)2(μ-OH)2Cl2](2+) cations built up from two [Ln(tepa)Cl](2+) ions linked by two -OH bridging groups and organic decorated {[Ln(tepa)]2(μ-OH)2(SbSe4)2}(2-) anions based on two [Ln(tepa)SbSe4] units bridged by two -OH groups. Although a few lanthanoid selenidoantimonates(V) under solvothermal conditions have been reported, their lanthanide complexes normally appear mononuclear. Hence, IIa-f are rare examples of lanthanoid selenidoantimonates based on dinuclear lanthanide complexes. A preliminary investigation of nine lanthanoid selenidoantimonates(V) shows that the well-known lanthanide contraction has a significant influence on the formation of lanthanoid selenidoantimonates(V) under solvothermal conditions. The absorption edges of all compounds have been investigated by UV-vis spectroscopy, and density functional theory calculations for Ia and IIc have also been performed.
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Electronegativity
Coordination number
Lanthanide contraction
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Abstract The formation constants of three lanthanide complexes of the macrocyclic tetraacetic acid (Ia) [Ln(III): Eu, Tb, Lu] and of some lanthanide complexes of (Ib) [Ln(III): Nd, Sm, Eu, Gd, Dy, Er, Yb] are measured by potentiometric and competition methods.
Europium
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The special photophysical properties of the lanthanoids are among the most fascinating characteristics of these elements and are the basis of many technological applications. The fundamental understanding of these properties is crucial for a further improvement of lanthanoid luminophores. At the same time, the photophysical characterisation of lanthanoid coordination compounds can help to understand their overall properties, such as their composition in solution. This chapter starts with a short introduction to the basic photophysical properties of trivalent lanthanoids and the most important implications for the design of luminescent lanthanoid coordination compounds. Afterwards, the established standard techniques for the characterisation of lanthanoid luminophores are introduced with concrete advice for the successful performance of the experiments. In the last section of the chapter short introductions to two emergent fields of study are given: The circularly polarised luminescence (CPL) of lanthanoids and energy transfer processes between lanthanoids.
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