Solvatomorphic Phase Transitions and Tunable Luminescence Emission in Lanthanide Metal-Organic Frameworks

IF 4.3 3区 材料科学 Q1 ENGINEERING, ELECTRICAL & ELECTRONIC
Alena A. Vasileva, Pavel A. Demakov, Tatiana Y. Guselnikova, Alexey A. Ryadun, Vladimir P Fedin, Danil N. Dybtsev
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Abstract

Four new metal-organic frameworks with the formulae [Sm2(phen)2(NO3)2(chdc)2]·2Solv, where Solv = N,N-dimethylformamide (DMF; 1), N,N-dimethylacetamide (DMA; 2), N,N-diethylformamide (DEF; 3), N-formylpiperidine (NFP; 4), phen = 1,10-phenanthroline and chdc2– = trans-1,4-cyclohexanedicarboxylate were synthesized and structurally characterized. These compounds are based on similar binuclear samarium(III)-carboxylate blocks, bound by flexible chdc linker into layered sql-type coordination networks. Different amide solvents drive different intralayer block orientations between 1 and 24 and different layer-to-layer packings in all the described compounds. A strong dependence of the emission color upon varying excitation wavelength was determined for 14, while relative impacts of Sm3+ and phen emission into overall luminescence were found to depend strongly on these packings, and their reasonable correlation to the distances between closest π-π-stacked phen moieties in the structures was revealed. Phase transitions between compounds 14 were studied by means of powder X-ray diffraction. Additionally, two-metal near-white luminophores were obtained for phases 3 and 4 by doping their synthetic systems by minor (~5%) additive of Tb3+. In general, this study shows a possibility of tuning the luminescence properties of porous metal-organic frameworks by minor structural differences induced by solvent-driven dynamics with no apparent quenching or other direct impact of the optical properties of the solvent included.
镧系元素金属有机框架中的溶胶形态相变和可调谐发光发射
四种新的金属有机框架的化学式为[Sm2(phen)2(NO3)2(chdc)2]-2Solv,其中 Solv = N,N-二甲基甲酰胺(DMF;1),N,N-二甲基乙酰胺(DMA;2),N,N-二乙基甲酰胺(DEF;3)、N-甲酰基哌啶(NFP;4)、phen = 1,10-菲罗啉和 chdc2- = 反式-1,4-环己烷二甲酸酯的合成及其结构特征。这些化合物以类似的双核钐(III)-羧酸盐块为基础,通过柔性 chdc 连接器结合成层状 sql 型配位网络。不同的酰胺溶剂会导致 1 和 2-4 层之间不同的层内嵌段取向,以及所有所述化合物中不同的层间排列。研究发现,1-4 的发射颜色与激发波长的变化有很大关系,而 Sm3+ 和 phen 发射对整体发光的相对影响与这些堆积有很大关系,并且它们与结构中最接近的 π-π-stacked phen 分子之间的距离有合理的相关性。通过粉末 X 射线衍射研究了化合物 1-4 之间的相变。此外,通过在合成体系中添加少量(约 5%)Tb3+,相 3 和相 4 获得了双金属近白发光体。总之,这项研究表明,多孔金属有机框架的发光特性可以通过溶剂驱动动力学引起的微小结构差异来调整,而不会受到所含溶剂的光学特性的明显淬灭或其他直接影响。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
CiteScore
7.20
自引率
4.30%
发文量
567
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