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Tunable 4f/5f Bimodal Emission in Europium-Incorporated Uranyl Coordination Polymers
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2018-01-03 00:00:00 , DOI: 10.1021/acs.inorgchem.7b02304
Jian Xie 1 , Yaxing Wang 1, 2 , Mark A. Silver 1 , Wei Liu 1 , Tao Duan 3 , Xuemiao Yin 1 , Lanhua Chen 1 , Juan Diwu 1 , Zhifang Chai 1 , Shuao Wang 1
Affiliation  

There have been numerous studies on emission-color regulation by the adjustment of molar amounts of multiple trivalent lanthanide cations, such as Eu3+, Tb3+, Dy3+, and others, in many types of solid host materials. Although uranyl emission originating from charge-transfer transitions has been well-recognized and investigated for many decades, as of now there is no report on tunable 4f/5f bimodal emission based on heterobimetallic lanthanide(III) and uranyl(VI) compounds. In most cases, complete energy transfer between uranyl(VI) and lanthanide(III) centers was observed. In this work, a series of isotypic-europium-incorporated uranyl coordination polymers, [email protected]2L(DMF) (L2– = 3,5-pyridinedicarboxylate, denoted as 110, which represent the different Eu contents in UO2L(DMF); DMF = N,N-dimethylformamide), has been synthesized by solvothermal reactions. Crystallographic evidence of this series unveiled one-dimensional chains of UO22+ as pentagonal-bipyramidal units bridged by pyridinedicarboxylate with no defined, crystallographically unique site containing Eu, even for the products with high concentrations of Eu in this series. However, emission bands characteristic of Eu3+ were clearly observed in every product along with the characteristic uranyl-emission feature when observed with UV–vis fluorescence spectroscopy. Laser-ablation inductively coupled plasma mass spectrometry indicated that europium was concomitant with uranium, corroborating the incorporation of europium into crystals of UO2L(DMF). Systematic control of the solvent ratio (VH2O/VDMF) in each reaction gives rise to an enrichment of Eu3+ in the interior of UO2L(DMF). In addition, the color of emission of these compounds changed significantly from bright red to bright green with decreasing Eu content. This phenomenon occurs from the highly efficient energy transfer between the UO22+ and Eu3+ centers within each sample, providing the first case of a tunable 4f/5f bimodal emission in a mixed 4f/5f-elements-bearing metal–organic-hybrid material.

中文翻译:

掺-铀酰配位聚合物中的可调4f / 5f双峰排放

在许多类型的固体基质材料中,已经通过调节多个三价镧系元素阳离子(例如Eu 3+,Tb 3+,Dy 3+等)的摩尔量来调节发射颜色的研究。尽管源自电荷转移跃迁的铀酰发射已得到公认,并已进行了数十年的研究,但截至目前,尚无基于异双金属镧系元素(III)和铀酰(VI)化合物的可调4f / 5f双峰发射的报道。在大多数情况下,观察到了铀酰(VI)和镧系元素(III)中心之间的完全能量转移。在这项工作中,一系列同型掺入铀的铀酰配位聚合物,[受电子邮件保护] 2 L(DMF)(L 2–= -3,5-吡啶,表示为1 - 10,其代表在UO不同的Eu含量2 L(DMF); DMF =N,N-二甲基甲酰胺),已经通过溶剂热反应合成。该系列的晶体学证据揭示了UO 2 2+的一维链,即由吡啶二羧酸盐桥接的五边形-双锥体单元,即使在该系列中含高浓度Eu的产品中,也没有明确的,晶体学上唯一的含Eu的位点。然而,Eu 3+的发射带特征用紫外可见荧光光谱法观察时,在每种产品中都清楚地观察到了尿烷的特征,同时还观察到了其特征性的铀酰发光特征。激光烧蚀电感耦合等离子体质谱表明indicated与铀同时存在,从而证实了the掺入UO 2 L(DMF)晶体中的情况。系统控制每个反应中的溶剂比(V H 2 O / V DMF)会导致U 3 2内部富集Eu 3+L(DMF)。另外,随着Eu含量的降低,这些化合物的发射颜色从鲜红色显着改变为鲜绿色。这种现象是由于每个样品中的UO 2 2+和Eu 3+中心之间进行了高效的能量转移而产生的,这是在含4f / 5f元素的金属-有机-混合金属中提供了可调谐4f / 5f双峰发射的第一种情况。混合材料。
更新日期:2018-01-03
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