Syntheses, structures and photophysical properties of new heterodinuclear cd-ln coordination complexes (Ln = sm, eu, tb, nd, ho, er)
Syntheses, structures and photophysical properties of new heterodinuclear cd-ln coordination complexes (Ln = sm, eu, tb, nd, ho, er)
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新型异双核cd-ln配位配合物（Ln = sm、eu、tb、nd、ho、er）的合成、结构和光物理性质
DOI：
10.1002/ejic.200800106
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发表时间：
2008-05-01
影响因子：
2.3
通讯作者：
Jin, Jing
中科院分区：
文献类型：
--
作者：
Chi, Yu-Xian;Niu, Shu-Yun;Jin, Jing
用水热法合成了6个新的异双核d-f配合物[LnCd(C8H7O3)(5)(Phen)(H2O)](Ln=Sm1，Eu2，Tb3，Nd4，Ho5，Er6；C8H7O3=4-甲氧基苯甲酸；phen=1，10-菲咯啉)，并用单晶X射线衍射法对其结构进行了表征。在室温下测定了六种配合物的红外光谱、UV/Vis/NIR吸收光谱和发光光谱。它们具有相同的分子结构，相邻的两个分子通过氢键或Ln中心点O弱相互作用连接起来形成二聚体晶体。在可见光区，配合物1-3的发射光谱显示了相应的Ln(III)离子的强烈特征带，这主要归因于d块到f块的有效能量转移，即d块的良好敏化。此外，在Cd-Ln配位络合物中，Cd中心点Ln的间距很小，Cd-III离子的4d轨道可能会影响Ln(III)离子的4f轨道，这可能会导致Ln(III)离子的一些f能级发生调整，这种影响可以在配合物的UV/VIS/NIR光谱中观察到。特别是在配合物4-6中，Ln(III)离子的某些能级发生了位移或分裂，相应的发射带在近红外区域出现了位移或分裂。(C)Wiley-VCH Verlag GmbH&Co.KGaA，69451，德国温海姆，2008年)。
Six novel heterodinuclear d-f coordination complexes [LnCd(C8H7O3)(5)(phen)(H2O)] (Ln = Sm 1, Eu 2, Tb 3, Nd 4, Ho 5, Er 6; C8H7O3 = 4-methoxybenzoato; phen = 1, 10-phenanthroline) were synthesized by the hydrothermal method, and their structures were studied by single-crystal X-ray diffraction. The IR and UV/Vis/NIR absorption spectra and the luminescence spectra of the six complexes were determined at room temperature. They have the same molecular structure, and two neighboring molecules are connected by hydrogen bonds or by a Ln center dot center dot center dot O weak interaction to form dimer crystals. In the visible region, the emission spectra of complexes 1-3 show the intense characteristic bands of the corresponding Ln(III) ions, which are mainly attributed to the efficient energy transfer from the d block to the f block, that is, to the good sensitization of the d block. Moreover, in the Cd-Ln coordination complexes, the Cd center dot center dot center dot Ln separation is very small, and the 4d orbitals of the Cd-III ion may influence the 4f orbitals of the Ln(III) ion, which probably causes some of the f levels of the Ln(III) ion to be adjusted, and this effect can be observed in the shifts or splittings of the absorption bands in the UV/Vis/NIR spectra of the complexes. Especially in complexes 4-6, some energy levels of the Ln(III) ions have shifts or splittings, hence the corresponding emission bands exhibit shifts or splittings in the NIR region. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).