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A mononuclear Dy(III) complex incorporating the dithienylethene unit: crystalline-phase photochromism, magnetic and luminescent properties

机译:包含二噻吩乙烯单元的单核Dy(III)配合物:晶相光致变色,磁性和发光性质

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摘要

A new dithienylethene compound 2-(4-diethylphosphonophenyl)-4,5-bis(2,5-dimethyl(3-thienyl))-1H-imidazole (dbi) has been synthesized and applied for the coordination-assembly generation of a mononuclear complex [Dy(hfac)(3)(dbi)(2)]center dot CH3OH (1) (hfac = hexafluoroacetylacetonate), in which dbi ligands coordinate to Dy(III) ion through phosphoryl oxygen atoms. In the crystal structure of dbi, each molecule shows a parallel conformation, and neighboring molecules are linked into an interesting helical chain through hydrogen bonds. In contrast, each dbi ligand in 1 exhibits a photoactive antiparallel conformation, thus resulting in crystalline-phase photochromism (CPP) behavior of 1. Before and after CPP reaction, 1 shows different magnetic and luminescence properties. After irradiation with 365 nm light, the shape of the chi(T)(M) vs. T plot revealed drastic changes, and field-induced chi(M)'' peaks were observed. Compound 1 exhibits ligand- and Dy(III)-centered fluorescence emissions. The irradiation with 365 nm light resulted in the red shift of dbi-centered emissions, and the decrease in intensity of Dy(III)-centered emission.
机译:合成了一种新的二噻吩乙烯化合物2-(4-二乙基膦酰基苯基)-4,5-双(2,5-二甲基(3-噻吩基)-1H-咪唑(dbi),并将其用于单核的配位组装配合物[Dy(hfac)(3)(dbi)(2)]中心点CH3OH(1)(hfac =六氟乙酰丙酮),其中dbi配体通过磷酰氧原子与Dy(III)离子配位。在dbi的晶体结构中,每个分子显示平行构象,并且相邻分子通过氢键连接成有趣的螺旋链。相反,1中的每个dbi配体均表现出光活性反平行构象,因此导致结晶相光致变色(CPP)行为为1。在CPP反应之前和之后,1均显示出不同的磁性和发光特性。用365 nm光照射后,chi(T)(M)与T的关系图的形状显示出剧烈的变化,并观察到了场诱导的chi(M)''峰。化合物1表现出以配体和Dy(III)为中心的荧光发射。 365 nm光的照射导致以dbi为中心的发射发生红移,并以Dy(III)为中心的发射强度降低。

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