Han Yongqiang, Yan Pengfei, Sun Jingwen, An Guanghui, Yao Xu, Li Yuxin, Li Guangming
Key Laboratory of Functional Inorganic Material Chemistry (MOE), School of Chemistry and Materials Science, Heilongjiang University, No. 74, Xuefu Road, Nangang District, Harbin 150080, People's Republic of China.
Dalton Trans. 2017 Apr 5;46(14):4642-4653. doi: 10.1039/c7dt00215g.
Two types of sixteen complexes 1-16, namely, {[Ln(TFBDC)(HO)]·2HO} [Ln = Pr (1) and Nd (2)] and {[Ln(TFBDC)(HO)]·HO} [Ln = Ce (3), Pr (4), Nd (5), Sm (6), Eu (7), Gd (8), Tb (9), Dy (10), Ho (11), Er (12), Yb (13) and Lu (14)], {[DyEu(TFBDC)(HO)]·HO} (15) and {[GdEuTb(TFBDC)(HO)]·HO} (16), were isolated by the reaction of LnCl·6HO with 2,3,5,6-tetrafluoroterephthalic acid (HTFBDC). X-ray crystallographic analysis revealed that 1 and 2 exhibit 3D network structures and complexes 3-14 feature 2D network structures formed via three different coordination modes of the ligand. Luminescence spectra revealed that these complexes exhibit broad-spectrum luminescence from the visible to the near-infrared (NIR) region. Unexpectedly, complex 1 exhibits a unique NIR luminescence pattern and the longest lifetime among reported molecular praseodymium complexes. White-light emission was realized via three approaches using the single-component complex 6 (Sm), the two-component complex 15 (Eu and Dy) and the three-component complex 16 (Eu, Tb and Gd). Complex 9 exhibits high sensitivity and selectivity in its luminescence response to benzaldehyde, which provides a promising luminescent sensor for the detection of benzaldehyde.
通过LnCl₃·6H₂O与2,3,5,6 - 四氟对苯二甲酸（HTFBDC）反应，分离得到了两种类型的十六种配合物1 - 16，即{[Ln(TFBDC)(H₂O)]·2H₂O} [Ln = Pr (1) 和Nd (2)] 以及{[Ln(TFBDC)(H₂O)]·H₂O} [Ln = Ce (3)、Pr (4)、Nd (5)、Sm (6)、Eu (7)、Gd (8)、Tb (9)、Dy (10)、Ho (11)、Er (12)、Yb (13) 和Lu (14)]，{[DyEu(TFBDC)(H₂O)]·H₂O} (15) 和{[GdEuTb(TFBDC)(H₂O)]·H₂O} (16)。X射线晶体学分析表明，1和2呈现三维网络结构，配合物3 - 14具有通过配体三种不同配位模式形成的二维网络结构。发光光谱表明，这些配合物在可见光到近红外（NIR）区域呈现广谱发光。出乎意料的是，配合物1呈现独特的近红外发光模式，且在已报道的分子镨配合物中具有最长的寿命。通过使用单一组分配合物6（Sm）、双组分配合物15（Eu和Dy）和三组分配合物16（Eu、Tb和Gd）的三种方法实现了白光发射。配合物9在对苯甲醛的发光响应中表现出高灵敏度和选择性，这为检测苯甲醛提供了一种有前景的发光传感器。
