Luminescence and Magnetic Properties of {LnIIICdII16} Metallacrown Complexes Centered with Compressed Tetragonal Antiprismatic Ln(III) Units

IF 3.2 2区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Crystal Growth & Design Pub Date : 2025-03-25 DOI:10.1021/acs.cgd.5c0008410.1021/acs.cgd.5c00084

Zhen Li, Ke Deng, Dan Li, Hui Kong, Ze-Yu Ruan, Si-Guo Wu* and Ming-Liang Tong*,

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Abstract

Metallacrown (MC) motifs are suitable elements for constructing functional lanthanide complexes, taking advantage of their versatile structural configurations and chemical tailoring capabilities. Herein, “triple-decker sandwich” MCs [LnCd₁₆(quinha)₁₆py₈](NO₃)₂(CF₃SO₃)·20H₂O·5DMF (1-Ln, Ln = Dy^III, Yb^III, and Nd^III) have been synthesized using the quinaldichydroxamic acid (H₂quinha) ligand. Structural analysis indicates that 1-Ln comprises two [12-MC_Cd(II)-4] rings coordinated with Ln^III on the upper and lower sides and an outer [24-MC_Cd(II)-8] macrocycle. 1-Ln possesses a compressed tetragonal antiprismatic coordination geometry with zenithal angles over 65°. 1-Yb and 1-Nd exhibit near-infrared emission with lifetimes of 23.55 and 7.12 μs, and the abnormal temperature-dependent intensity might be caused by the hot band absorption. 1-Dy displays fast magnetization relaxation in the low-temperature region due to the inappropriate crystal field environment.

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以压缩反棱镜Ln（III）单元为中心的{LnIIICdII16}金属冠配合物的发光和磁性能

金属王冠（MC）基序具有多种结构构型和化学裁剪能力，是构建功能镧系配合物的合适元素。本文以双羟基喹啉酸（H2quinha）为配体，合成了“三层三明治”MCs [LnCd16(quinha)16py8](NO3)2（CF3SO3）·20H2O·5DMF （1-Ln, Ln = DyIII, YbIII, NdIII）。结构分析表明，1-Ln由两个[12-MCCd(II)-4]环和一个外环[24-MCCd(II)-8]环组成，上下两侧与LnIII协调。1-Ln具有压缩的四边形反棱镜配位几何，顶角大于65°。1-Yb和1-Nd表现出近红外辐射，寿命分别为23.55和7.12 μs，异常的温度依赖强度可能是由热带吸收引起的。由于晶体场环境不适宜，1-Dy在低温区表现出快速的磁化弛豫。

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来源期刊

Crystal Growth & Design 化学-材料科学：综合

CiteScore

6.30

自引率

10.50%

发文量

650

审稿时长

1.9 months

期刊介绍： The aim of Crystal Growth & Design is to stimulate crossfertilization of knowledge among scientists and engineers working in the fields of crystal growth, crystal engineering, and the industrial application of crystalline materials. Crystal Growth & Design publishes theoretical and experimental studies of the physical, chemical, and biological phenomena and processes related to the design, growth, and application of crystalline materials. Synergistic approaches originating from different disciplines and technologies and integrating the fields of crystal growth, crystal engineering, intermolecular interactions, and industrial application are encouraged.