同手性金属有机框架(MOFs)维度的精准调控及荧光性质的研究

doi:10.6023/A21100474

摘要/Abstract

精准调控不同维度和拓扑的结构, 特别是具有同组分的手性结构代表了当今合成化学所面临的最具挑战性的问题之一. 基于配位化学的不同维度杂化材料的自组装被认为是能够解决上述问题的一种有效途径. 本工作采用了已报道的一维管(HMOF-2)和二维层(HMOF-3)合成所需的5,5'-N,N-二间苯二甲酸-(1R,2R)-环己烷二酰胺(R,R-CHCAIP)配体和锌盐(Zn²⁺), 在高温(100 ℃)溶剂热反应条件下自组装而成新的三维孔MOFs (HMOF-4). 提出了辅助配体和反应温度协同作用的策略, 进而精准调控获得了这三个结构多样化、维度不同的手性MOFs, 在目前已报道的多维MOFs中, 这类具有同组分的多维手性MOFs是极为罕见的. 研究了其荧光性质, 用时间依赖的密度泛函理论(TDDFT)计算解释了其发光机理. 它们发射光谱的微小差异说明Zn-MOFs的维度对荧光的影响较小. 这项工作为精准调控不同维度的同手性MOFs提供了一个有特色的构筑方法.

关键词: 精准调控, 同手性金属有机框架(MOFs), 维度, 协同作用, 荧光

To precisely control the construction of different dimensional and topological structure represents one of the most challenging issues facing synthetic chemistry nowadays, especially synthesizing different dimensions of chiral materials with identical compositions. Self-assembly of structural dimension of hybrid materials based on coordination chemistry has been regarded as an effective means addressed this issue. Herein, self-assembly of Zn salts with R,R-CHCAIP (5,5′-((1R,2R)-cyclohexane dicarbonyl bis(azanediyl)) diisophthalic acid) generates a new 3D homochiral metal-organic framework Zn_1.5(R,R-CHCAIP)(H₂O)₂ (HMOF-4) that uses the same ligand and metal as our reported 1D tube Zn₂(R,R-CHCAIP)Py₂(H₂O) (HMOF-2) and 2D layer [Zn₄(R,R-CHCAIP)₂(4,4′-bipy)₂(H₂O)₅]•5H₂O•3DMA (HMOF-3, DMA, N,N-dimethylacetamide) under the solvothermal reaction at high temperature (100 ℃). Based on a new strategy of the synergistic action of the auxiliary ligand and temperature, the structural diversity for HMOF-2, HMOF-3 and HMOF-4 from 1D to 2D and 3D is modulated during the assembly process, and the resulting multidimensional homochiral MOFs with identical composition are extremely rare in currently reported MOFs with different dimensions. The fluorescence of HMOF-4 and HMOF-2, HMOF-3 is investigated, and their fluorescent mechanisms are interpreted by time-dependent density functional theory (TDDFT) calculation. The tiny difference of their fluorescent emission spectra indicates the dimensions of Zn-MOFs have little effect on fluorescence. This work provides a distinctive construction means for precise control of the different dimension of homochiral MOFs.

Key words: precise control, homochiral metal-organic frameworks (MOFs), dimension, synergistic action, fluorescence

引用此文

赵彦武, 李星, 张富强, 张祥. 同手性金属有机框架(MOFs)维度的精准调控及荧光性质的研究[J]. 化学学报, 2021, 79(11): 1409-1414.

Yan-Wu Zhao, Xing Li, Fu-Qiang Zhang, Xiang Zhang. Precise Control of the Dimension of Homochiral Metal-Organic Frameworks （MOFs) and Their Luminescence Properties[J]. Acta Chimica Sinica, 2021, 79(11): 1409-1414.

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图/表 7

图1. 同手性的一维金属有机纳米管(HMOF-2)、二维类波浪层(HMOF-3)和三维框架(HMOF-4)的构筑途径

Figure 1. The construction of homochiral 1D metal-organic nanotube (HMOF-2), 2D wave-like layer (HMOF-3) and 3D framework of HMOF-4

图2. (a) HMOF-4中Zn的配位环境图. 对称操作: a: 1–y, 1–x, 1/2–z; b: 1/2+x, 1/2–y, 3/4–z; c: –1/2+x, 3/2–y, 3/4–z; (b) HMOF-4的拓扑类型: flu (sqc169), (4,8)-连接的网络(亮绿色代表Zn2(COO)4(H2O)2 SBUs; 蓝紫色代表R,R-CHCAIP 配体); (c) HMOF-4中有机配体R,R-CHCAIP的配位模式; (d)和(e)含有八面体构型Zn1和四面体构型Zn2的三核簇

Figure 2. (a) Representation of Zn coordination environment in HMOF-4. Symmetry operation: a: 1–y, 1–x, 1/2–z; b: 1/2+x, 1/2–y, 3/4–z; c: –1/2+x, 3/2–y, 3/4–z; (b) topological type: flu (sqc169), (4,8)-connected net in HMOF-4 (bright green: Zn2(COO)4(H2O)2 SBUs, bluish violet: R,R-CHCAIP ligand); (c) coordination mode of organic ligand R,R-CHCAIP in HMOF-4; (d) and (e) trinuclear cluster with the coordination around Zn1 and Zn2, showing octahedral and tetrahedral geometries, respectively

图3. HMOF-4的XPS谱: (a) 全谱, (b) Zn 2p, (c) C 1s, (d) O 1s和(e) N 1s

Figure 3. XPS spectra of HMOF-4: (a) survey spectra, (b) Zn 2p, (c) C 1s, (d) O 1s and (e) N 1s

图4. 有机配体(紫色线)和HMOF-4(黑色线)的红外光谱图

Figure 4. IR spectra of the organic ligand (violet line) and HMOF-4 (black line)

图5. HMOF-4的TGA曲线

Figure 5. TGA curve of HMOF-4

图6. (a) 固态的HMOF-4的荧光激发谱和发射谱; (b) 固态的有机配体R,R-CHCAIP、HMOF-2、HMOF-3和HMOF-4的荧光发射光谱

Figure 6. (a) Excitation and emission spectra of solid HMOF-4; (b) emission spectra of solid R,R-CHCAIP ligand, HMOF-2, HMOF-3 and HMOF-4

图7. 描述由(a)有机配体, (b) HMOF-2和(c) HMOF-3的最低能量吸收带组成的主要跃迁能级图

Figure 7. Energy-level diagram depicting the dominant transitions that comprise the lowest-energy absorption bands for (a) organic ligand, (b) HMOF-2 and (c) HMOF-3

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