巨型给-受体分子开关化合物的合成及性质研究

doi:10.6023/A22060283

摘要/Abstract

以构象可变的间苯二酚杯[4]芳烃孔穴化合物(Cavitand)为分子开关母体, 合成了一种新颖的给-受体(D-A)型分子开关化合物(化合物1), 该分子是目前已知分子量最大的D-A型间苯二酚杯[4]芳烃Cavitand (分子量为3064.9966). 其中, 以卟啉为给体, 富勒烯为受体. 在pH诱导下, 化合物1可发生构象变化, 即由原来的关闭状(vase)转为打开状(kite); 而在降低温度和引入Zn²⁺的条件下, 不能促使化合物1发生构象变化. pH诱导构象发生变化的原因, 是酸的加入会导致喹喔啉手臂上的N原子发生质子化, 从而使得形成的静电排斥作用促使手臂之间相互远离. 此外, 对化合物1的光物理性质研究表明, 存在卟啉向富勒烯的单线态能量转移, 其单线态能量转移速率常数为1.1×10⁷ s^-1, 单线态能量转移效率为9.63%.

关键词: 分子开关, 给-受体, 卟啉-富勒烯, 杯[4]芳烃孔穴化合物, 能量转移

A novel donor-acceptor (D-A) molecular switch compound (compound 1) in which porphyrin is the donor and fullerene is the acceptor was synthesized using a conformationally variable resorcin[4]arene cavitand as the molecular switch parent. As far as we know, this molecule is the largest D-A resorcin[4]arene cavitand (molecular weight: 3064.9966). In order to synthesize this D-A molecular switch, firstly, compounds 4 and 9 were synthesized by Sonogashira coupling and Suzuki coupling, respectively. Then, both compounds 4 and 9 react with compound 5 to obtain arm compounds 6 and 10. Considering the low yield in the process of synthesizing porphyrins, compound 6 was first reacted with resorcin[4]arene 11 to obtain compound 12. Undoubtedly, a by-product with two compound 6 arms simultaneously will be produced. So, compound 12 can be obtained in a higher yield by adding compound 6 in batches. Then compound 13 can be obtained by the Prato reaction, and finally, compound 1 can be obtained by reacting with porphyrin arm 10. The structure of 1 was thoroughly confirmed by ¹H NMR spectroscopy (nuclear magnetic resonance spectroscopy), ¹³C NMR spectroscopy, 2D (two-dimensional) NMR spectroscopy and HRMS (high-resolution mass spectrometry). Under pH induction, compound 1 can undergo a conformational change from the original contracted state (vase) to the expanded state (kite). However, the conformational change of 1 cannot be induced under the conditions of lowering the temperature and introducing Zn²⁺. The reason for the pH-induced conformational change may be that the addition of acid causes the protonation of the N atom on the quinoxaline arm, which makes the formed electrostatic repulsion push the arms away from each other. In addition, the photophysical properties of 1 were also studied. The photophysical processes were investigated with steady-state UV-visible absorption and transient fluorescence spectroscopies. Compound 1 shows efficient intramolecular singlet-singlet energy transfer from the porphyrin moiety to the fullerene moiety. The rate constants and eﬃciency of the singlet-singlet energy transfer are calculated at 1.1×10⁷ s^-1 and 9.63%, respectively.

Key words: molecular switch, donor-acceptor, porphyrin-fullerene, resorcin[4]arene cavitand, energy transfer

引用此文

眭玉光, 周锦荣, 廖攀, 梁文杰, 徐海. 巨型给-受体分子开关化合物的合成及性质研究[J]. 化学学报, 2022, 80(8): 1061-1065.

Yuguang Sui, Jinrong Zhou, Pan Liao, Wenjie Liang, Hai Xu. A Gaint Donor-Acceptor Molecular Switch Compound: Synthesis and Properties[J]. Acta Chimica Sinica, 2022, 80(8): 1061-1065.

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图/表 6

图1. 不同功能修饰手臂的间苯二酚杯[4]芳烃孔穴化合物

Figure 1. Resorcin[4]arene cavitands with differently functional arms

图式1. 化合物1的合成路线

Scheme 1. The synthetic route to compound 1

图2. 化合物1在不同pH条件下的1H NMR谱图(c=7.4×10-3 mol/L, 溶剂: 氘代氯仿)

Figure 2. 1H NMR of compound 1 at different pH (c=7.4×10-3 mol/L, solvent: CDCl3) at different pH (c=7.4×10-3 mol/L, solvent: CDCl3)

图3. 化合物1在不同温度条件下的1H NMR谱图(c=8.2×10-3 mol/L, 溶剂: 氘代二氯甲烷)

Figure 3. 1H NMR of compound 1 at different temperatures (c=8.2×10-3 mol/L, solvent: CD2Cl2)

图4. (a) 化合物10、13和1的紫外-可见吸收光谱(c=2.5×10-6 mol/L, 溶剂: 甲苯). 插图: 局部放大; (b) 化合物10和1的稳态荧光发射光谱(c=2.5×10-6 mol/L, λex=425 nm, 溶剂: 甲苯)

Figure 4. UV-Vis absorption spectra of compounds 10, 13 and 1 (c=2.5×10-6 mol/L, solvent: toluene). Inset: partial magnification; (b) steady fluorescence emission spectra of compounds 10 and 1 (c=2.5×10-6 mol/L, λex=425 nm, solvent: toluene)

图5. (a) 化合物10和1在665 nm的荧光延迟曲线(c=2.5×10-6 mol/L, λex=425 nm, 溶剂: 甲苯)

Figure 5. Fluorescence decay curves of compounds 10 and 1 at 665 nm (c=2.5×10-6 mol/L, λex=425 nm, solvent: toluene)

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