A Conjugated Molecular Crown Containing a Single Pyrenyl Unit: Synthesis, Characterization, and Photophysical Properties

doi:10.6023/cjoc202012011

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (6): 2401-2407.DOI: 10.6023/cjoc202012011 Previous Articles Next Articles

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含单一芘基冠状共轭分子的合成、表征和光物理性质

李璟奭^a, 庄桂林^b, 黄强^a, 王进义^a, 吴亚宇^a(), 杜平武^a^,^*

a 中国科学技术大学化学与材料科学学院合肥 230026
b 浙江工业大学化学工程学院杭州 310032

收稿日期:2020-12-05 修回日期:2021-02-08 发布日期:2021-02-26
通讯作者: 杜平武
基金资助:
国家重点研发计划(2017YFA0402800); 国家自然科学基金(21971229); 国家自然科学基金(51925206); 国家自然科学基金(U1932214); 浙江省自然科学基金(LR19B010001)

A Conjugated Molecular Crown Containing a Single Pyrenyl Unit: Synthesis, Characterization, and Photophysical Properties

Jingshi Li^a, Guilin Zhuang^b, Qiang Huang^a, Jinyi Wang^a, Yayu Wu^a(), Pingwu Du^a

a Department of Materials Science and Engineering, University of Science and Technology of China, Hefei 230026
b College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032

Received:2020-12-05 Revised:2021-02-08 Published:2021-02-26
Contact: Pingwu Du
Supported by:
National Key Research and Development Program of China(2017YFA0402800); National Natural Science Foundation of China(21971229); National Natural Science Foundation of China(51925206); National Natural Science Foundation of China(U1932214); Zhejiang Provincial Natural Science Foundation(LR19B010001)

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Abstract

Macrocyclic π-conjugated materials have attracted much attention due to their unique structures and physical properties. The synthetic methods and physical properties of a π-extended molecular crown containing a single pyrenyl unit, cyclo[7]paraphenylene-2,7-pyrenylene ([7]CPPPy _2,7), were report. This macrocycle was achieved by a rationally designed Suzuki-Miyanra coupling of a curved precursor and pyrene-2,7-bis(boronate), followed by reductive aromatization with stannous acid, and confirmed by various physical characterizations, such as HR-MS and a series of NMR spectroscopies. The photophysical properties of [7]CPPPy_2,7 were further studied by UV-vis spectroscopy and other analysis, and its maximum absorption peak was located at 326 nm, which was consistant with density functional theory (DFT) calculations. The fluorescence emission spectrum of [7]CPPPy_2,7 was further studied. Under 350 nm excitation, the emission peak appeared at 492 nm. The computational result indicates the strain energy of [7]CPPPy_2,7 is as high as 299.17 kJ•mol^–1.

Key words: π-conjugated macrocycle, molecular crown, polyaromatic hydrocarbon, pyrene

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Jingshi Li, Guilin Zhuang, Qiang Huang, Jinyi Wang, Yayu Wu, Pingwu Du. A Conjugated Molecular Crown Containing a Single Pyrenyl Unit: Synthesis, Characterization, and Photophysical Properties[J]. Chinese Journal of Organic Chemistry, 2021, 41(6): 2401-2407.

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Fig. & Tab. 6

Scheme 1. Molecular structures of (a) [n+4]cycloparaphenyl- ene ([n+4]CPP), and (b) a molecular crown containing a single pyrenyl unit, [7]CPPPy2,7

Scheme 2. Synthetic route for [7]CPPPy2,7 Reaction conditions: (a) (diacetoxyiodo)benzene, MeOH, r.t., 72 h, 80%; (b) imidazole, trimethyl chlorosilane, CH2Cl2, 0 ℃, 16 h, 95%; (c) (diacetoxyiodo)benzene, THF/MeCN/H2O, r.t., 16 h, 68%; (d) (1) NaH, THF, 0 ℃, 3 h; (2) 1,4-dibromobenzene, n-BuLi, THF, –78 ℃, 2 h; (3) NaH, MeI, THF, 0 ℃, 8 h, 62% (three steps from compound 3); (e) (1) n-BuLi, THF, –78 ℃, 2 h; (2) NaH, MeI, THF, 0 ℃, 8 h, 57% (two steps from compound 4); (f) Pd(PPh3)4, KOH, THF/H2O, 80 ℃, 48 h; (g) H2SnCl4, THF, r.t., 4 h, 21% (two steps from compound 5)

Figure 1. Characterization spectra for [7]CPPPy2,7 (a) Partial HR-MS (MALDI-TOF) data. (b) Partial1H NMR spectra of [7]CPPPy2,7 in CDCl3. (c) Partial 13C NMR spectra of [7]CPPPy2,7 in CDCl3. (d) Classification of protons in [7]CPPPy2,7. (e) Expanded 2D 1H-1H COSY NMR spectra (400 MHz, CDCl3) of [7]CPPPy2,7. (f) Expanded 2D 1H-1H NOESY NMR spectra (400 MHz, CDCl3) of [7]CPPPy2,7

Figure 2. (a) UV-vis absorption (solid lines) and fluorescence spectra (short dot lines) of pyrene (blue), [9]CPP (red) and [7]CPPPy2,7 (black) in CH2Cl2 (inset: photographs of the fluorescence of [9]CPP (left) and [7]CPPPy2,7 (right) in CH2Cl2 under UV irradiation (λ=365 nm)); (b) Emission lifetime measured at λ=492 nm for [7]CPPPy2,7 in CH2Cl2 (insert: curve-fitting residuals for [7]CPPPy2,7)

Figure 3. Concentration-dependent fluorescence spectra of (a) pyrene and (b) [7]CPPPy2,7 in CH2Cl2 All the fluorescence spectra were obtained by exciting samples at λ=350 nm

Figure 4. Comparison of some frontier molecular orbitals of [7]CPPPy2,7and [9]CPP

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含单一芘基冠状共轭分子的合成、表征和光物理性质

A Conjugated Molecular Crown Containing a Single Pyrenyl Unit: Synthesis, Characterization, and Photophysical Properties

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