Circular Polarized Luminescence of Hydrogen-Bonded Molecular Assemblies of Chiral Pyrene Derivatives
Circular Polarized Luminescence of Hydrogen-Bonded Molecular Assemblies of Chiral Pyrene Derivatives
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DOI：
10.1021/acs.jpcc.7b12747
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发表时间：
2018-03-22
影响因子：
3.7
通讯作者：
Akutagawa, Tomoyuki
中科院分区：
文献类型：
--
作者：
Anetai, Hayato;Takeda, Takashi;Akutagawa, Tomoyuki
手性烷基酰胺取代芘衍生物的吸收光谱和荧光光谱（R-1）（n）和（S-1）（n）在甲基环己烷（MCH）、甲苯、氯仿（CHCl_3）和四氢呋喃（THF）中的形成与N-H中心点中心点O=氢键螺旋π堆积一维（1D）超分子（R-1）（n）和（S-1）（n）的形成一致; π-堆叠结构和聚集数（n）由浓度（C）和溶剂极性控制。（R-1）（n）和（S-1）（n）在MCH和甲苯中的聚集程度远大于在THF和CHCl_3中的聚集程度，在所有溶剂中均观察到激发态（R-1）（n）（*）和（S-1）（n）（*）（n >= 2）超分子的激基缔合物发射。有趣的是，（R-1）（n）（*）和（S-1）（n）（*）的圆偏振发光（CPL）光谱显示在MCH中c > 1 × 10（-6）M时g（lum）值为0.03。圆二色性和CPL光谱揭示了氢键螺旋一维超分子组装体的形成在基态和激发态。（R-1）（n）和（S-1）（n）在CHCl_3中的一维超分子组装体的螺旋度与在MCH和THF中的相反。溶剂的极性和浓度对N-H中心点、中心点、中心点O=氢键一维超分子组装体的π-堆积结构和螺旋构型敏感。
The absorption and fluorescence spectra of chiral alkylamide-substituted pyrene derivatives (R-1 and S-1) in the solution phase were consistent with the formation of N-H center dot center dot center dot O= hydrogen-bonded helical pi-stacked one-dimensional (1D) supramolecules (R-1)(n) and (S-1)(n) in methylcyclohexane (MCH), toluene, chloroform (CHCl3), and tetrahydrofuran (THF); the pi-stacked structures and aggregation number (n) were governed by the concentration (c) and solvent polarity. The aggregation of (R-1)(n) and (S-1)(n) in MCH and toluene was much greater than that in THF and CHCl3, and excimer emission of excited-state (R-1)(n)(*) and (S-1)(n)(*) supramolecules with n >= 2 was observed in all solvents. Interestingly, the circular polarized luminescence (CPL) spectra of (R-1)(n)(*) and (S-1)(n)(*) revealed a g(lum) value of 0.03 in MCH at c > 1 X 10(-6) M. Circular dichroism and CPL spectra revealed the formation of hydrogen-bonded helical 1D supramolecular assemblies in the ground and excited states. The helicities of the 1D supramolecular assemblies of (R-1)(n), and (S-1)(n) in CHCl3 were inverted as compared to those in MCH and THF. The solvent polarity and concentration were sensitive to the pi-stacked structure and helical configuration of the N-H center dot center dot center dot O= hydrogen-bonded 1D supramolecular assemblies.