Synthesis and Properties of a Decacyclene Monoimide and a Naphthalimide Derivative as Three-Dimensional Acceptor-Donor-Acceptor Systems.
Synthesis and Properties of a Decacyclene Monoimide and a Naphthalimide Derivative as Three-Dimensional Acceptor-Donor-Acceptor Systems.
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DOI：
10.1002/asia.201701668
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发表时间：
2018-04
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通讯作者：
Yuma Yamamoto;M. Yoshida;Takuya Morii;J. Nishida;C. Kitamura;T. Kawase
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作者：
Yuma Yamamoto;M. Yoshida;Takuya Morii;J. Nishida;C. Kitamura;T. Kawase
以双并[1，2-b；1‘，2’-d]噻吩类化合物(DAT)为原料，通过Diels-Alder(DA)环加成反应合成了十环烯单酰亚胺(DCMIs)。反应生成相应的1：2加合物(BAIA)和1：1加合物(DCMI)作为主要产物。通过X-射线单晶分析，确定了BAIAb(N-辛基衍生物)的分子结构为具有内、内空间构型的双加合物。相对于十环烯三亚胺(DCTIa，N-2-乙基己基衍生物)的吸收光谱，类似的N-2-乙基己基取代的单加合物DCMIa的吸收光谱发生了红移，尽管它具有较少的离域π电子体系。DCMIa在各种有机溶剂中不发光，而DCTIa在CH2Cl2中发出黄色荧光，量子产率较低(ΦSN)。此外，CDCl3中的DCMIa具有浓度依赖性的核磁共振氢谱行为，表明它在20℃时自聚集，其缔合常数(Ka)为(193±50)m-1，尽管DCMIa中存在四个大量的叔丁基，但其聚集体形成的Ka值与不含叔丁基取代基的DCTIa[(495±42)m-1]相当。双加合物BAIAA(N-2-乙基己基衍生物)的光谱研究表明，它表现出明显的溶剂-荧光变色，对应的发射最大位移(ΔλEM)为10 0 nm。密度泛函理论对BAIAc(N-甲基导数)的计算结果表明，HOMO和LUMO系数分布之间存在相当大的空间间隔，这表明新型三维受体-施主-受体BAIAa体系的基态到激发态的跃迁应该具有分子内电荷转移特性。
A method involving the Diels-Alder (DA) cycloaddition of diacenaphtheno[1,2-b;1',2'-d]thiophenes (DATs) with N-alkylacenaphthylene-5,6-dicarboximides (AIs) was developed to synthesize decacyclene monoimides (DCMIs). The reactions generate the corresponding 1:2 adducts (BAIAs) as major products together with 1:1 adducts (the DCMIs). The molecular structure of BAIAb (N-octyl derivative) was unambiguously assigned as the bis-adduct having an endo,endo spatial disposition of the two acenaphthylene-5,6-dicarboximide moieties by using X-ray crystallographic analysis. Relative to the absorption spectrum of decacyclene triimide (DCTIa, N-2-ethylhexyl derivative), that of the analogous N-2-ethylhexyl-substituted monoadduct, DCMIa, is bathochromically shifted despite the fact that it possesses a less delocalized π-electron system. DCMIa does not fluoresce in various organic solvents, whereas DCTIa emits yellow fluorescence in CH2 Cl2 with a low quantum yield (ΦSN ). Moreover, DCMIa in CDCl3 displays concentration-dependent 1 H NMR spectroscopy behavior, which suggests that it self-aggregates with an association constant (Ka ) of (193±50) m-1 at 20 °C. Despite the presence of four bulky tert-butyl groups in DCMIa, its Ka value for aggregate formation is comparable to that of DCTIa [(495±42) m-1 ], which does not contain tert-butyl substituents. Spectroscopic studies with the bis-adduct BAIAa (N-2-ethylhexyl derivative) show that it displays remarkable solvatofluorochromism corresponding to an emission maximum shift (ΔλEM ) of 100 nm. The results of density functional theory calculations on BAIAc (N-methyl derivative) demonstrate that a considerable spatial separation exists between the HOMO and LUMO coefficient distributions, which indicates that the ground-to-excited state transition of the novel three-dimensional acceptor-donor-acceptor BAIAa system should have intramolecular charge-transfer character.