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Defined Merocyanine Dye Stacks from a Dimer up to an Octamer by Spacer-Encoded Self-Assembly Approach
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2019-04-23 , DOI: 10.1021/jacs.9b01835
Eva Kirchner 1 , David Bialas 1 , Franziska Fennel 2 , Matthias Grüne 1 , Frank Würthner 1, 2
Affiliation  

A series of well-defined chromophore stacks is obtained upon self-assembly of merocyanine and bis(merocyanine) dyes in nonpolar solvents. Careful design of the spacer moieties linking the dipolar chromophores within the bis(merocyanine) dyes allows one to direct the dipole-dipole interaction driven aggregation into stacks of desired size from dimer up to octamer. The spacer-encoded self-assembly process was investigated by UV/vis absorption spectroscopy showing an increase of the hypsochromic shift with increasing stack size. The structure of the largest aggregate comprising eight chromophores was analyzed by 1D and 2D nuclear magnetic resonance spectroscopic studies revealing a perfectly interdigitated centrosymmetric organization of the dipolar dyes and concomitant annihilation of the ground state dipole moment is observed in the UV/vis absorption spectra. This unprecedented series of dye stacks from dimer to octamer enabled a systematic study of the optical absorption properties in dependence of the stack size disclosing that the absorption features can be rationalized by molecular exciton theory. Our results show that the noncovalent synthesis approach based on dipolar aggregation is suitable for the design of well-defined dye aggregates of specific size, allowing in-depth studies to manifest structure-property relationships.

中文翻译:

通过间隔编码自组装方法定义从二聚体到八聚体的部花青染料堆栈

通过部花青和双(部花青)染料在非极性溶剂中的自组装,获得了一系列明确定义的发色团堆栈。仔细设计连接双(部花青)染料内偶极发色团的间隔部分,可以将偶极-偶极相互作用驱动的聚集引导到从二聚体到八聚体的所需大小的堆叠中。通过紫外/可见吸收光谱研究了间隔编码的自组装过程,表明随着堆叠尺寸的增加,吸色位移增加。通过一维和二维核磁共振光谱研究分析了包含八个发色团的最大聚集体的结构,揭示了偶极染料的完美交叉中心对称组织,并且在紫外/可见吸收光谱中观察到基态偶极矩的伴随湮灭。这种前所未有的从二聚体到八聚体的染料堆栈系列能够根据堆栈尺寸系统地研究光学吸收特性,揭示了可以通过分子激子理论合理化吸收特征。我们的结果表明,基于偶极聚集的非共价合成方法适用于设计明确定义的特定尺寸的染料聚集体,允许深入研究以证明结构-性质关系。这种前所未有的从二聚体到八聚体的染料堆栈系列能够根据堆栈尺寸系统地研究光学吸收特性,揭示了可以通过分子激子理论合理化吸收特征。我们的结果表明,基于偶极聚集的非共价合成方法适用于设计明确定义的特定尺寸的染料聚集体,允许深入研究以证明结构-性质关系。这种前所未有的从二聚体到八聚体的染料堆叠系列能够根据堆叠尺寸对光学吸收特性进行系统研究,揭示了可以通过分子激子理论合理化吸收特征。我们的结果表明,基于偶极聚集的非共价合成方法适用于设计明确定义的特定尺寸的染料聚集体,允许深入研究以证明结构-性质关系。
更新日期:2019-04-23
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