A class of dithienophenazine derivatives, 9,10-difluoro-2,5-dialkyldithieno[3,2-a:2′,3′-c]phenazine (F-n, n = 4, 5, 6, 7 and 8), modified with various lengths of linear alkyl chains were synthesized and used as building blocks to assemble luminescent one-dimensional (1D) nano/microcrystals. It was demonstrated that the side-chain length can dramatically influence the self-assembled morphologies of the 1D nano/micromaterials. The self-assembly behaviors of F-n have been studied based on the methods of crystallization in the solution phase and solvent evaporation on a substrate. For F-4, F-6 and F-7 molecules, well-defined 1D twisted microstructures (including ribbons, fibers and bundles) were obtained. F-5 molecules can self-assemble into nearly criss-cross (orthogonal) network patterns interconnected by 1D wires. F-8 molecules with longer alkyl chains predominantly formed flattened wires. Single crystal X-ray structure studies of F-n (n = 4, 5 and 8) demonstrated that alkyl chains with different lengths result in distinctly different intermolecular interactions and molecular packing modes, which provides a reasonable explanation for the alkyl chain length-dependent assembly morphologies and emission of F-n-based nano/micromaterials. It has been demonstrated that anisotropic noncovalent interactions and mirror-symmetrical crystallization dominated the 1D assembly behaviors of this class of molecules.

中文翻译：

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基于烷基氟取代的二噻吩并吩嗪的一维发光晶体的可控形态和自组装†

一类二噻吩并吩嗪衍生物9,10-二氟-2,5-二烷基二噻吩并[3,2- a：2'，3'- c ]吩嗪（F- n，n = 4、5、6、7和8）合成了各种长度的线性烷基链修饰的，并用作构建发光一维（1D）纳米/微晶的基础。结果表明，侧链的长度可以极大地影响一维纳米/微材料的自组装形态。F- n的自组装行为基于溶液相中结晶的方法和在基板上蒸发溶剂的方法，已经进行了研究。对于F-4，F-6和F-7分子，获得了定义明确的一维扭曲微结构（包括带，纤维和束）。F-5分子可以自组装成由一维导线互连的几乎纵横交错的（正交）网络模式。具有较长烷基链的F-8分子主要形成扁平线。F- n（n = 4、5和8）的单晶X射线结构研究表明，不同长度的烷基链导致分子间的相互作用和分子堆积方式截然不同，这为依赖于烷基链长度的现象提供了合理的解释F- n的组装形态和发射基纳米/微材料。已经证明，各向异性的非共价相互作用和镜像对称结晶支配了这类分子的一维组装行为。