Organic Synthesis of Ancient Windmill‐Like Window Nanogrid at Molecular Scale

Abstract

A series of the windmill‐like fluorenoid nanogrid were synthesized by BF3·Et2O‐mediated Friedel–Crafts reaction. Two typical routes to synthesize square windmill‐like nanogrid (WG4) were developed. A one step synthesis using an I‐shaped building block with a yield of 18 % and by‐products of triangular nanogrid (WG3) and pentagon nanogrid (WG5) as well as multi‐step synthesis using an l‐shaped building block with a higher total yield of 53 %. Meanwhile, two isomers were separated for the triangle nanogrids (WG3), one of which has been confirmed by single‐crystal X‐ray diffraction.

Synthesis and Application of Cyclopentadithiophene Derivatives

“…在 CPDT 结构中, 通过理论研究类芴结构 CPDT 基的风 车格 [36] (WG-CPDT)(图 4)表现出降低的重组能, 四元 [37][38] , 其具有棱角分明的结构骨架、可延伸拓展、可 安装以及可程序化移植等能力, 受启于中国方圆文化与 古代窗格智慧, 我们将构筑格芳烃的方法称为格子化. 目前我们已经设计并合成出五类芴基格芳烃, 分别为: 缺角格 [38] 、梯形格 [39][40] 、风车格 [41] 、菱形格 [42] 以及"井" 字形格 [43] . 基于此, 我们开始向类芴结构拓展, CPDT 作 为类芴结构将成为格子化的关键构筑合成子单元, 可以 构建系列 CPDT 基格芳烃.…”

Organic semiconductors based on complex diarylfluorenes via Friedel-Crafts protocols of fluorenols

“…(ⅲ) 环状及纳米格类的CDAFs. 由于芴醇具有特 殊的空间位阻结构, 以及咔唑、噻吩、三苯胺等反应 位点的空间限制, 位阻基团的非直线型连接发生格子 化反应, 从而能够形成诸如口字型的Grid [55] 、风车型 的WG3 [54] 、日字型 [72] 以及三棱柱型 [57] 等纳米格大分 子(图8中的20~22), 具有立体网状堆积的笼结构, 为构 筑三维多孔半导体提供了新的方法 [73] . .…”

“…本课题组 [52,53] 也设计了AB2型和AB4型等 一系列芴醇单体, 进而合成了一系列超支化与树枝状 的共轭打断型聚合物(图4(b)). (3) 傅克关环模式: 利用 AB单体聚合 [54] 或A2+B2 [55] 合成了二元环和多元类环 状寡聚物(图4(c))或格子化产物 [56] , A2+B3合成了空间 立体的三维网状笼 [57] . ( 4 面结构的大体积分子基团(图6) [60] , 富电子的芘基团引 起π-π堆积聚集; CzPy-PyFM分子中引入空穴传输功能 的吡啶基咔唑基团 [61] , 构筑高效的有机发光二极管 (organic light emitting diode, OLED)功能材料; DF-PTMPF分子是将抗氧化的受阻胺引入到芴基蓝光有机 半导体材料中 [62] , 以提高材料的光谱稳定性.…”

Over one century after discovery: pyrylium salt chemistry emerging as a powerful approach for the construction of complex macrocycles and metallo-supramolecules

“…For the conventional approaches to shape-persistent macrocycles, many synthetic methods have been explored, including intermolecular coupling reaction between monomers, [98][99][100][101][102][103][104] and intramolecular cyclization of long linear precursors. [105][106][107] The former strategy involved just one step reaction, but byproducts with different member rings are inevitable, leading to a tedious separation process and quite low yields (4-6%).…”