当前位置：
X-MOL 学术
›
Chem. Sci.
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
Highly conducting Wurster-type twisted covalent organic frameworks
Chemical Science ( IF 7.6 ) Pub Date : 2020-10-27 , DOI: 10.1039/d0sc03909h Julian M. Rotter 1, 2, 3, 4 , Roman Guntermann 1, 2, 3, 4 , Michael Auth 4, 5, 6, 7 , Andre Mähringer 1, 2, 3, 4 , Andreas Sperlich 4, 5, 6, 7 , Vladimir Dyakonov 4, 5, 6, 7 , Dana D. Medina 1, 2, 3, 4 , Thomas Bein 1, 2, 3, 4
Chemical Science ( IF 7.6 ) Pub Date : 2020-10-27 , DOI: 10.1039/d0sc03909h Julian M. Rotter 1, 2, 3, 4 , Roman Guntermann 1, 2, 3, 4 , Michael Auth 4, 5, 6, 7 , Andre Mähringer 1, 2, 3, 4 , Andreas Sperlich 4, 5, 6, 7 , Vladimir Dyakonov 4, 5, 6, 7 , Dana D. Medina 1, 2, 3, 4 , Thomas Bein 1, 2, 3, 4
Affiliation
|
Covalent organic frameworks (COFs) define a versatile structural paradigm combining attractive properties such as crystallinity, porosity, and chemical and structural modularity which are valuable for various applications. For the incorporation of COFs into optoelectronic devices, efficient charge carrier transport and intrinsic conductivity are often essential. Here, we report the synthesis of two imine-linked two-dimensional COFs, WTA and WBDT, featuring a redox-active Wurster-type motif based on the twisted tetragonal N,N,N′,N′-tetraphenyl-1,4-phenylenediamine node. By condensing this unit with either terephthalaldehyde (TA) or benzodithiophene dialdehyde (BDT), COFs featuring a dual-pore kagome-type structure were obtained as highly crystalline materials with large specific surface areas and mesoporosity. In addition, the experimentally determined high conduction band energies of both COFs render them suitable candidates for oxidative doping. The incorporation of a benzodithiophene linear building block into the COF allows for high intrinsic macroscopic conductivity. Both anisotropic and average isotropic electrical conductivities were determined with van der Pauw measurements using oriented films and pressed pellets, respectively. Furthermore, the impact of different dopants such as F4TCNQ, antimony pentachloride and iodine on the conductivities of the resulting doped COFs was studied. By using the strong organic acceptor F4TCNQ, a massive increase of the radical cation density (up to 0.5 radicals per unit cell) and long-term stable electrical conductivity as high as 3.67 S m−1 were achieved for the anisotropic transport in an oriented film, one of the highest for any doped COF to date. Interestingly, no significant differences between isotropic and anisotropic charge transport were found in films and pressed pellets. This work expands the list of possible building nodes for electrically conducting COFs from planar systems to twisted geometries. The achievement of high and stable electrical conductivity paves the way for possible applications of new COFs in organic (opto)electronics.
中文翻译：
高传导性的Wurster型扭曲共价有机骨架
共价有机骨架（COF）定义了一种通用的结构范式，结合了诸如结晶度，孔隙率以及化学和结构模块性等吸引人的特性，这些特性对于各种应用都很有价值。对于将COF集成到光电设备中，有效的电荷载流子传输和固有电导率通常是必不可少的。在这里，我们报告两个亚胺连接的二维COFs，WTA和WBDT的合成，其特征在于基于扭曲的四边形N，N，N ′，N的氧化还原活性Wurster型基序′-四苯基-1，4-苯二胺节点。通过将该单元与对苯二甲醛（TA）或苯并二噻吩二醛（BDT）进行缩合，可得到具有双孔kagome型结构的COF，是具有大比表面积和介孔性的高度结晶材料。此外，实验确定的两种COF的高导带能量都使其成为氧化掺杂的合适候选物。将苯并二噻吩线性结构单元并入COF可实现较高的固有宏观电导率。各向异性电导率和平均各向同性电导率分别通过使用定向膜和压制颗粒的van der Pauw测量确定。此外，不同掺杂物（例如F 4）的影响研究了TCNQ，五氯化锑和碘对所得掺杂COFs电导率的影响。通过使用强有机受体F 4 TCNQ，自由基阳离子密度大大增加（每个晶胞高达0.5个自由基），长期稳定的电导率高达3.67 S m -1在定向薄膜中各向异性传输达到了最高，这是迄今为止任何掺杂的COF中最高的。有趣的是，在薄膜和压丸中，各向同性和各向异性电荷传输之间没有显着差异。这项工作扩展了用于将COF从平面系统传导到扭曲几何形状的可能的建筑节点的清单。高而稳定的电导率的实现为新型COF在有机（光电）电子领域的可能应用铺平了道路。
更新日期：2020-11-25
中文翻译：
高传导性的Wurster型扭曲共价有机骨架
共价有机骨架（COF）定义了一种通用的结构范式，结合了诸如结晶度，孔隙率以及化学和结构模块性等吸引人的特性，这些特性对于各种应用都很有价值。对于将COF集成到光电设备中，有效的电荷载流子传输和固有电导率通常是必不可少的。在这里，我们报告两个亚胺连接的二维COFs，WTA和WBDT的合成，其特征在于基于扭曲的四边形N，N，N ′，N的氧化还原活性Wurster型基序′-四苯基-1，4-苯二胺节点。通过将该单元与对苯二甲醛（TA）或苯并二噻吩二醛（BDT）进行缩合，可得到具有双孔kagome型结构的COF，是具有大比表面积和介孔性的高度结晶材料。此外，实验确定的两种COF的高导带能量都使其成为氧化掺杂的合适候选物。将苯并二噻吩线性结构单元并入COF可实现较高的固有宏观电导率。各向异性电导率和平均各向同性电导率分别通过使用定向膜和压制颗粒的van der Pauw测量确定。此外，不同掺杂物（例如F 4）的影响研究了TCNQ，五氯化锑和碘对所得掺杂COFs电导率的影响。通过使用强有机受体F 4 TCNQ，自由基阳离子密度大大增加（每个晶胞高达0.5个自由基），长期稳定的电导率高达3.67 S m -1在定向薄膜中各向异性传输达到了最高，这是迄今为止任何掺杂的COF中最高的。有趣的是，在薄膜和压丸中，各向同性和各向异性电荷传输之间没有显着差异。这项工作扩展了用于将COF从平面系统传导到扭曲几何形状的可能的建筑节点的清单。高而稳定的电导率的实现为新型COF在有机（光电）电子领域的可能应用铺平了道路。
京公网安备 11010802027423号