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首页> 外文期刊>Chemistry: A European journal >Novel Extended Tetrathiafulvalenes Based on Acetylenic Spacers: Sybnthesis and Electronic Properties
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Novel Extended Tetrathiafulvalenes Based on Acetylenic Spacers: Sybnthesis and Electronic Properties

机译：基于乙炔间隔基的新型扩展四硫富瓦烯：合成和电子性质

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摘要

A selection of mono-and diacetylenic dithiafulvalenes was synthesized and employed for the construction of extended tetrahiafulvalenes (TTFs) with hexa-2,4-diyne-1m,6-diylidene or deca-2,4,6m,8-tetrayne-1,10-diylidene spacers between the two 1,3-dithiole rings. By stepwise acetylenic scaffolding using (E)-1,2-diethynylethene (DEE) building blocks, an extended TTF containing a total of 18 C(sp) and C(sp~2) atoms in the spacer was prepared. The versatility of the acetylenic dithiafulvene modules was also established by the efficient synthesis of a thiophene-spaced TTF, employing a palladium-catalyzed cross-coupling reaction. The developed synthetic protocols allow functionalization of the extended TTFs in three general ways: with 1) peripheral substituents on the fulvalene cores, 2) alkynyl moieties laterally appended to the spacer, and 3) cobalt clusters involving acetylenic moieties. Strong chromophoric properties of the extended TTFs were revealed by linear and nonlinear optical spectrsocopies. Extensive electrochemical studies and calculations on these compounds are also reported, as well as X-ray crystallographic analyses.
机译：合成了一些单和二炔二硫富富烯，并将其用于构建带有hexa-2,4-diyne-1m，6-diylidene或deca-2,4,6m，8-tetrayne-1的扩展四硫富瓦烯（TTF），两个1,3-二硫醇环之间的10-二亚甲基间隔基。通过使用（E）-1,2-二乙炔（DEE）构件逐步进行炔基骨架制备，制备了在间隔物中总共包含18个C（sp）和C（sp〜2）原子的扩展TTF。还通过钯催化的交叉偶联反应，通过噻吩间隔的TTF的有效合成，建立了乙炔二硫富烯模块的多功能性。已开发的合成方案允许以三种通用方式对扩展的TTF进行功能化：1）在富马烯核上的周边取代基，2）侧向连接至间隔基的炔基部分和3）涉及炔基部分的钴簇。线性和非线性光学光谱揭示了扩展的TTF的强发色性质。还报道了对这些化合物的广泛电化学研究和计算，以及X射线晶体学分析。

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