Nielsen Mogens Brøndsted, Utesch Nils F, Moonen Nicolle N P, Boudon Corinne, Gisselbrecht Jean-Paul, Concilio Simona, Piotto Stefano P, Seiler Paul, Günter Peter, Gross Maurice, Diederich François
Laboratorium für Organische Chemie, ETH-Hönggerberg, HCI 8093 Zürich, Switzerland.
Chemistry. 2002 Aug 16;8(16):3601-13. doi: 10.1002/1521-3765(20020816)8:16<3601::AID-CHEM3601>3.0.CO;2-N.
A selection of mono- and diacetylenic dithiafulvalenes was synthesized and employed for the construction of extended tetrathiafulvalenes (TTFs) with hexa-2,4-diyne-1,6-diylidene or deca-2,4,6,8-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 spectroscopies. Extensive electrochemical studies and calculations on these compounds are also reported, as well as X-ray crystallographic analyses.
合成了一系列单乙炔和二乙炔二硫富瓦烯，并用于构建在两个1,3 - 二硫杂环戊烯环之间带有己 - 2,4 - 二炔 - 1,6 - 二亚基或癸 - 2,4,6,8 - 四炔 - 1,10 - 二亚基间隔基的扩展四硫富瓦烯（TTF）。通过使用（E）-1,2 - 二乙炔基乙烯（DEE）构建块进行逐步炔烃骨架构建，制备了一种在间隔基中总共含有18个C(sp)和C(sp²)原子的扩展TTF。通过钯催化的交叉偶联反应高效合成噻吩间隔的TTF，也证明了炔烃二硫富烯模块的通用性。所开发的合成方案允许以三种一般方式对扩展TTF进行功能化：1）在富瓦烯核上带有外围取代基，2）在间隔基上横向连接炔基部分，3）涉及炔基部分的钴簇。扩展TTF的强发色特性通过线性和非线性光谱学得以揭示。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。
