González Susana, Martín Nazario, Guldi Dirk M
Radiation Laboratory, University of Notre Dame, Notre Dame, Indiana 46556, USA.
J Org Chem. 2003 Feb 7;68(3):779-91. doi: 10.1021/jo020412l.
Novel C(60)/pi-extended tetrathiafulvalene (exTTF) diads (12a-c) and triads [D(2)A (14a-c) and DA(2) (25, 27a-c)] have been synthesized by the Bingel cyclopropanation reaction of the respective exTTF-containing malonates and [60]fullerene. The reaction of exTTF-bismalonates with C(60) affords the respective C(60)-exTTF diads (26a-c) together with the triad C(60)-exTTF-C(60) (25, 27a-c) and a regioisomeric mixture of bisadducts (28b-c). Theoretical calculations (PM3) predict the favored geometry for triads 14a-c depending upon the orientation (up and down) of the 1,3-dithiole rings in the exTTFs, as well as the more stable regioisomers for the bisadducts 28. Cyclic voltammetry measurements reveal that C(60) and exTTF units do not intereact in the ground state. Compounds 26a-c and 27a-c are not electrochemically stable. A photoinduced electron transfer leading to the formation of the radical pair (C(60)(-)-exTTF(*+)) has been observed for compounds 14a-c.
新型C(60)/π-扩展四硫富瓦烯（exTTF）二元化合物（12a - c）和三元化合物[D(2)A（14a - c）和DA(2)（25、27a - c）]已通过相应含exTTF的丙二酸酯与[60]富勒烯的宾格尔环丙烷化反应合成。exTTF - 双丙二酸酯与C(60)反应生成相应的C(60)-exTTF二元化合物（26a - c）以及三元化合物C(60)-exTTF-C(60)（25、27a - c）和双加合物的区域异构体混合物（28b - c）。理论计算（PM3）根据exTTF中1,3 - 二硫杂环的取向（向上和向下）预测了三元化合物14a - c的有利几何构型，以及双加合物28更稳定的区域异构体。循环伏安法测量表明，C(60)和exTTF单元在基态下不相互作用。化合物26a - c和27a - c在电化学上不稳定。已观察到化合物14a - c发生光诱导电子转移导致形成自由基对（C(60)(-)-exTTF(*+)）。
