Molecular compasses and gyroscopes. II. Synthesis and characterization of molecular rotors with axially substituted bis[2-(9-triptycyl)ethynyl]arenes

被引:138
作者
Godinez, CE
Zepeda, G
Garcia-Garibay, MA [1 ]
机构
[1] Univ Calif Los Angeles, Dept Biochem & Chem, Los Angeles, CA 90095 USA
[2] IPN, Escuela Nacl Ciencias Biol, Dept Quim Organ, Mexico City 11340, DF, Mexico
关键词
D O I
10.1021/ja012550i
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
We have developed a simple convergent procedure for the synthesis of molecular rotors consisting of a central aromatic group coupled with two axially positioned ethynyltriptycenes. Molecular rotors with 1,4-phenylene (1), 1,4'-1,1'-biphenylene (2), 9,10-anthracenylene (3), and 2,7-pyrenylene (4) groups were prepared by Pd(0)-catalyzed coupling of ethynyl triptycenes with the corresponding dibromoarenes. Although compounds 1-4 were not expected to have free rotation in the solid state, the rotational potentials of 1 and 3 were analyzed by semiempirical methods and the crystal packing of 1 was analyzed to design the structures most likely to yield a functional rotor in the solid state. Semiempirical PM3 calculations predict compounds 1, 2, and 4 to have frictionless internal rotation even at temperatures as low as 25 K, while compound 3 is expected to have a barrier of ca. 4 kcal/mol.
引用
收藏
页码:4701 / 4707
页数:7
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