Syntheses, Structural Studies, and Copper Iodide Complexes of Macrocycles Derived from Williamson Ether Syntheses Involving 2,9-Bis(4-hydroxyphenyl)-1,10-phenanthroline, alpha,omega-Dibromides, and Resorcinol or 2,7-Dihydroxynaphthalene

摘要

1,3-Bis(6-bromohexyloxy)benzene, 2,7-bis(6-bromohexyloxy)naphthalene, 1,3-bis(4-bromomethylbenzyloxy)benzene, and 1,3-bis(3-bromomethylbenzyloxy)benzene were prepared via Williamson ether synthesis using resorcinol or 2,7-dihydroxynaphthalene and 1,6-dibromohexane, 1,4-bis(bromomethyl)benzene, or 1,3-bis(bromomethyl)benzene (21-47% yield). These dibromides were condensed with 2,9-bis(4-hydroxyphenyl)-1,10-phenanthroline in the presence of K2CO3 to give the corresponding 31- to 35-membered macrocycles (3a-d, 22-63% yield). When 3a-d were treated with CuI, mononuclear 1:1 complexes formed, in which the CuI chelates to the nitrogen donor atoms of the phenanthroline moiety (4a-d, 40-80% yield). The crystal structures of 3a-c and 4a-c were determined and analyzed using density functional theory calculations and in the context of rotaxanes that could be formed by treatment of 4a-d with terminal alkynes (e.g. macrocycle dimensions, void volumes). The copper and iodide atoms in 4a-c significantly protrude from the least-squares plane of the phenanthroline moiety (0.46-0.63 angstrom and 1.65-2.07 angstrom).