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RESEARCH ARTICLE
Contents Vol 70(4)

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

Zuzana Baranová A , Hashem Amini A , Madhav Neupane A , Sydney C. Garrett A , Andreas Ehnbom A , Nattamai Bhuvanesh A , Joseph H. Reibenspies A and John A. Gladysz A B
+ Author Affiliations
- Author Affiliations

A Department of Chemistry, Texas A&M University, PO Box 30012, College Station, Texas 77843-3012, USA.

B Corresponding author. Email: gladysz@mail.chem.tamu.edu

Australian Journal of Chemistry 70(4) 373-386 https://doi.org/10.1071/CH16587
Submitted: 14 October 2016  Accepted: 16 November 2016   Published: 23 December 2016

Abstract

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 Å and 1.65–2.07 Å).


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