Synthesis of a Helical Analogue of Kekulene: A Flexible π-Expanded Helicene with Large Helical Diameter Acting as a Soft Molecular Spring.

Abstract

A π-expanded helicene that is the helically twisted analogue of kekulene was synthesized using a 6-fold ring-closing olefin metathesis (RCM) reaction as a key step. The π-expanded geometry with large helical diameter ( dh = 10.2 Å), consisting only of carbon and hydrogen atoms (C54H30), was unambiguously determined by single-crystal X-ray analysis. We found that the π-expanded helicene with large helical diameter will act as a soft molecular spring with a small spring constant. Interestingly, the mechanical properties of the molecular springs roughly satisfied a physical formula for macroscopic spring materials; i.e., the force constant of the elongation of a molecular spring ( k) is inversely proportional to the third power of the helical diameter ( k ∝ dh-3).