A fluorenylidene-acridane that becomes dark in color upon grinding-ground state mechanochromism by conformational change

Abstract

We report mechanochromic color change controlled by conformational change (between folded and twisted conformers) of fluorenylidene-acridanes (FAs). FAs with four N-alkyl groups (methyl, ethyl, n-butyl and n-octyl) were synthesized via the Barton-Kellogg reaction of diazofluorene and electrophilic N-tert-butoxy carbonyl thioacridone, deprotection of the tert-butoxy carbonyl group gives fluorenylacridine, and alkylation on the nitrogen atom is done using alkyl tosylate or triflate. FAs were characterized by NMR, UV-vis absorption and photoluminescence spectroscopy, theoretical calculation, cyclic voltammetry, and powder and single-crystal X-ray analyses. The color and folded/twisted conformation of the FAs were changed by the choice of substituent on the nitrogen atom, physical state (solution or solid), and morphology (crystalline or amorphous). Grinding of N-methyl FA solids, using an agate mortar, caused the morphology to change from a crystalline to amorphous state, which induced a conformational change from the folded to the twisted conformer, and a mechanochromic color change from yellow to dark green. The reverse color change, along with a morphological and conformational change to the folded conformer, was performed by solvent vapor exposure (chloroform). The twisted and folded conformers showed ambipolar (hole/electron) and hole-only transport properties, respectively.