Conformational Dynamics of Monomer- versus Dimer-like Features in a Naphthalenediimide-Based Conjugated Cyclophane

Angew Chem Int Ed Engl. 2020 Mar 23;59(13):5254-5258. doi: 10.1002/anie.201914414. Epub 2020 Feb 4.

Abstract

The design and synthesis of an enantiomeric pair of 1,8-diethynylanthracene-bridged naphthalenediimide (NDI)-based cyclophanes (Cyclo-NDIs) are reported. Each enantiomer of Cyclo-NDI exhibits a circularly polarized luminescence signal with a relatively large luminescence dissymmetry factor (glum =±8×10-3 ). We have further investigated the modulation of through-space electronic communication between co-facially oriented NDIs in a discrete Cyclo-NDI with changes in the temperature. Tuning of the electronic communication results from the conformational transformation of monomer- versus dimer-like features of Cyclo-NDI, as confirmed by UV/Vis, fluorescence, circular dichroic, and NMR spectroscopic analysis. The temperature-dependent optical response in the Cyclo-NDI through the conformational transformation could be utilized as a highly sensitive and reversible optical thermometer in a wide temperature range (100 to -80 °C).

Keywords: circularly polarized luminescence; conformational transformations; cyclophanes; naphthalenediimide dimers; optical thermometry.