Tunable Fluorescence in Two-Component Hydrogen-Bonded Organic Frameworks Based on Energy Transfer

Abstract

A dumbbell-shaped compound (TPAD) with four 2,4-diaminotriazine moieties as H-bond units and a benzene ring as a bridge group was found to form hydrogen-bonded organic frameworks (HOFs) with strong cyan fluorescence. An energy acceptor, 6,6',6″,6‴-(((benzo[c][1,2,5]thiadiazole-4,7-diylbis-(4,1-phenylene))bis(azanetriyl))tetrakis(benzene-4,1-diyl))tetrakis(1,3,5-triazine-2,4-diamine) (BTAD), with the same molecular skeleton as TPAD and a longer emission wavelength could homogeneously distribute within the framework of TPAD through occupying the locations of TPAD. As a result, two-component HOFs (TC-HOFs) were formed. The nonradiative energy transfer from TPAD as the donor to BTAD as the acceptor happens within frameworks owing to the efficient spectral overlap between the emission of TPAD and the absorption of BTAD. Moreover, the emission wavelengths and colors of TC-HOFs could be easily and continuously modulated by the content of the acceptor. The fluorescence color changed from cyan to orange when the content of BTAD gradually increased. This finding affirms that TC-HOFs with continuously adjustable composition can be constructed from two molecules with the same molecular skeleton, and highly efficient nonradiative energy transfer may happen in porous TC-HOFs. To the best of our knowledge, these TC-HOFs are the first example of TC-HOFs involved in energy transfer.