Femto- to Millisecond Time-Resolved Photodynamics of a Double-Functionalized Push–Pull Organic Linker: Potential Candidate for Optoelectronically Active MOFs

Abstract

The design of improved organic linkers for the further engineering of smarter metal–organic framework (MOF) materials has become a paramount task for a wide number of material scientists. In this report, a luminescent double-functionalized push–pull (electron donor–acceptor) archetype organic molecule, dimethyl 4-amino-8-cyanonaphthalene-2,6-dicarboxylate (Me2CANADC), has been synthesized and characterized. The optical steady-state properties of Me2CANADC are strongly influenced by the surrounding environment as a direct consequence of its strong charge transfer (CT) character. The relaxation from its first electronically excited singlet state follows a double pathway: (1) on one side deactivating from its local excited (LE) state in the sub-picosecond or picosecond time domain, and (2) on the other side undergoing an ultrafast intramolecular charge transfer (ICT) reaction that is slowing down in viscous solvents. The deactivation to the ground state of these species with CT character is the origin of the Me2CANADC luminescence, and they present solvent-dependent lifetime values ranging from 8 to 18 ns. The slow photodynamics of Me2CANADC unveils the coexistence of a non-emissive triplet excited state and the formation of a long-lived charge separated state (2 µs). These observations highlight the promising optical properties of Me2CANADC linker, opening a window for the design of new functional MOFs with huge potential to be applied in the fields of luminescent sensing and optoelectronics.

Keywords

• intramolecular charge transfer
• ultrafast spectroscopy
• photochemistry
• solvatochromism