Donor–Acceptor\nMOF Enabling Efficient Electrochemiluminescence\nBased on TSCT-TADF

Electrochemiluminescence (ECL) is an extensively studied\nluminescence\ntechnique recognized for its efficacy in investigating surface energy\nstates. Effective utilization of ECL to explore and probe the charge\ntransfer mechanisms facilitated by novel luminescent materials is\ncrucial. In this study, we demonstrate thermally activated delayed\nfluorescence (TADF) based on spatial charge transfer through the precisely\ncontrolled synthesis of luminescent materials, which is achieved by\nincorporating phenyl-carbazole derivatives as donor guests within\nacceptor-hosted metal–organic frameworks (D-A MOFs). These\nhybrid structures exhibit superior ECL intensities compared with their\nmonomeric counterparts. Mechanistic investigation by DFT calculation\nreveals that the physically separated yet spatially closed D-A configuration\ninduces efficient intermolecular through-spatial charge transfer (TSCT),\nleading to efficient ECL through tuning of the dihedral angle of the\nguest molecules to enhance π–π interactions. This\nstudy introduces a strategy for precise modulation of spatial charge\ntransfer at the molecular level in the programmable synthesis of ECL\nluminophores.