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Luminescence of open-shell 3d metal complexes is often quenched due toultrafast intersystem crossing (ISC) and cooling into a dark metal-centeredexcited state. We demonstrate successful activation of fluorescence fromindividual nickel phthalocyanine (NiPc) molecules in the junction of a scanningtunneling microscope (STM) by resonant energy transfer from other metalphthalocyanines at low temperature. By combining STM, scanning tunnelingspectroscopy, STM- induced luminescence, and photoluminescence experiments aswell as time-dependent density functional theory, we provide evidence thatthere is an activation barrier for the ISC, which in most experimentalconditions is overcome. We show that this is also the case in anelectroluminescent tunnel junction where individual NiPc molecules adsorbed onan ultrathin NaCl decoupling film on a Ag(111) substrate are probed. However,when placing an MPc (M = Zn, Pd, Pt) molecule close to NiPc by means of STMatomic manipulation, resonant energy transfer can excite NiPc withoutovercoming the ISC activation barrier, leading to Q-band fluorescence. Thiswork demonstrates that the thermally activated population of darkmetal-centered states can be avoided by a designed local environment at lowtemperatures paired with a directed molecular excitation into vibrationallycold electronic states. Thus, we can envisage the use of luminophores based onmore abundant transition metal complexes that do not rely on Pt or Ir.

Activating the fluorescence of a Ni(II) complex by energy transfer