Transition-metal complexes are used as photosensitizers, in light-emitting diodes, for biosensing and in photocatalysis. A key feature in these applications is excitation from the ground state to a charge-transfer state; the long charge-transfer-state lifetimes typical for complexes of ruthenium and other precious metals are often essential to ensure high performance. There is much interest in replacing these scarce elements with Earth-abundant metals, with iron and copper being particularly attractive owing to their low cost and non-toxicity. But despite the exploration of innovative molecular designs, it remains a formidable scientific challenge to access Earth-abundant transition-metal complexes with long-lived charge-transfer excited states. No known iron complexes are considered photoluminescent at room temperature, and their rapid excited-state deactivation precludes their use as photosensitizers. Here we present the iron complex [Fe(btz)] (where btz is 3,3'-dimethyl-1,1'-bis(p-tolyl)-4,4'-bis(1,2,3-triazol-5-ylidene)), and show that the superior σ-donor and π-acceptor electron properties of the ligand stabilize the excited state sufficiently to realize a long charge-transfer lifetime of 100 picoseconds (ps) and room-temperature photoluminescence. This species is a low-spin Fe(iii) d complex, and emission occurs from a long-lived doublet ligand-to-metal charge-transfer (LMCT) state that is rarely seen for transition-metal complexes. The absence of intersystem crossing, which often gives rise to large excited-state energy losses in transition-metal complexes, enables the observation of spin-allowed emission directly to the ground state and could be exploited as an increased driving force in photochemical reactions on surfaces. These findings suggest that appropriate design strategies can deliver new iron-based materials for use as light emitters and photosensitizers.

Iron’s abundance and rich coordination chemistry are potentially appealing features for photochemical applications. However, the photoexcitable charge-transfer states of most iron complexes are limited by picosecond or subpicosecond deactivation through low-lying metal-centered states, resulting in inefficient electron-transfer reactivity and complete lack of photoluminescence. In this study, we show that octahedral coordination of iron(III) by two mono-anionic facialtris-carbene ligands can markedly suppress such deactivation. The resulting complex [Fe(phtmeimb)2]+, where phtmeimb is {phenyl[tris(3-methylimidazol-1-ylidene)]borate}−, exhibits strong, visible, room temperature photoluminescence with a 2.0-nanosecond lifetime and 2% quantum yield via spin-allowed transition from a doublet ligand-to-metal charge-transfer (2LMCT) state to the doublet ground state. Reductive and oxidative electron-transfer reactions were observed for the2LMCT state of [Fe(phtmeimb)2]+in bimolecular quenching studies with methylviologen and diphenylamine.

Although significant improvements have been achieved for organic photovoltaic cells (OPVs), the top-performing devices still show power conversion efficiencies far behind those of commercialized solar cells. One of the main reasons is the large driving force required for separating electron−hole pairs. Here, we demonstrate an efficiency of 14.7% in the single-junction OPV by using a new polymer donor PTO2 and a nonfullerene acceptor IT-4F. The device possesses an efficient charge generation at a low driving force. Ultrafast transient absorption measurements probe the formation of loosely bound charge pairs with extended lifetime that impedes the recombination of charge carriers in the blend. The theoretical studies reveal that the molecular electrostatic potential (ESP) between PTO2 and IT-4F is large, and the induced intermolecular electric field may assist the charge generation. The results suggest OPVs have the potential for further improvement by judicious modulation of ESP.

The iron carbene complex [Fe(btz)](PF) (where btz = 3,3'-dimethyl-1,1'-bis(p-tolyl)-4,4'-bis(1,2,3-triazol-5-ylidene)) has been synthesized, isolated, and characterized as a low-spin ferrous complex. It exhibits strong metal-to-ligand charge transfer (MLCT) absorption bands throughout the visible spectrum, and excitation of these bands gives rise to a MLCT state with a 528 ps excited-state lifetime in CHCN solution that is more than one order of magnitude longer compared with the MLCT lifetime of any previously reported Fe complex. The low potential of the [Fe(btz)]/[Fe(btz)] redox couple makes the MLCT state of [Fe(btz)] a potent photoreductant that can be generated by light absorption throughout the visible spectrum. Taken together with our recent results on the [Fe(btz)] form of this complex, these results show that the Fe and Fe oxidation states of the same Fe(btz) complex feature long-lived MLCT and LMCT states, respectively, demonstrating the versatility of iron N-heterocyclic carbene complexes as promising light-harvesters for a broad range of oxidizing and reducing conditions.

All-inorganic CsPbI3 perovskite quantum dots (QDs) have attracted intense attention for their successful application in photovoltaics (PVs) and optoelectronics that are enabled by their superior absorption capability and great photoluminescence (PL) properties. However, their photostability remains a practical bottleneck and further optimization is highly desirable. Here, we studied the photostability of as-obtained colloidal CsPbI3 QDs suspended in hexane. We found that light illumination does induce photodegradation of CsPbI3 QDs. Steady-state spectroscopy, X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, and transient absorption spectroscopy verified that light illumination leads to detachment of the capping agent, collapse of the CsPbI3 QD surface, and finally aggregation of surface Pb0. Both dangling bonds containing surface and Pb0 serve as trap states causing PL quenching with a dramatic decrease of PL quantum yield. Our work provides a detailed insight about the correlation between the structural and photophysical consequences of the photodegradation process in CsPbI3 QDs and may lead to the optimization of such QDs toward device applications.