Iron Photoredox Catalysis-Past, Present, and Future.

Photoredox catalysis of organic reactions driven by iron has attracted substantial attention throughout recent years, due to potential environmental and economic benefits. In this Perspective, three major strategies were identified that have been employed to date to achieve reactivities comparable to the successful noble metal photoredox catalysis: (1) Direct replacement of a noble metal center by iron in archetypal polypyridyl complexes, resulting in a metal-centered photofunctional state. (2) In situ generation of photoactive complexes by substrate coordination where the reactions are driven via intramolecular electron transfer involving charge-transfer states, for example, through visible-light-induced homolysis. (3) Improving the excited-state lifetimes and redox potentials of the charge-transfer states of iron complexes through new ligand design. We seek to give an overview and evaluation of recent developments in this rapidly growing field and, at the same time, provide an outlook on the future of iron-based photoredox catalysis.

High-Efficiency Photoinduced Charge Separation in Fe(III)carbene Thin Films.

Symmetry-breaking charge separation in molecular materials has attracted increasing attention for optoelectronics based on single-material active layers. To this end, Fe(III) complexes with particularly electron-donating N-heterocyclic carbene ligands offer interesting properties with a 2LMCT excited state capable of oxidizing or reducing the complex in its ground state. In this Communication, we show that the corresponding symmetry-breaking charge separation occurs in amorphous films of pristine [Fe(III)L2]PF6 (L = [phenyl(tris(3-methylimidazol-2-ylidene))borate]-). Excitation of the solid material with visible light leads to ultrafast electron transfer quenching of the 2LMCT excited state, generating Fe(II) and Fe(IV) products with high efficiency. Sub-picosecond charge separation followed by recombination in about 1 ns could be monitored by transient absorption spectroscopy. Photoconductivity measurements of films deposited on microelectrode arrays demonstrated that photogenerated charge carriers can be collected at external contacts.

Monitoring training load in youth soccer players: effects of a six-week preparatory training program and the association between external and internal loads.

This study examined the effects of a six-week preparatory training program on physical performance and physiological adaptations in junior soccer players. Additionally, we investigated whether a relationship existed between external and internal loads. Youth soccer players (aged 16 years old) from a youth football academy participated in six weeks of pre-conditioning training. Wireless Polar Team Pro and Polar heart rate sensors (H10) were used to monitor physical performance indicators (sprint and acceleration scores, covered distance, maximum and average speed and duration), physiological responses (maximum and average heart rate [HR] and R-R interval, time in HR zones 4+5, and heart rate variability [HRV]), and training load score. Additionally, muscle status and rating of perceived exertion (RPE) scores were measured using digital questionnaires. Significant increases were observed in the majority of physical performance indicators [i.e., sprints (p = 0.015, ES = 1.02), acceleration (p = 0.014, ES = 1), total distance (p = 0.02, ES = 0.87), as well as maximum speed (p = 0.02, ES = 0.87)]. A trend towards improvement was observed in the remaining performance indicators (i.e., distance/min and avg speed; ES = 0.6), training load (ES = 0.2), muscle status (ES = 0.3)), and all physiological responses parameters (ES = 0.1 to 0.6). Significant correlations were found between the majority of external load parameters (i.e., performance indicators) and objective (i.e., physiological responses) and subjective (i.e., RPE, muscle status) internal load parameters (p < 0.001). The highest number of moderate-large correlations were registered between performance indicators and time in HR zone 4+5 (0.58 < r < 0.82), training load (0.53 < r < 0.83), average HR (0.50 < r < 0.87), maximal HR (0.51 < r < 0.54) and average R-R interval (0.58 < r < 0.76). HR zone 4+5, average and maximal HR, average R-R interval, and training load score may help control training parameters and reduce the risk of under- or over-training in youth soccer players. However, these conclusions should be confirmed and replicated in future studies with more diverse subject populations.

Photophysical Integrity of the Iron(III) Scorpionate Framework in Iron(III)-NHC Complexes with Long-Lived 2LMCT Excited States.

Fe(III) complexes with N-heterocyclic carbene (NHC) ligands belong to the rare examples of Earth-abundant transition metal complexes with long-lived luminescent charge-transfer excited states that enable applications as photosensitizers for charge separation reactions. We report three new hexa-NHC complexes of this class: [Fe(brphtmeimb)2]PF6 (brphtmeimb = [(4-bromophenyl)tris(3-methylimidazol-2-ylidene)borate]-, [Fe(meophtmeimb)2]PF6 (meophtmeimb = [(4-methoxyphenyl)tris(3-methylimidazol-2-ylidene)borate]-, and [Fe(coohphtmeimb)2]PF6 (coohphtmeimb = [(4-carboxyphenyl)tris(3-methylimidazol-2-ylidene)borate]-. These were derived from the parent complex [Fe(phtmeimb)2]PF6 (phtmeimb = [phenyltris(3-methylimidazol-2-ylidene)borate]- by modification with electron-withdrawing and electron-donating substituents, respectively, at the 4-phenyl position of the ligand framework. All three Fe(III) hexa-NHC complexes were characterized by NMR spectroscopy, high-resolution mass spectroscopy, elemental analysis, single crystal X-ray diffraction analysis, electrochemistry, Mößbauer spectroscopy, electronic spectroscopy, magnetic susceptibility measurements, and quantum chemical calculations. Their ligand-to-metal charge-transfer (2LMCT) excited states feature nanosecond lifetimes (1.6-1.7 ns) and sizable emission quantum yields (1.7-1.9%) through spin-allowed transition to the doublet ground state (2GS), completely in line with the parent complex [Fe(phtmeimb)2]PF6 (2.0 ns and 2.1%). The integrity of the favorable excited state characteristics upon substitution of the ligand framework demonstrates the robustness of the scorpionate motif that tolerates modifications in the 4-phenyl position for applications such as the attachment in molecular or hybrid assemblies.

Competing dynamics of intramolecular deactivation and bimolecular charge transfer processes in luminescent Fe(iii) N-heterocyclic carbene complexes.

Steady state and ultrafast spectroscopy on [FeIII(phtmeimb)2]PF6 (phtmeimb = phenyl(tris(3-methylimidazol-2-ylidene))borate) was performed over a broad range of temperatures. The intramolecular deactivation dynamics of the luminescent doublet ligand-to-metal charge-transfer (2LMCT) state was established based on Arrhenius analysis, indicating the direct deactivation of the 2LMCT state to the doublet ground state as a key limitation to the lifetime. In selected solvent environments photoinduced disproportionation generating short-lived Fe(iv) and Fe(ii) complex pairs that subsequently undergo bimolecular recombination was observed. The forward charge separation process is found to be temperature-independent with a rate of ∼1 ps-1. Subsequent charge recombination takes place in the inverted Marcus region with an effective barrier of 60 meV (483 cm-1). Overall, the photoinduced intermolecular charge separation efficiently outcompetes the intramolecular deactivation over a broad range of temperatures, highlighting the potential of [FeIII(phtmeimb)2]PF6 to perform photocatalytic bimolecular reactions.

Ferrous and ferric complexes with cyclometalating N-heterocyclic carbene ligands: a case of dual emission revisited.

Iron N-heterocyclic carbene (FeNHC) complexes with long-lived charge transfer states are emerging as a promising class of photoactive materials. We have synthesized [FeII(ImP)2] (ImP = bis(2,6-bis(3-methylimidazol-2-ylidene-1-yl)phenylene)) that combines carbene ligands with cyclometalation for additionally improved ligand field strength. The 9 ps lifetime of its 3MLCT (metal-to-ligand charge transfer) state however reveals no benefit from cyclometalation compared to Fe(ii) complexes with NHC/pyridine or pure NHC ligand sets. In acetonitrile solution, the Fe(ii) complex forms a photoproduct that features emission characteristics (450 nm, 5.1 ns) that were previously attributed to a higher (2MLCT) state of its Fe(iii) analogue [FeIII(ImP)2]+, which led to a claim of dual (MLCT and LMCT) emission. Revisiting the photophysics of [FeIII(ImP)2]+, we confirmed however that higher (2MLCT) states of [FeIII(ImP)2]+ are short-lived (<10 ps) and therefore, in contrast to the previous interpretation, cannot give rise to emission on the nanosecond timescale. Accordingly, pristine [FeIII(ImP)2]+ prepared by us only shows red emission from its lower 2LMCT state (740 nm, 240 ps). The long-lived, higher energy emission previously reported for [FeIII(ImP)2]+ is instead attributed to an impurity, most probably a photoproduct of the Fe(ii) precursor. The previously reported emission quenching on the nanosecond time scale hence does not support any excited state reactivity of [FeIII(ImP)2]+ itself.

High turnover photocatalytic hydrogen formation with an Fe(III) N-heterocyclic carbene photosensitiser.

Herein we report the first high turnover photocatalytic hydrogen formation reaction based on an earth-abundant FeIII-NHC photosensitiser. The reaction occurs via reductive quenching of the 2LMCT excited state that can be directly excited with green light and employs either Pt-colloids or [Co(dmgH)2pyCl] as proton reduction catalysts and [HNEt3][BF4] and triethanolamine/triethylamine as proton and electron donors. The outstanding photostability of the FeIII-NHC complex enables turnover numbers >1000 without degradation.

Photoredox catalysis via consecutive 2LMCT- and 3MLCT-excitation of an Fe(iii/ii)-N-heterocyclic carbene complex.

Fe-N-heterocyclic carbene (NHC) complexes attract increasing attention as photosensitisers and photoredox catalysts. Such applications generally rely on sufficiently long excited state lifetimes and efficient bimolecular quenching, which leads to there being few examples of successful usage of Fe-NHC complexes to date. Here, we have employed [Fe(iii)(btz)3]3+ (btz = (3,3'-dimethyl-1,1'-bis(p-tolyl)-4,4'-bis(1,2,3-triazol-5-ylidene))) in the addition of alkyl halides to alkenes and alkynes via visible light-mediated atom transfer radical addition (ATRA). Unlike other Fe-NHC complexes, [Fe(iii/ii)(btz)3]3+/2+ benefits from sizable charge transfer excited state lifetimes ≥0.1 ns in both oxidation states, and the Fe(iii) 2LMCT and Fe(ii) 3MLCT states are strong oxidants and reductants, respectively. The combined reactivity of both excited states enables efficient one-electron reduction of the alkyl halide substrate under green light irradiation. The two-photon mechanism proceeds via reductive quenching of the Fe(iii) 2LMCT state by a sacrificial electron donor and subsequent excitation of the Fe(ii) product to its highly reducing 3MLCT state. This route is shown to be more efficient than the alternative, where oxidative quenching of the less reducing Fe(iii) 2LMCT state by the alkyl halide drives the reaction, in the absence of a sacrificial electron donor.