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Captivating bimolecular photoredox dynamics of a ligand-to-metal charge transfer complex

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Názov: Captivating bimolecular photoredox dynamics of a ligand-to-metal charge transfer complex
Autori: Wegeberg, Christina, Calvet, Neus A., Krafft, Mila, Chábera, Pavel, Yartsev, Arkady, Persson, Petter
Prispievatelia: Lund University, Faculty of Engineering, LTH, LTH Profile areas, LTH Profile Area: Nanoscience and Semiconductor Technology, Lunds universitet, Lunds Tekniska Högskola, LTH profilområden, LTH profilområde: Nanovetenskap och halvledarteknologi, Originator, Lund University, Profile areas and other strong research environments, Lund University Profile areas, LU Profile Area: Light and Materials, Lunds universitet, Profilområden och andra starka forskningsmiljöer, Lunds universitets profilområden, LU profilområde: Ljus och material, Originator, Lund University, Profile areas and other strong research environments, Strategic research areas (SRA), NanoLund: Centre for Nanoscience, Lunds universitet, Profilområden och andra starka forskningsmiljöer, Strategiska forskningsområden (SFO), NanoLund: Centre for Nanoscience, Originator, Lund University, Faculty of Science, Department of Chemistry, Physical and theoretical chemistry, Chemical Physics, Lunds universitet, Naturvetenskapliga fakulteten, Kemiska institutionen, Enheten för fysikalisk och teoretisk kemi, Kemisk fysik, Originator, Lund University, Faculty of Engineering, LTH, LTH Profile areas, LTH Profile Area: Photon Science and Technology, Lunds universitet, Lunds Tekniska Högskola, LTH profilområden, LTH profilområde: Avancerade ljuskällor, Originator, Lund University, Profile areas and other strong research environments, Strategic research areas (SRA), eSSENCE: The e-Science Collaboration, Lunds universitet, Profilområden och andra starka forskningsmiljöer, Strategiska forskningsområden (SFO), eSSENCE: The e-Science Collaboration, Originator, Lund University, Faculty of Science, Department of Chemistry, Physical and theoretical chemistry, Computational Chemistry, Lunds universitet, Naturvetenskapliga fakulteten, Kemiska institutionen, Enheten för fysikalisk och teoretisk kemi, Beräkningskemi, Originator
Zdroj: Chemical Science. 16(46):21975-21990
Predmety: Natural Sciences, Chemical Sciences, Physical Chemistry (including Surface- and Colloid Chemistry), Naturvetenskap, Kemi, Fysikalisk kemi (Här ingår: Yt- och kolloidkemi)
Popis: Transition metal complexes featuring ligand-to-metal charge transfer (LMCT) excited states have been identified as promising candidates for driving electron transfer processes. To obtain an efficient system based on photo-induced bimolecular electron transfer, it is required that (1) photo-induced charge separation (CS) is faster than charge recombination (CR) of the separated charges, and (2) CR is slower than their spatial separation via cage escape (CE). Here, we investigate this competitive sequence of processes by the photocycle of a rhenium(II) complex featuring a strongly oxidizing 2LMCT excited state. Intrinsic CS and CR rates were measured up to multimolar concentrations for several electron donors to elucidate both the diffusion-controlled and close-contact regimes over a wide range of thermodynamic driving forces. Ultrafast dynamics (<200 fs) suggest that CS is dominated by a hot electron transfer component competing with 2LMCT vibrational relaxations in the high-concentration/close-contact regime.The intrinsic CS and CR rates related to the relaxed 2LMCT state dominate the dynamics at intermediate concentrations and show concentration-dependence at 3–50 vol% electron donor concentration and concentration-independence at higher concentrations with τCS = 0.5 ps and τCR = 2 ps, for the prototype donor anisole. The ratio between CS and CR rates was altered systematically by the thermodynamic driving force of electron transfer, utilizing the fact that the processes lie in the Marcus normal and inverted regions, respectively, and with deviations from classical Marcus behavior accounted for by using Marcus–Jortner–Levich theory. Our findings provide unique insight into the complex competition between kinetic factors controlling the fundamental dynamics of the charge-separated pairs inside the solvent cage for photocycles driven by 2LMCT excited states.
Prístupová URL adresa: https://doi.org/10.1039/d5sc03839a
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  Data: Transition metal complexes featuring ligand-to-metal charge transfer (LMCT) excited states have been identified as promising candidates for driving electron transfer processes. To obtain an efficient system based on photo-induced bimolecular electron transfer, it is required that (1) photo-induced charge separation (CS) is faster than charge recombination (CR) of the separated charges, and (2) CR is slower than their spatial separation via cage escape (CE). Here, we investigate this competitive sequence of processes by the photocycle of a rhenium(II) complex featuring a strongly oxidizing 2LMCT excited state. Intrinsic CS and CR rates were measured up to multimolar concentrations for several electron donors to elucidate both the diffusion-controlled and close-contact regimes over a wide range of thermodynamic driving forces. Ultrafast dynamics (&lt;200 fs) suggest that CS is dominated by a hot electron transfer component competing with 2LMCT vibrational relaxations in the high-concentration/close-contact regime.The intrinsic CS and CR rates related to the relaxed 2LMCT state dominate the dynamics at intermediate concentrations and show concentration-dependence at 3–50 vol% electron donor concentration and concentration-independence at higher concentrations with τCS = 0.5 ps and τCR = 2 ps, for the prototype donor anisole. The ratio between CS and CR rates was altered systematically by the thermodynamic driving force of electron transfer, utilizing the fact that the processes lie in the Marcus normal and inverted regions, respectively, and with deviations from classical Marcus behavior accounted for by using Marcus–Jortner–Levich theory. Our findings provide unique insight into the complex competition between kinetic factors controlling the fundamental dynamics of the charge-separated pairs inside the solvent cage for photocycles driven by 2LMCT excited states.
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