A photosensitizer–polyoxometalate dyad that enables the decoupling of light and dark reactions for delayed on-demand solar hydrogen production

Amthor, Sebastian; Knoll, Sebastian; Heiland, Magdalena; Zedler, Linda; Li, Chunyu; Nauroozi, Djawed; Tobaschus, Willi; Mengele, Alexander K.; Anjass, Montaha; Schubert, Ulrich S.; Dietzek‐Ivanšić, Benjamin; Rau, Sven; Streb, Carsten

doi:10.1038/s41557-021-00850-8

Cited by 86 publications

(75 citation statements)

References 48 publications

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“…Ru(phenphen) decomposed to 65% in 24 h, while Ru(phenphen)Ru and Ru(phenphen)Pt only degraded to 32% and 30% in 24 h, respectively, exhibiting significantly higher photostability for the binuclear complexes. The similar photostability of Ru(phenphen)Ru and Ru(phenphen)Pt is in line with the absence of quenching by the Pt-center as the population of metal-to-metal charge transfer (MMCT) states typically leads to an increase in photostability by making the population of dissociative metal centered ( 3 MC) states 44,45 less likely. Although low catalytic concentrations of the photocatalyst are used, under prolonged illumination intermolecular electron transfer from a Ru moiety to an (un)chelated phenanthroline moiety may become significant.…”

Section: Resultssupporting

confidence: 55%

“…typically leads to an increase in photostability by making the population of dissociative metal centered ( 3 MC) states 44,45 less likely. Although low catalytic concentrations of the photocatalyst are used, under prolonged illumination intermolecular electron transfer from a Ru moiety to an (un)chelated phenanthroline moiety may become significant.…”

Section: Dalton Transactions Papermentioning

confidence: 99%

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Insights into the different mechanistic stages of light-induced hydrogen evolution of a 5,5′-bisphenanthroline linked RuPt complex

et al. 2022

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Section: Resultssupporting

confidence: 55%

Section: Dalton Transactions Papermentioning

confidence: 99%

Insights into the different mechanistic stages of light-induced hydrogen evolution of a 5,5′-bisphenanthroline linked RuPt complex

et al. 2022

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“…A key characteristic of MLCT excited states is their predisposition to undergo electron transfer reactions, , as nowadays widely exploited in photoredox catalysis − ,, and in solar energy conversion. ,,− To further corroborate the finding of a photoactive excited state with substantial MLCT character in [Co(L CNC ) 2 ](PF 6 ), it therefore seemed useful to investigate to what extent this state can indeed trigger photoinduced electron transfer reactions. Toward this end, 30 μM [Co(L CNC ) 2 ](PF 6 ) in acetonitrile was excited selectively at 430 nm in the presence of 150 mM methyl viologen hexafluorophosphate (MV(PF 6 ) 2 ).…”

Section: Results and Discussionmentioning

confidence: 99%

Cobalt(III) Carbene Complex with an Electronic Excited-State Structure Similar to Cyclometalated Iridium(III) Compounds

et al. 2022

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Many organometallic iridium(III) complexes have photoactive excited states with mixed metal-to-ligand and intraligand charge transfer (MLCT/ILCT) character, which form the basis for numerous applications in photophysics and photochemistry. Cobalt(III) complexes with analogous MLCT excited-state properties seem to be unknown yet, despite the fact that iridium(III) and cobalt(III) can adopt identical low-spin d 6 valence electron configurations due to their close chemical relationship. Using a rigid tridentate chelate ligand (L CNC ), in which a central amido π-donor is flanked by two σ-donating N-heterocyclic carbene subunits, we obtained a robust homoleptic complex [Co(L CNC ) 2 ](PF 6 ), featuring a photoactive excited state with substantial MLCT character. Compared to the vast majority of isoelectronic iron(II) complexes, the MLCT state of [Co(L CNC ) 2 ](PF 6 ) is long-lived because it does not deactivate as efficiently into lower-lying metal-centered excited states; furthermore, it engages directly in photoinduced electron transfer reactions. The comparison with [Fe(L CNC ) 2 ](PF 6 ), as well as structural, electrochemical, and UV–vis transient absorption studies, provides insight into new ligand design principles for first-row transition-metal complexes with photophysical and photochemical properties reminiscent of those known from the platinum group metals.

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“…Subsequently, they further used a fully integrated photochemical molecular dyad consisting of a Ru photosensitizer covalently attached to a Wells-Dawson POM, which can act as an electron storage and hydrogen evolving catalyst. The molecular photosensitizer-POM dyad shows excellent chemical and photochemical stability [43].…”

Section: Covalent Photosensitizer-pom Attached and Used As A Photocat...mentioning

confidence: 99%

Metal-Oxo Cluster Catalysts for Photocatalytic Water Splitting and Carbon Dioxide Reduction

Lan

Jin

Yang

et al. 2022

Trans. Tianjin Univ.

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Photocatalytic water splitting and carbon dioxide photoreduction are considered effective strategies for alleviating the energy crisis and environmental pollution. Polynuclear metal-oxo clusters possess excellent electron storage/release ability and unique catalytic properties via intermetallic synergy, which enables them with great potential in environmentally friendly photosynthesis. Importantly, metal-oxo clusters with precise structure can not only act as high-efficiency catalysts but also provide well-defined structural models for exploring structure–activity relationships. In this review, we systematically summarize recent progress in the catalytic application of polynuclear metal-oxo clusters, including polyoxometalate clusters, low-cost transition metal clusters, and metal-oxo-cluster-based metal–organic frameworks for water splitting and CO2 reduction. Furthermore, we discuss the challenges and solutions to the problems of polynuclear metal-oxo clusters in photocatalysis.

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A photosensitizer–polyoxometalate dyad that enables the decoupling of light and dark reactions for delayed on-demand solar hydrogen production

Cited by 86 publications

References 48 publications

Insights into the different mechanistic stages of light-induced hydrogen evolution of a 5,5′-bisphenanthroline linked RuPt complex

Insights into the different mechanistic stages of light-induced hydrogen evolution of a 5,5′-bisphenanthroline linked RuPt complex

Cobalt(III) Carbene Complex with an Electronic Excited-State Structure Similar to Cyclometalated Iridium(III) Compounds

Metal-Oxo Cluster Catalysts for Photocatalytic Water Splitting and Carbon Dioxide Reduction

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