Comparison of rhenium–porphyrin dyads for CO<sub>2</sub>photoreduction: photocatalytic studies and charge separation dynamics studied by time-resolved IR spectroscopy

Windle, Christopher D.; George, Michael W.; Perutz, Robin N.; Summers, Peter A.; Sun, Xue; Whitwood, Adrian C.

doi:10.1039/c5sc02099a

Cited by 88 publications

(70 citation statements)

References 101 publications

(194 reference statements)

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“…Interestingly, compound Zn‐Re (Figure ) reported by Perutz and co‐workers showed a TON CO of 260 using triethylamine as an electron donor and illumination at λ >520 nm for 6 hours . In this system, the Re I moiety is connected to a phenyl group in the meso ‐position of the porphyrin through an aliphatic amide bond, which, on the one hand, gives a rather flexible connection and, on the other hand, a rather large distance between the functional units.…”

Section: Introductionmentioning

confidence: 92%

Sensitized Photochemical CO₂ Reduction by Hetero‐Pacman Compounds Linking a Re^I Tricarbonyl with a Porphyrin Unit

Lang

Pfrunder

Quach

et al. 2019

Chemistry A European J

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The hetero‐Pacman architecture places two different metal coordination sites in close proximity, which can support efficient energy and/or electron transfer and allow for cooperative activation of small molecules. Here, the synthesis of dyads consisting of a porphyrin unit as photosensitizer and a rhenium unit as catalytically active site, which are held together by the rigid xanthene backbone, is presented. Mononuclear [(NN)Re(CO)3(Cl)] complexes for CO2 reduction in which NN represents a bidentate diimine ligand (e.g., bipyridine or phenanthroline) lack light absorption in the visible region, resulting in poor photocatalysis upon illumination with visible light. To improve their visible‐light absorption, we have focused on the incorporation of a strongly absorbing free base or zinc porphyrin unit. Resulting photocatalytic experiments showed a strong dependence of the catalytic performance on both the type of photosensitizer and the excitation wavelengths. Most notably, the intramolecular hetero‐Pacman system containing a zinc porphyrin unit showed much better catalytic activity in the visible region (excitation wavelengths >450 nm) than the free base porphyrin version or the corresponding mononuclear rhenium compound or an intermolecular system comprised of a 1:1 mixture of the mononuclear analogues.

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Section: Introductionmentioning

confidence: 92%

Sensitized Photochemical CO₂ Reduction by Hetero‐Pacman Compounds Linking a Re^I Tricarbonyl with a Porphyrin Unit

Lang

Pfrunder

Quach

et al. 2019

Chemistry A European J

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“…3 In addition, certain isotopes of rhenium are used in medical imaging, diagnostics, and therapeutics. 4 Although not found in natural heme systems, a few examples of rhenium porphyrins have been synthesized, including Buchler’s first report of high-valent Re V (O)(X) porphyrins.…”

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confidence: 99%

Rhenium(v)–oxo corrolazines: isolating redox-active ligand reactivity

2016

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“…Aplicações recentes envolvem a adsorção de catalisadores de Ru(II) em óxidos metálicos dopados, 208 imobilização de catalisadores e fotossensibilizadores em nanotubos proteicos, 209,210 entre outras alternativas que vêm sendo investigadas. 211,212 Nesta revisão, o foco será restrito a catalisadores homogêneos moleculares para fotorredução de CO 2 , para os quais os mecanismos envolvidos já estão melhor elucidados.…”

Section: Figura 8 Estruturas Dos Compostos Fac-{re(phen)(co)unclassified

A importância do estado excitado 3MLCT de compostos de Ru(II), Re(I) e Ir(III) no desenvolvimento de fotossensores, OLEDS e fotorredução de CO2

Müller¹,

Gonçalves²,

Ramos³

et al. 2016

Quim. Nova

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. The photochemistry and photophysics of coordination compounds have been extensively investigated not only because their structure, stability, reactivity dependence on the metal center oxidation state and the coordinated ligand; but also for their electronic transitions in a wide range of visible radiation. The knowledge of light absorption, excited state deactivation, sensitization and quenching processes are crucial to their manipulation aiming the development of systems capable of execute useful functions such as photosensors and/or probes, luminescent devices and molecular systems to convert sunlight into other types of energy. In this review, the progresses and challenges of biomolecules photosensors, organic light emitting diodes and CO 2 photoreduction catalysts based on ruthenium(II), rhenium(I) or iridium(III) coordination compounds are discussed based on their photochemical and photophysical processes.Keywords: Coordination chemistry; inorganic photochemistry; biomolecules photosensors; organic light emitting diodes; CO 2 photocatalysts. INTRODUÇÃOO desenvolvimento e a compreensão de sistemas baseados em estruturas moleculares que utilizam fótons como reagente para a ocorrência de processos químicos e físicos é o foco da fotoquímica, ciência que vem adquirindo cada vez mais destaque, principalmente, devido às potenciais aplicações em processos de conversão de energia 1-8 ou em sistemas biológicos. 9-16Compostos de coordenação apresentam grande potencial para aplicações em sistemas fotoquímicos 17-26 devido à possibilidade de incorporar diferentes ligantes a centros metálicos para formar subunidades com funcionalidades específicas que podem estar relacionadas às suas transições eletrônicas. O processo fotoquímico, que se inicia com a absorção de luz por uma espécie química e resulta na transição de um elétron do estado fundamental para um estado excitado, pode ter seu mecanismo representado por um diagrama de Jablonski, Figura 2.28-30 Na transição eletrônica, um elétron do orbital molecular ocupado de mais alta energia (Highest Occupied Molecular Orbital, HOMO) passa a ocupar, no estado excitado, um orbital molecular não-ocupado, produzindo uma nova espécie química com características distintas daquelas do estado fundamental.31 Estas novas características permitem que reações que não são observadas em processos térmicos ocorram quando a espécie é exposta à luz.O estado excitado inicialmente populado, segundo o princípio de Franck-Condon, envolverá níveis vibrônicos de maior energia e é seguido da desativação térmica dentro do mesmo poço de potencial até o orbital molecular não-ocupado de menor energia (Lowest Unoccupied Molecular Orbital, LUMO), ou seja, ocorre um decaimento térmico sem variação na multiplicidade de spin, denominado conversão interna. Após a conversão interna, pode existir o cruzamento intersistema, no qual ocorre a alteração da multiplicidade de spin, o que leva a um novo conjunto de poços de potencial e novos estados excitados possíveis de serem atingidos. Este processo é facilitado ...

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Comparison of rhenium–porphyrin dyads for CO₂photoreduction: photocatalytic studies and charge separation dynamics studied by time-resolved IR spectroscopy

Abstract: A new dyad for photocatalytic CO2 reduction produces ten times more CO and much longer-lived charge-separation than earlier rhenium-porphyrin dyads.

Cited by 88 publications

References 101 publications

Sensitized Photochemical CO₂ Reduction by Hetero‐Pacman Compounds Linking a Re^I Tricarbonyl with a Porphyrin Unit

Sensitized Photochemical CO₂ Reduction by Hetero‐Pacman Compounds Linking a Re^I Tricarbonyl with a Porphyrin Unit

Rhenium(v)–oxo corrolazines: isolating redox-active ligand reactivity

A importância do estado excitado 3MLCT de compostos de Ru(II), Re(I) e Ir(III) no desenvolvimento de fotossensores, OLEDS e fotorredução de CO2

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Comparison of rhenium–porphyrin dyads for CO2photoreduction: photocatalytic studies and charge separation dynamics studied by time-resolved IR spectroscopy

Abstract: A new dyad for photocatalytic CO2 reduction produces ten times more CO and much longer-lived charge-separation than earlier rhenium-porphyrin dyads.

Cited by 88 publications

References 101 publications

Sensitized Photochemical CO2 Reduction by Hetero‐Pacman Compounds Linking a ReI Tricarbonyl with a Porphyrin Unit

Sensitized Photochemical CO2 Reduction by Hetero‐Pacman Compounds Linking a ReI Tricarbonyl with a Porphyrin Unit

Rhenium(v)–oxo corrolazines: isolating redox-active ligand reactivity

A importância do estado excitado 3MLCT de compostos de Ru(II), Re(I) e Ir(III) no desenvolvimento de fotossensores, OLEDS e fotorredução de CO2

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Comparison of rhenium–porphyrin dyads for CO₂photoreduction: photocatalytic studies and charge separation dynamics studied by time-resolved IR spectroscopy

Sensitized Photochemical CO₂ Reduction by Hetero‐Pacman Compounds Linking a Re^I Tricarbonyl with a Porphyrin Unit

Sensitized Photochemical CO₂ Reduction by Hetero‐Pacman Compounds Linking a Re^I Tricarbonyl with a Porphyrin Unit