Synthesis and properties of a novel tripodal bipyridyl ligand tb-carbinol and its Ru(II)–Re(I) trimetallic complexes: investigation of multimetallic artificial systems for photocatalytic CO<sub>2</sub>reduction

Bian, Zhaoyong; Sumi, Katsuhiro; Furue, Masaoki; Sato, Shunsuke; Koike, Kazuhide; Ishitani, Osamu

doi:10.1039/b814340d

Cited by 68 publications

(42 citation statements)

References 54 publications

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“…[7,8] Since then, researchers have tried to improve its efficiency by (i) modifying the nature of the ligands in the coordination sphere to improve catalysis and to shift the absorption properties in the visible range, [9][10][11][12][13][14][15] and/or (ii) incorporating photosensitizers to photo-activate the catalyst in the visible spectral window. [16][17][18][19][20][21][22][23][24][25][26] From turnover numbers (TON) of 5-20 when it was first published, current improvements show TONs of ca. 3000.…”

Section: Isotope Labelingmentioning

confidence: 99%

“…Visible light was used to drive an optimized photocatalytic reduction using a ruthenium trisbipyridine complex as a sensitizer and a rhenium bipyridyl carbonyl complex as a catalyst to perform an efficient reduction of CO 2 to CO, which was then simultaneously utilized in a palladium-catalyzed aminocarbonylation reaction at room temperature. [16][17][18][19][20][21][22][23][24][25][26] From turnover numbers (TON) of 5-20 when it was first published, current improvements show TONs of ca. There is a consensus that we have to develop a circular economy scheme in order to drop to a zero-carbon emission scenario.…”

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confidence: 99%

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Visible‐Light‐Driven Reduction of CO₂ to CO and Its Subsequent Valorization in Carbonylation Chemistry and ¹³C Isotope Labeling

et al. 2018

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A convenient and safe approach in valorizing carbon monoxide (CO) produced from the photocatalytic reduction of carbon dioxide (CO 2 ) has been investigated. Visible light was used to drive an optimized photocatalytic reduction using a ruthenium trisbipyridine complex as a sensitizer and a rhenium bipyridyl carbonyl complex as a catalyst to perform an efficient reduction of CO 2 to CO, which was then simultaneously utilized in a palladium-catalyzed aminocarbonylation reaction at room temperature. This approach provides safe handling of the produced CO which also opens the way for a more efficient application of 13 C-isotope and 14 C-radioisotope-labeled CO 2 in pharmaceutically relevant drug labeling.The constraints we are exerting on our environment due to the extensive use of fossil fuels have reached alarming levels. There is a consensus that we have to develop a circular economy scheme in order to drop to a zero-carbon emission scenario. One challenge in front of chemists is to convert the everincreasing CO 2 level into a fuel or to use it as a source of carbon in chemical transformations. However, due to its high chemical stability, its activation or reduction is scientifically challenging, requiring appropriate catalyst and energy input. [1][2][3][4][5][6] The energy can be ideally provided by solar energy, a strategic scheme of artificial photosynthesis.One of the most robust and selective photocatalyst for CO 2 reduction was first reported by Lehn et al. using fac-Re(bpy)(-CO) 3 Cl. [7,8] Since then, researchers have tried to improve its efficiency by (i) modifying the nature of the ligands in the coordination sphere to improve catalysis and to shift the absorption properties in the visible range, [9][10][11][12][13][14][15] and/or (ii) incorporating photosensitizers to photo-activate the catalyst in the visible spectral window. [16][17][18][19][20][21][22][23][24][25][26] From turnover numbers (TON) of 5-20 when it was first published, current improvements show TONs of ca. 3000. [27] Efforts are also guided towards designing photocatalysts employing earth-abundant metals (Cu, Ni, Co, Mn, Fe) for cost efficiency and such systems show equally promising results. [28] Though most studies in photocatalytic reduction of CO 2 to CO have focused on improving the efficiency, selectivity, cost, and stability of the catalyst, only little has been reported in addressing the need for capturing and storing the produced CO. The reduced product can be segregated from the headspace mixture by techniques such as swing adsorption, [29] cryogenic distillation, [30] and membrane gas separation, [31] but these usually employ specialized equipment, and high pressure and temperature, which require extra energy input. Furthermore, the inherent toxicity and flammability of CO gas impose strict handling precautions and safety procedures.In nature, CO dehydrogenase enzymes transport the CO produced from the catalytic reduction of CO 2 in its C cluster site to the acetyl CoA synthase via direct gas channels to insert CO in a carbony...

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Section: Isotope Labelingmentioning

confidence: 99%

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confidence: 99%

Visible‐Light‐Driven Reduction of CO₂ to CO and Its Subsequent Valorization in Carbonylation Chemistry and ¹³C Isotope Labeling

et al. 2018

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“…Especially high-performance catalysts of this kind are heterotrimetallic complexes with tripodal, biyridine-carrying units, which simultaneously contain Re I and Ru II as metal ions. [325] Albeit significant progress has been made in this area, there is still a considerable need for further development. [326] Up to now, the low energy efficiency has been prohibitive.…”

Section: Photocatalytic Activation Of Carbon Dioxidementioning

confidence: 99%

Chemical Technologies for Exploiting and Recycling Carbon Dioxideinto the Value Chain

et al. 2011

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While experts in various fields discuss the potential of carbon capture and storage (CCS) technologies, the utilization of carbon dioxide as chemical feedstock is also attracting renewed and rapidly growing interest. These approaches do not compete; rather, they are complementary: CCS aims to capture and store huge quantities of carbon dioxide, while the chemical exploitation of carbon dioxide aims to generate value and develop better and more-efficient processes from a limited part of the waste stream. Provided that the overall carbon footprint for the carbon dioxide-based process chain is competitive with conventional chemical production and that the reaction with the carbon dioxide molecule is enabled by the use of appropriate catalysts, carbon dioxide can be a promising carbon source with practically unlimited availability for a range of industrially relevant products. In addition, it can be used as a versatile processing fluid based on its remarkable physicochemical properties.

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“…As principais abordagens envolvem a fotogeração de H 2 a partir da oxidação da água 170-177 ou a produção de substâncias contendo carbono a partir da fotorredução de CO 2 . [178][179][180][181][182][183][184][185][186][187][188][189][190][191][192][193][194][195] O CO 2 é uma molécula muito estável (DG f 0 = -394 kJ mol -1 ) e sua redução por um elétron levando à formação de •CO 2 -é muito desfavorável (DE = -1,9 V vs NHE; DG f = 182 kJ mol -1 ) e um sobrepotencial elevado é necessário para superar as restrições cinéticas 3 [CNB(C 6 197 Para auxiliar na cinética deste processo, catalisadores que diminuem o sobrepotencial por meio da estabilização do estado de transição entre o CO 2 e o produto pretendido podem ser utilizados. O CO 2 pode ser reduzido diretamente em superfícies metálicas, entretanto, o sobrepotencial ainda é extremamente alto e ocorre o envenenamento da superfície do metal.…”

Section: Conversão De Luz Em Energia Químicaunclassified

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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Synthesis and properties of a novel tripodal bipyridyl ligand tb-carbinol and its Ru(II)–Re(I) trimetallic complexes: investigation of multimetallic artificial systems for photocatalytic CO₂reduction

Cited by 68 publications

References 54 publications

Visible‐Light‐Driven Reduction of CO₂ to CO and Its Subsequent Valorization in Carbonylation Chemistry and ¹³C Isotope Labeling

Visible‐Light‐Driven Reduction of CO₂ to CO and Its Subsequent Valorization in Carbonylation Chemistry and ¹³C Isotope Labeling

Chemical Technologies for Exploiting and Recycling Carbon Dioxideinto the Value Chain

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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Synthesis and properties of a novel tripodal bipyridyl ligand tb-carbinol and its Ru(II)–Re(I) trimetallic complexes: investigation of multimetallic artificial systems for photocatalytic CO2reduction

Cited by 68 publications

References 54 publications

Visible‐Light‐Driven Reduction of CO2 to CO and Its Subsequent Valorization in Carbonylation Chemistry and 13C Isotope Labeling

Visible‐Light‐Driven Reduction of CO2 to CO and Its Subsequent Valorization in Carbonylation Chemistry and 13C Isotope Labeling

Chemical Technologies for Exploiting and Recycling Carbon Dioxideinto the Value Chain

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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Synthesis and properties of a novel tripodal bipyridyl ligand tb-carbinol and its Ru(II)–Re(I) trimetallic complexes: investigation of multimetallic artificial systems for photocatalytic CO₂reduction

Visible‐Light‐Driven Reduction of CO₂ to CO and Its Subsequent Valorization in Carbonylation Chemistry and ¹³C Isotope Labeling

Visible‐Light‐Driven Reduction of CO₂ to CO and Its Subsequent Valorization in Carbonylation Chemistry and ¹³C Isotope Labeling