Transition-metal-mediated photochemical disproportionation of carbon dioxide

Belmore, Kenneth A.; Vanderpool, Richard A.; Tsai, Jing Cherng; Khan, Masood A.; Nicholas, Kenneth M.

doi:10.1021/ja00214a076

Cited by 67 publications

(26 citation statements)

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“…The essential requirement for a DSSC of high efficiency is a dye with a high energy LUMO level and a low energy HOMO level, and several approaches have been reported in which the HOMO energy level in this type of complex has been lowered. Furthermore, it is likely that NHC complexes may have potential for many further applications, since similar phosphorescent transition metal complexes which do not contain NHC ligands are suitable in applications such as biological labelling agents (mainly rhenium and ruthenium derivatives), [7][8][9] charge-transfer reactions in DNA, 10 antitumoral agents (gold and platinum complexes), 11,12 phosphorescent sensors, 13 photocatalysis for CO 2 reduction 14 and photochemical water splitting. 15,16 Luminescent M-NHC complexes and applications…”

Section: Introductionmentioning

confidence: 99%

N-heterocyclic carbene metal complexes: photoluminescence and applications

2014

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This review covers the advances made in the synthesis of luminescent transition metal complexes containing N-heterocyclic carbene (NHC) ligands. The presence of a high field strength ligand such as an NHC in the complexes gives rise to high energy emissions, and consequently, to the desired blue colour needed for OLED applications. Furthermore, the great versatility of NHC ligands for structural modifications, together with the use of other ancillary ligands in the complex, provides numerous possibilities for the synthesis of phosphorescent materials, with emission colours over the entire visible spectra and potential future applications in fields such as photochemical water-splitting, chemosensors, dye-sensitised solar cells, oxygen sensors, and medicine.

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Section: Introductionmentioning

confidence: 99%

N-heterocyclic carbene metal complexes: photoluminescence and applications

2014

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“…The products of the reductive disproportionation of carbon dioxide have been observed for a number of low-valent transition metal systems, ,, and in a number of cases, disproportionation has been unequivocally established through 13 CO 2 isotopic labeling studies. ,, The disproportionation process typically proceeds through the reaction of a metal–CO 2 complex, where the CO 2 is bound either in an η 1 (C)-CO 2 or η 2 (C,O)-CO 2 coordination mode, with a second equivalent of carbon dioxide to give free or coordinated carbonyl and carbonate products (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

Fe(0)-Mediated Reductive Disproportionation of CO₂

Jurd

Bhadbhade

et al. 2020

Organometallics

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The zero-valent iron phosphine [Fe(N 2 )(dmpe) 2 ] (2) reacts with CO 2 to form the(3) through the reductive coupling of two molecules of carbon dioxide. The formation of metalacycle 3 proceeds through a stepwise reaction with carbon dioxide to form, initially, the isolable 1), which reacts with a second molecule of CO 2 to form the 5-membered metalacycle. This sequence represents the first experimental evidence for the formation of a κ 2 C,O-FeC 2 O 4 metalacycle via an η 2 (C,O)-CO 2 precursor. Isotopic labeling was used to demonstrate that the initial coordinated CO 2 molecule forms the metal-bound carbonyl moiety in the metalacycle, while the second molecule of CO 2 forms the carbonyl β to the iron center. The metalo-2,4-dioxolane-3,5-dione cis-[Fe(C(O)OC(O)O-κ 2 C,O)(dmpe) 2 ] (3) breaks down with loss of CO to yield the iron carbonate cis-[Fe(CO 3 -κ 2 O,O)(dmpe) 2 ] (5). In the presence of a CO scavenger such as [Fe(N 2 )(dmpe) 2 ], CO is trapped to give [Fe(CO)(dmpe) 2 ] (4). This is the first direct experimental evidence for a κ 2 C,O-C 2 O 4 metalacycle being a key intermediate in the reductive disproportionation of CO 2 to CO and CO 3 2− .

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“…These complexes can also be used as sensitisers for outer-sphere electron-transfer reactions [6,7], photoreductants [8], biological labelling reagents [9], photocatalysts for CO 2 reduction [10], as well as the singlet oxygen sensitisers [11]. Among these Ir (III) complexes, green-and red-emitting materials in OLEDs with high quantum efficiencies have been known from years [12].…”

Section: Introductionmentioning

confidence: 99%

The effect of substituted moiety on the optoelectronic and photophysical properties of tris (phenylbenzimidazolinato) Ir (III) carbene complexes and the OLED performance: a theoretical study

Srivastava

2015

Molecular Physics

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To cite this article: Ruby Srivastava (2015): The effect of substituted moiety on the optoelectronic and photophysical properties of tris (phenylbenzimidazolinato) Ir (III) carbene complexes and the OLED performance: a theoretical study, Density functional theory (DFT) and time-dependent density functional theory (TDDFT) are used to analyse theoretically the optoelectronic, photophysical properties and organic light-emitting diode performance of a series of fac-mer blue-emitting Iridium (III) carbene complexes. Swain-Lupton constant is used to discuss the substituents effect. 5d-orbital splitting and d-d * transitions are calculated to assess the efficiency of the studied complexes. The reorganisation energies (λ), transfer integrals, mobilities, radiative decay rate (k r ), and triplet exciton generation fraction (χ T ) are also calculated. Due to the higher χ T of these complexes, the formation of triplet exciton will be more and it will cause a faster intersystem crossing. Two host materials are proposed and host-guest match (Dexter-Förster energy) is also discussed. We hope that this unified work will surely help to design new blue-emitting phosphorescent materials in future. IntroductionIridium (III) cyclometalated complexes have shown enormous potential as emissive dopants in organic light-emitting diodes (OLEDs) [1][2][3][4][5]. These complexes can also be used as sensitisers for outer-sphere electron-transfer reactions [6,7], photoreductants [8], biological labelling reagents [9], photocatalysts for CO 2 reduction [10], as well as the singlet oxygen sensitisers [11]. Among these Ir (III) complexes, green-and red-emitting materials in OLEDs with high quantum efficiencies have been known from years [12]. However, achieving blue phosphorescence with high quantum efficiency at room temperature is still a challenge [13]. One method to deal with this difficulty is to increase the contribution from the metal to ligand charge transfer ( 3 MLCT) configuration in the low-lying triplet state structure. Recently, FIrpic [14] and FIr6 [15] have become the excellent materials for greenish-blue-and sky-blue-emitting phosphorescent materials. Though efforts have been made to substitute the piconate ligand with ancillary chelates as triazolate or tetrazolate to afford the FIrtaz [16] and FIrN4 [17] heterocyclic complexes to produce blue emitting phosphorescent materials. While changing the emitting material of OLED from fluorescent [18] to phosphorescent complexes, the external quantum efficiencies of the OLED device were increased from 1% to 7.5%. Kido and co-workers [19] have also reported the efficiency of 29% using iridium complexes [20]. A blue phosphorescent complex has a higher energy emission state ( 3 MLCT) due to the large transition

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Transition-metal-mediated photochemical disproportionation of carbon dioxide

Cited by 67 publications

References 2 publications

N-heterocyclic carbene metal complexes: photoluminescence and applications

N-heterocyclic carbene metal complexes: photoluminescence and applications

Fe(0)-Mediated Reductive Disproportionation of CO₂

The effect of substituted moiety on the optoelectronic and photophysical properties of tris (phenylbenzimidazolinato) Ir (III) carbene complexes and the OLED performance: a theoretical study

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Transition-metal-mediated photochemical disproportionation of carbon dioxide

Cited by 67 publications

References 2 publications

N-heterocyclic carbene metal complexes: photoluminescence and applications

N-heterocyclic carbene metal complexes: photoluminescence and applications

Fe(0)-Mediated Reductive Disproportionation of CO2

The effect of substituted moiety on the optoelectronic and photophysical properties of tris (phenylbenzimidazolinato) Ir (III) carbene complexes and the OLED performance: a theoretical study

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Fe(0)-Mediated Reductive Disproportionation of CO₂