Photosensitizers based on Ir(III) complexes for highly efficient photocatalytic hydrogen generation

Wang, Yue; Zhao, Xinyu; Zhao, Yaohua; Yang, Tianzhi; Liu, Xingman; Xie, Jiaxin; Li, Guangfu; Zhu, Dongxia; Tan, Huaqiao; Su, Zhong‐Min

doi:10.1016/j.dyepig.2019.107547

Cited by 19 publications

(16 citation statements)

References 48 publications

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“…Molecular dyes are utilized in applications including displays, − photocatalysis of organic reactions, , photodynamic cancer therapy, dye-sensitized solar cells, − and photoelectrodes that produce solar fuels. , Dye-sensitized systems incorporate a thin, often a molecular layer of dye, typically on the surface of a semiconductor (SC). − ,− The majority of dye-sensitized systems employ transition-metal complexes as dyes. , Ru– − ,, and Ir– , polypyridyl systems are the most common because they offer good conversion efficiencies, they are readily modified, and form long-living triplet excited states by intersystem crossing (ISC). These systems can be costly and toxic.…”

Section: Introductionmentioning

confidence: 99%

“…1−3,7−12 The majority of dye-sensitized systems employ transition-metal complexes as dyes. 13,14 Ru− [8][9][10]15,16 and Ir− 15,17 polypyridyl systems are the most common because they offer good conversion efficiencies, they are readily modified, and form long-living triplet excited states by intersystem crossing (ISC). These systems can be costly and toxic.…”

Section: ■ Introductionmentioning

confidence: 99%

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Carbazole–Cyanobenzene Dyes Electrografted to Carbon or Indium-Doped Tin Oxide Supports for Visible Light-Driven Photoanodes and Olefin Isomerizations

Rasu

Amiri

Bergens

2021

ACS Appl. Mater. Interfaces

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The organic carbazole−cyanobenzene push−pull dye 1,2,3,5tetrakis(carbazol-9-yl)-4,6-dicyanobenzene was derivatized and attached to carbon or indium-doped tin oxide (ITO) electrodes by simple diazonium electrografting. The surface-bound dye is active and stable for the visible light photosynthetic isomerization of a wide range of functionalized stilbene and cinnamic acid derivatives. Up to 87,000 net turnovers were obtained for the isomerization of trans-stilbene. The isomerizations can be carried out in air with a 33% reduction in the rate. The ITO photoelectrodes are also active and stable toward photo-oxidations under basic and acidic conditions.

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Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Carbazole–Cyanobenzene Dyes Electrografted to Carbon or Indium-Doped Tin Oxide Supports for Visible Light-Driven Photoanodes and Olefin Isomerizations

Rasu

Amiri

Bergens

2021

ACS Appl. Mater. Interfaces

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“…Unfortunately, due to limited visible light absorption and unsatisfactory thermodynamic properties, existing iridium(III) photosensitizers are of limited use. Efforts to circumvent their poor visible light harvesting include covalently linking additional chromophores, − engineering the HOMO–LUMO gap through ligand modifications − and changing the nature of the emissive excited states. , Here, we report access to iridium complexes (Chart and Figure ) that are strong photo-oxidants with a molar absorption coefficient suitable for visible-light-driven applications. Furthermore, excited-state electron transfer studies reported herein reveal a small reorganization energy, demonstrating that these new Ir complexes hold promise for visible-light-driven applications from both a kinetic and thermodynamic point of view.…”

mentioning

confidence: 97%

“…25 Unfortunately, due to limited visible light absorption and unsatisfactory thermodynamic properties, existing iridium(III) photosensitizers are of limited use. Efforts to circumvent their poor visible light harvesting include covalently linked additional chromophores [27][28][29] , engineering the HOMO-LUMO gap through ligand modifications [30][31][32][33] and changing the nature of the emissive excited states. [34][35] Here, we report access to iridium complexes (Chart 1 and Figure 1) that are strong photo-oxidants with molar absorption coefficient suitable for visible-light-driven applications.…”

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confidence: 99%

Improved Visible Light Absorption of Potent Iridium(III) Photo-oxidants for Excited-State Electron Transfer Chemistry

et al. 2020

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Three iridium photosensitizers, [Ir(dCF 3 ppy) 2 (N−N)] + , where N−N is 1,4,5,8-tetraazaphenanthrene (TAP), pyrazino[2,3-a]phenazine (pzph), or benzo[a]pyrazino[2,3-h]phenazine (bpph) and dCF 3 ppy is 2-(3,5-bis(trifluoromethylphenyl)pyridine), were found to be remarkably strong photo-oxidants with enhanced light absorption in the visible region. In particular, judicious ligand design provided access to Ir-bpph, with a molar absorption coefficient, ε = 9800 M −1 cm −1 , at 450 nm and an excited-state reduction potential, E(Ir + * /0 ) = 1.76 V vs NHE. These complexes were successful in performing light-driven charge separation and energy storage, where all complexes photo-oxidized seven different electron donors with rate constants (0.089−3.06) × 10 10 M −1 s −1 . A Marcus analysis provided a total reorganization energy of 0.7 ± 0.1 eV for excited-state electron transfer.

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“…For such as a neutral Ir(III) complex [Ir(ppy) 2 (L H )] (ppy = phenylpyridine and L H = pyridylpyrrole) designed by Yi and co-workers, its photocatalytic duration can last to 144 h with a turnover number (TON, a typically benchmark for HER) of 1768 . (ii) Modifying special groups on the ancillary ligand to increase the electron transfer rate of PS – . − For example, a series of Ir(III) PSs with formyl moieties has been constructed by Fang et al , enabling molecular assembly to the surface of the colloidal platinum catalyst with a photocatalytic longevity of 5 h and a TON of 6364. (iii) Introducing an ancillary ligand with sterically bulky groups to prevent the photoinduced solvolysis of PS.…”

Section: Introductionmentioning

confidence: 99%

Construction of Robust Iridium(III) Complex-Based Photosensitizer for Boosting Hydrogen Evolution

et al. 2023

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Developing a photosensitizer with high efficiency and long-term stability for photocatalytic hydrogen evolution is highly desirable yet remains a challenge. Herein, a novel Ir(III) complex-based photosensitizer (Ir3) bearing coumarin and triphenylamine groups is designed. Ir3 exhibits record activity and durability among reported transition metal complexes for photocatalytic hydrogen evolution, with a TON of 198,363 and a duration of 214 h. The excellent photocatalytic performance of Ir3 can be attributed to the synergistic effect of coumarin and triphenylamine, which improves the visible light absorption, charge separation, and electron transfer capacity of photosensitizers. This is an efficient and long-lived Ir(III) photosensitizer constructed on the basis of a synergistic approach, which could provide a new insight for the development of high-performance Ir(III) photosensitizers at the molecular level.

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Photosensitizers based on Ir(III) complexes for highly efficient photocatalytic hydrogen generation

Cited by 19 publications

References 48 publications

Carbazole–Cyanobenzene Dyes Electrografted to Carbon or Indium-Doped Tin Oxide Supports for Visible Light-Driven Photoanodes and Olefin Isomerizations

Carbazole–Cyanobenzene Dyes Electrografted to Carbon or Indium-Doped Tin Oxide Supports for Visible Light-Driven Photoanodes and Olefin Isomerizations

Improved Visible Light Absorption of Potent Iridium(III) Photo-oxidants for Excited-State Electron Transfer Chemistry

Construction of Robust Iridium(III) Complex-Based Photosensitizer for Boosting Hydrogen Evolution

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