Photochemical hydrogen production from 3d transition-metal complexes bearing o-phenylenediamine ligands

Yoshida, Masaki; Ueno, Show; Okano, Yuka; Usui, Akane; Kobayashi, Atsushi; Kato, Masako

doi:10.1016/j.jphotochem.2015.05.028

Cited by 6 publications

(2 citation statements)

References 56 publications

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“…o ‐Phenylenediamine as a typical redox‐active ligand, which has three relatively stable redox states (i. e., o ‐phenylenediamido, o ‐diiminosemiquinonato, and o ‐diiminoquinone), [5b,7] is known to undergo the multiproton/multielectron transfer process accompanied by π‐reconstruction in response to protonation [8] . For example, octahedral transition metal complexes bearing o ‐diiminosemiquinonate ligands have been investigated as hydrogen production/storage materials using the multistep redox processes [8c,d] . However, the pH dependence of the redox potential is almost insensitive in π‐planar metal complexes with o ‐diiminosemiquinonate ligands, [9] indicating the little proton‐electron coupling.…”

Section: Methodsmentioning

confidence: 99%

Strong Proton‐Electron Coupling in π‐Planar Metal Complex with Redox‐Active Ligands

et al. 2022

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Proton-coupled electron transfer (PCET) of metal complexes has been widely studied, especially in biochemistry and catalytic chemistry. Although metal complexes bearing redox-active ligands play a part in these research areas, those with π-planar structure remain entirely unexplored, which are vital for future development of iono-electronics. Here, proton-electron coupling of a π-planar nickel complex bearing redoxactive N,S-ligands, Ni(itsq) 2 , was investigated by combining experimental and theoretical approaches. Strong proton-electron coupling was manifested in a large potential shift, which is twice greater than that of a typical PCET-type π-planar metal complex with redoxinactive ligands, [Ni(dcpdt) 2 ] 2À . Theoretical calculations affirmed that the stabilization of frontier orbitals by protonation is greater in Ni(itsq) 2 than that in [Ni-(dcpdt) 2 ] 2À . These results indicate that π-planar metal complexes with redox-active ligands are promising for developing novel PCET-type materials.

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Section: Methodsmentioning

confidence: 99%

Strong Proton‐Electron Coupling in π‐Planar Metal Complex with Redox‐Active Ligands

et al. 2022

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“…Masaki Yoshida et al [65] developed a series of 3D-transition metal complexes with o-phenylenediamine (opda) ligands for hydrogen production due to the following properties: (a) aromatic amine undergoes homolytic N-H bond cleavage by photoexcitation [66] which is applicable for hydrogen production under mild condition, and (b) opda complexes have extensively been obsessed as reversible multielectron or multiproton pooling ability because of its multistep redox processes between o-phenylenediamine(opda), semibenzoquinodiamine (s-bqdi), and o-benzoquinodiimine (bqdi) which is useful for reversible hydrogen production. [M(opda) 3 ], M = Mn 2+ ,Fe 2+ ,Co 2+ ,Ni 2+ , and Zn +2 complexes (1-5) shown in Table 1 have photochemical hydrogen production ability.…”

Section: Photochemical Hydrogen Production From a Series Of 3d Transition Metal Complexes Bearing O-phenylenediamine Ligandmentioning

confidence: 99%

Recent Progress of Electrocatalysts and Photocatalysts Bearing First Row Transition Metal for Hydrogen Evolution Reaction (HER)

Sagar¹,

Kanaparthi²,

Tiwari³

et al. 2021

Photophysics, Photochemical and Substitution Reactions - Recent Advances

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The design and modification of metal-organic complexes for hydrogen (H 2 ) gas production by water splitting have been intensively investigated over the recent decades. In most reported mechanistic pathways, metal hydride species are considered as crucial intermediates for H 2 formation where the metal present at the active site plays an imperative role in the transfer of electron and proton. In the last few decades, much consideration has been done on the development of non-precious metal-organic catalysts that use solar energy to split water into hydrogen (H 2 ) and oxygen (O 2 ) as alternative fossil fuels. This review discussed the design, fabrication, and evaluation of the catalysts for electrocatalytic and photocatalytic hydrogen production. Mechanistic approach is addressed here in order to understand the fundamental design principle and structural properties relationship of electrocatalysts and photocatalysts. Finally, we discuss some challenges and opportunities of research in the near future in this promising area.

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Methanol‐Triggered Vapochromism Coupled with Solid‐State Spin Switching in a Nickel(II)‐Quinonoid Complex

et al. 2017

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A highly methanol‐selective vapochromic response has been realized in a NiII‐quinonoid complex, [Ni(HLMe)2] (H2LMe=4‐methylamino‐6‐methyliminio‐3‐oxocyclohexa‐1,4‐dien‐1‐olate) which exhibits a reversible structural transformation including a coordination geometrical change between the square‐planar and octahedral structure by the selective uptake of methanol vapor. This was accompanied by a remarkable color change between purple and orange, as well as temperature‐robust spin‐state switching in the solid state under ambient conditions. It is remarkable that the properties are derived by the fine structural modification of the quinonoid ligand such as methyl or ethyl analogues. Such a system has high potential for applications in memory devices as well as chemical sensors and smart responsive materials.

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Photochemical hydrogen production from 3d transition-metal complexes bearing o-phenylenediamine ligands

Cited by 6 publications

References 56 publications

Strong Proton‐Electron Coupling in π‐Planar Metal Complex with Redox‐Active Ligands

Strong Proton‐Electron Coupling in π‐Planar Metal Complex with Redox‐Active Ligands

Recent Progress of Electrocatalysts and Photocatalysts Bearing First Row Transition Metal for Hydrogen Evolution Reaction (HER)

Methanol‐Triggered Vapochromism Coupled with Solid‐State Spin Switching in a Nickel(II)‐Quinonoid Complex

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