An OsII-NiII-PdII Trimetallic Complex as an Electro-Switchable-Photoinduced-Electron-Transfer Device

Zahavy, Eran; Fox, Marye Anne

doi:10.1002/(sici)1521-3765(19980904)4:9<1647::aid-chem1647>3.0.co;2-z

Cited by 31 publications

(17 citation statements)

References 18 publications

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“…In every sense of the term, these open-ended complexes are themselves ligands, or “modules,” for the systematic creation of higher-order assemblies incorporating other metal ions with the capacity for a specific function. Zahavy and Fox, for example, described trimetallic [(bpy) 2 Os(tpbz)Ni(tpbz)Pd(dppb)] 6+ (Figure ), the synthesis of which proceeded through open-ended [(bpy) 2 Os(tpbz)] 2+ , as a photoinduced Os → Pd electron transfer device with gating controlled by the redox state at Ni …”

Section: Introductionmentioning

confidence: 99%

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Open-Ended Metallodithiolene Complexes with the 1,2,4,5-Tetrakis(diphenylphosphino)benzene Ligand: Modular Building Elements for the Synthesis of Multimetal Complexes

et al. 2021

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Open-ended, singly metalated dithiolene complexes with 1,2,4,5-tetrakis(diphenylphosphino)benzene (tpbz) are prepared either by ligand transfer to [Cl 2 M(tpbz)] from (R 2 C 2 S 2 )SnR′ 2 (R = CN, R′ = Me; R = Me, R′ = n Bu) or by a direct reaction between tpbz and [M(S 2 C 2 R 2 ) 2 ] (M = Ni, Pd, Pt; R = Ph, p -anisyl) in a 1:1 ratio. The formation of dimetallic [(R 2 C 2 S 2 )M(tpbz)M(S 2 C 2 R 2 )] attends these syntheses in modest amounts, but the open-ended compounds are readily separated by silica chromatography. As affirmed by X-ray crystallographic characterization of numerous members of the set, the [(R 2 C 2 S 2 )M(tpbz)] compounds show dithiolene ligands in their fully reduced ene-1,2-dithiolate form conjoined with divalent Group 10 ions. Minor amounts of octahedral [(Ph 2 C 2 S 2 ) 2 Pt IV (tpbz)], a presumed intermediate, are isolated from the preparation of [(Ph 2 C 2 S 2 )Pt II (tpbz)]. Heterodimetallic [(Ph 2 C 2 S 2 )Pt(tpbz)Ni(S 2 C 2 Me 2 )] is prepared from [(Ph 2 C 2 S 2 )Pt II (tpbz)]; its cyclic voltammogram, upon anodic scanning, shows two pairs of closely spaced, but resolved, 1e – oxidations corresponding first to [R 2 C 2 S 2 2 – ] – 1e – → [R 2 C 2 S • S – ] and then to [R 2 C 2 S • S – ] – 1e – → [R 2 (C=S) 2 ]. The open diphosphine of [(R 2 C 2 S 2 )M(tpbz)] can be oxidized to afford open-ended [(R 2 C 2 S 2 )M(tpbzE 2 )] (E = O, S). Synthesis of the octahedral [(dppbO 2 ) 3 Ni][I 3 ] 2 [dppbO 2 = 1,2-bis(diphenylphosphoryl)benzene] ...

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Section: Introductionmentioning

confidence: 99%

“…A previously reported tpbz-linked heterotrimetallic complex designed to support gated photoinduced electron transfer.…”

Section: Introductionmentioning

confidence: 99%

Open-Ended Metallodithiolene Complexes with the 1,2,4,5-Tetrakis(diphenylphosphino)benzene Ligand: Modular Building Elements for the Synthesis of Multimetal Complexes

et al. 2021

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“…1) have been shown to be effective binucleating ligands in some transition metal complexes, and as parts of the monomeric units in coordination oligomers and polymers [8][9][10][11][12]. Some of the latter compounds have displayed attractive electrical and optical properties [8,11,13]. However, more detailed spectroscopic and electrochemical measurements have suggested that the metal centers in bimetallic complexes based on 3a-b lack effective electronic through-ligand coupling due to the absence of a low energy empty ligand-based orbital [14].…”

Section: Introductionmentioning

confidence: 99%

New synthetic route to polyphosphine ligands bearing 1,2,4,5-tetrakis(phosphino)benzene framework: structural characterizations of 1,4-(PPh2)2-2,5-(PR2)2-C6F2 (R=Ph, iPr, Et)

Kongprakaiwoot

Luck

Urnéžius

2004

Journal of Organometallic Chemistry

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“…For example, Zahavy and Fox have reported on the use of an osmium-nickel-palladium complex as an electro-switchable-photoinduced-electrontransfer device (ESPET). 16 Brewer and co-workers have extensively investigated the properties of trimeric hetero-metallic osmium, ruthenium and iridium polypyridyl complexes. 17,18 They have synthesised a ruthenium-iridium-ruthenium complex which functions as a device for photoinitiated electron collection, whereby the bridging ligands linking the two ruthenium centres to the iridium core are photoreduced by one electron and the electrons are delivered to a substrate.…”

Section: Introductionmentioning

confidence: 99%

Ground vs. excited state electron transfer: Adsorbed monolayers and trimers in solution

2002

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Transient emission spectroscopy has been used to probe the rate of photoinduced electron transfer between metal centres within a novel trimeric complex {[Os(bpy) 2 (bpe) 2 ][Os(bpy) 2 Cl] 2 } 4+ , where bpy is 2,2 0 -bipyridyl and bpe is trans-1,2-bis-(4pyridyl)ethylene. Transient emission experiments on the trimer, and on [Os(bpy) 2 (bpe) 2 ] 2+ in which the [Os(bpy) 2 Cl] + quenching moieties are absent, reveal that the rate of photoinduced electron transfer (PET) across the bpe bridge is 1.3 AE 0.1 Â 10 8 s À1 . Investigations into the driving forces for oxidation and reduction of the electronically excited state within the trimer indicate that quenching of the [Os(bpy) 2 (bpe) 2 ] 2+* centre within the trimer involves electron transfer from the [bpe Os(bpy) 2 Cl] + centres to the electronically excited state with a driving force of À0.3 eV. Monolayers of the complex, [Os(bpy) 2 bpe pyridine] 2+ , have been formed by spontaneous adsorption onto platinum microelectrodes and used to probe the dynamics of electron transfer across the trans-1,2bis-(4-pyridyl)ethylene bridge in the ground state. These monolayers are stable and exhibit well defined voltammetric responses for the Os 2+/3+ redox reaction. Cyclic voltammograms recorded at high scan rates can be accurately modelled according to a nonadiabatic electron transfer model based on the Marcus theory using a standard heterogeneous electron transfer rate constant, k , of 3.1 AE 0.2 Â 10 4 s À1 and a reorganization energy of 0.4 AE 0.1 eV. This rate constant is a factor of approximately two orders of magnitude smaller than that found for photoinduced electron transfer across the same bpe bridge for identical driving forces. This significant difference is interpreted in terms of both the nature of the orbitals involved in electrochemically and optically driven electron transfer, as well as the strength of electronic coupling between two molecular components as opposed to a molecular component and a metal electrode.

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An OsII-NiII-PdII Trimetallic Complex as an Electro-Switchable-Photoinduced-Electron-Transfer Device

Cited by 31 publications

References 18 publications

Open-Ended Metallodithiolene Complexes with the 1,2,4,5-Tetrakis(diphenylphosphino)benzene Ligand: Modular Building Elements for the Synthesis of Multimetal Complexes

Open-Ended Metallodithiolene Complexes with the 1,2,4,5-Tetrakis(diphenylphosphino)benzene Ligand: Modular Building Elements for the Synthesis of Multimetal Complexes

New synthetic route to polyphosphine ligands bearing 1,2,4,5-tetrakis(phosphino)benzene framework: structural characterizations of 1,4-(PPh2)2-2,5-(PR2)2-C6F2 (R=Ph, iPr, Et)

Ground vs. excited state electron transfer: Adsorbed monolayers and trimers in solution

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