Synthesis and characterization of conjugated Dawson-type polyoxometalate–porphyrin copolymers

Azcarate, Iban; Ahmed, Iftikhar; Farha, Rana; Goldmann, Michel; Wang, Xiaoxia; Xu, Hualong; Hasenknopf, Bernold; Lacôte, Emmanuel; Ruhlmann, Laurent

doi:10.1039/c3dt50850a

Cited by 45 publications

(25 citation statements)

References 71 publications

(85 reference statements)

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“…The same also holds true for the four reduction processes which were assigned to the cluster; the first two are expected to occur on the V(V) centers. According to the available literature report, these reductions might be observed either as three individual one-electron or two separated processes, in which a one-electron reduction is followed by a two-electron reduction [41]. The latter is in line with the experimental data.…”

Section: Synthesis and Characterization Of The Photosensitizer-polyoxsupporting

confidence: 83%

Towards Covalent Photosensitizer-Polyoxometalate Dyads-Bipyridyl-Functionalized Polyoxometalates and Their Transition Metal Complexes

et al. 2019

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A triol-functionalized 2,2′-bipyridine (bpy) derivative has been synthesized and used for the tris-alkoxylation of polyoxometalate (POM) precursors. The resultant POM-bpy conjugates of the Wells–Dawson- and Anderson-type feature a C–C bond as a linkage between the POM and bpy fragments. This structural motif is expected to increase the hydrolytic stability of the compounds. This is of particular relevance with respect to the application of POM-bpy metal complexes, as photocatalysts, in the hydrogen-evolution reaction (HER) in an aqueous environment. Accordingly, Rh(III) and Ir(III) complexes of the POM-bpy ligands have been prepared and characterized. These catalyst-photosensitizer dyads have been analyzed with respect to their electrochemical and photophysical properties. Cyclic and square-wave voltammetry, as well as UV/vis absorption and emission spectroscopy, indicated a negligible electronic interaction of the POM and metal-complex subunits in the ground state. However, emission–quenching experiments suggested an efficient intramolecular electron-transfer process from the photo-excited metal centers to the POM units to account for the non-emissive nature of the dyads (thus, suggesting a strong interaction of the subunits in the excited state). In-depth photophysical investigations, as well as a functional characterization, i.e., the applicability in the HER reaction, are currently ongoing.

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Section: Synthesis and Characterization Of The Photosensitizer-polyoxsupporting

confidence: 83%

Towards Covalent Photosensitizer-Polyoxometalate Dyads-Bipyridyl-Functionalized Polyoxometalates and Their Transition Metal Complexes

et al. 2019

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“…Monomers POM‐l3,3 and POM‐l4,4 were prepared as previously described 13b. Using the same synthetic strategy, we synthesized two other organo‐POM monomers, namely, POM‐s4,4 and POM‐m3,3 .…”

Section: Resultsmentioning

confidence: 99%

“…The absence of demetalation of ZnOEP was verified by UV/Vis spectroscopy. We prepared POM–porphyrin copolymer films from the four different Dawson‐type POM(py) 2 monomers 13b…”

Section: Resultsmentioning

confidence: 99%

Generation of Photocurrent by Visible‐Light Irradiation of Conjugated Dawson Polyoxophosphovanadotungstate–Porphyrin Copolymers

Azcarate

Huo

Farha

et al. 2015

Chemistry A European J

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Four hybrid polyoxometalate-porphyrin copolymer films were obtained by the electrooxidation of zinc octaethylporphyrin in the presence of four different Dawson-type polyoxometalates bearing two pyridyl groups (POM(py)2) with various spacers. The POM monomers were designed around 1,3,5-trisubstituted benzene rings. Two of the substituents of the benzene ring are linked to the pyridyl groups, and the third is connected to the POM subunit. The four monomers vary in the relative positions of the nitrogen atoms of the pyridine rings or in the distance from the carbonyl group. The monomers were fully characterized by (1)H, (31)P, and (13)C NMR spectroscopy, electrospray mass spectrometry, IR and UV/Vis spectroscopy, and electrochemistry. The copolymers were characterized by UV/Vis spectroscopy, X-ray photoelectron spectroscopy, electrochemistry, and AFM. Their photovoltaic performance under visible light irradiation was investigated by photocurrent transient measurements under visible illumination.

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“…The syntheses of the copolymers were achieved via our electropolymerization method, as reported earlier [29,31,32]. It relied on the addition of the dipyridyl-substituted Lindqvist-type polyoxovanadate [V 6 O 13 {(OCH 2 ) 3 CNHCO(4-C 5 H 4 N)} 2 ] 2-(Py-POM-Py) to an electro-generated dicationic porphyrin by iterative scans between -1.10 V and +1.60 V vs. SCE (Fig.…”

Section: Electropolymerization Of the Two Pom-porphyrin Copolymersmentioning

confidence: 99%

“…The covalent approach offers several advantages; in particular it should enhance the directionality and the interaction between POMs and organic components such as ferrocenyl [19,20], pyrene and perylene [21][22][23], Ru and Ir complexes [22,24], and porphyrins [25][26][27]. We reported the formation of a mixed POMporphyrin copolymer film with an Anderson type POM [MnMo 6 9À and ZnOEP, via an original electropolymerization/deposition process [29]. Both of them exhibited remarkable photocatalytical properties under visible light illumination.…”

Section: Introductionmentioning

confidence: 97%

Synthesis and characterization of Lindqvist-type polyoxometalate–porphyrin copolymers

Huo

Zang

Farha

et al. 2015

Electrochimica Acta

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Synthesis and characterization of conjugated Dawson-type polyoxometalate–porphyrin copolymers

Cited by 45 publications

References 71 publications

Towards Covalent Photosensitizer-Polyoxometalate Dyads-Bipyridyl-Functionalized Polyoxometalates and Their Transition Metal Complexes

Towards Covalent Photosensitizer-Polyoxometalate Dyads-Bipyridyl-Functionalized Polyoxometalates and Their Transition Metal Complexes

Generation of Photocurrent by Visible‐Light Irradiation of Conjugated Dawson Polyoxophosphovanadotungstate–Porphyrin Copolymers

Synthesis and characterization of Lindqvist-type polyoxometalate–porphyrin copolymers

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