Porphyrin–polyoxometalate hybrids connected via a Tris-alkoxo linker for the generation of photocurrent

Ahmed, Iftikhar; Farha, Rana; Huo, Zhaohui; Allain, Clémence; Wang, Xiaoxia; Xu, Hualong; Goldmann, Michel; Hasenknopf, Bernold; Ruhlmann, Laurent

doi:10.1016/j.electacta.2013.02.045

Cited by 36 publications

(22 citation statements)

References 53 publications

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“…We recently reported an example of Langmuir–Schaefer transfer of a covalent porphyrin–POM conjugate leading to photocurrent generation under visible‐light illumination 8. The results were particularly encouraging, but if one wishes to elaborate a functional device, processability becomes an essential issue to solve.…”

Section: Introductionmentioning

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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Section: Introductionmentioning

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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“…In addition, the nonfunctionalized POM K 3 [PW 12 O 40 ] also gave useful results (see Supplementary Materials, Figure S5). In the presence of LiCl or NaCl, introduced in matrix solutions, the anions [PW 12 This inorganic compound could be ionized by laser desorption ionization (LDI), i.e., without matrix addition, employing a high laser fluence. Yet, LDI spectra display, even in the presence of added LiCl, only PW 12 O 39 -ions (having undergone loss of one oxygen atom).…”

Section: Presence Of Cations In Fragment Ions Of Pomc12mentioning

confidence: 99%

“…The large variability of POM structures has resulted in a wide range of different properties and a corresponding range of potential chemical and biological applications. For example, POMs have found industrial applications for organic compound oxidation or dehydration [11], and they are promising tools for photovoltaic applications [12].…”

Section: Introductionmentioning

confidence: 99%

Negative Ion MALDI Mass Spectrometry of Polyoxometalates (POMs): Mechanism of Singly Charged Anion Formation and Chemical Properties Evaluation

Boulicault

Alvès

Cole

2016

J. Am. Soc. Mass Spectrom.

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Abstract. MALDI-MS has been developed for the negative ion mode analysis of polyoxometalates (POMs). Matrix optimization was performed using a variety of matrix compounds. A first group of matrixes offers MALDI mass spectra containing abundant intact singly charged anionic adduct ions, as well as abundant in-source fragmentations at elevated laser powers. A relative ranking of the ability to induce POM fragmentation is found to be: DAN > CHCA > CNA > DIT> HABA > DCTB > IAA. Matrixes of a second group provide poorer quality MALDI mass spectra without observable fragments. Sample preparation, including the testing of salt additives, was performed to optimize signals for a model POM, POMc12, the core structure of which bears four negative charges. The matrix 9-cyanoanthracene (CNA) provided the best signals corresponding to singly charged intact POMc12 anions. Decompositions of these intact anionic species were examined in detail, and it was concluded that hydrogen radical-induced mechanisms were not prevalent, but rather that the observed prompt fragments originate from transferred energy derived from initial electronic excitation of the CNA matrix. Moreover, in obtained MALDI mass spectra, clear evidence of electron transfer to analyte POM species was found: a manifestation of the POMs ability to readily capture electrons. The affinity of polyanionic POMc12 toward a variety of cations was evaluated and the following affinity ranking was established: Fe 3+ > Al 3+ > Li + > Ga 3+ > Co 2+ > Cr 3+ > Cu 2+ > [Mn 2+ , Mg 2+ ] > [Na + , K + ]. Thus, from the available cationic species, specific adducts are preferentially formed, and evidence is given that these higher affinity POM complexes are formed in the gas phase during the early stages of plume expansion.

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“…Porph-(Py + -POM-Py + -Porph) nPy + -POM-Py + (2n+1)H + + (4n+2) e -(where Porph = porphyrin) (2) We were unable to determine the polymerization degree n by gel permeation chromatography because of the very high affinity of the compound to the column used. We tested the solubility of the small molecule Porph-Py + -POM-Py + -Porph obtained by electrosynthesis (using 0.7 V as applied potential), which was sufficiently soluble.…”

Section: Electropolymerization Of the Two Pom-porphyrin Copolymersmentioning

confidence: 99%

“…One of the most attractive features of POMs is that the metal-oxygen framework can undergo reversible, stepwise, multielectron-transfer reactions, which are the basis for many catalytic processes [1,2]. Therefore POMs have been widely used for the preparation of hybrid materials and functional devices [3,4].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of Lindqvist-type polyoxometalate–porphyrin copolymers

Huo

Zang

Farha

et al. 2015

Electrochimica Acta

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Porphyrin–polyoxometalate hybrids connected via a Tris-alkoxo linker for the generation of photocurrent

Cited by 36 publications

References 53 publications

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

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

Negative Ion MALDI Mass Spectrometry of Polyoxometalates (POMs): Mechanism of Singly Charged Anion Formation and Chemical Properties Evaluation

Synthesis and characterization of Lindqvist-type polyoxometalate–porphyrin copolymers

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