Photochemistry, spectroscopy, and X-ray structure of an intermolecular charge-transfer complex between an organic substrate and a polyoxometallate, α-H3PMo12O40·6(tetramethylurea)

Prosser-McCartha, Christina M.; Kadkhodayan, Miryam; Williamson, Michael M.; Bouchard, Donald A.; Hill, Craig L.

doi:10.1039/c39860001747

Cited by 49 publications

(26 citation statements)

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“…A similar comparison of Mo3d5/2 and Mo3d3/2 of (2) with that of H3PMo1204o'xH20 shows that the spectral shape of (2) is obviously different to that of H3PMot204o.xH20; the area ratio Mo 5 +/Mo 6+ of (2) is larger than that for H3PMo~zO4o'xH/O. This result demonstrates that some hexavalent molybdenum of HTPMo~zO4o.xH/O has accepted electrons from pMezNC6H4NH 2 and is reduced to pentavalent molybdenum.…”

Section: Xps Spectrasupporting

confidence: 49%

“…spectra Figure 1 shows the u.v. spectra of (1) and (2) in DMSO solution. The p-M%NC6H4NH 2 peaks at 206 and 245nm, the HTPMO12040-12H20 peaks at 220nm and the H3PMo1204o.xH20 peaks at 216nm are absent in (1) and (2), while the peaks at 315 and 317 nm, which symbolize CT between bridging-oxygen (Oh,o) and molybdenum within the Mo3013 unit, still exist, showing that the heteropoly anion units in both (1) and (2) still retain their Keggin structure.…”

Section: Resultsmentioning

confidence: 99%

“…The p-M%NC6H4NH 2 peaks at 206 and 245nm, the HTPMO12040-12H20 peaks at 220nm and the H3PMo1204o.xH20 peaks at 216nm are absent in (1) and (2), while the peaks at 315 and 317 nm, which symbolize CT between bridging-oxygen (Oh,o) and molybdenum within the Mo3013 unit, still exist, showing that the heteropoly anion units in both (1) and (2) still retain their Keggin structure. Meanwhile, new, relatively strong peaks at 262 nm in (1) and 259 nm in (2) demonstrate that a new conjugative system has been created in both complexes. Figure lc shows the vis.…”

Section: Resultsmentioning

confidence: 99%

“…Figure 3 shows the e.s.r, spectra of (1) and (2) at room temperature and 77 K. The room temperature spectra of (1) and (2) show only a single signal [9 = 2.005 for (1) and 2.003 for (2)], which is ascribed to pMe2NC6H4NH 2 isotropic radical. At 77 K the spectra of both (1) and (2) show a signal [9 = 1.941 for (1) and 1.946 for (2)] which is ascribed the pentavalent molybdenum, in addition to the radical signal of p- Table 2. I.r.…”

Section: Xps Spectramentioning

confidence: 99%

“…The negative sign of )(3) for both (1) and (2) indicates that light propagating in these two materials should be selfdefocused-a property having wide applications in the protection of optical sensors, like night-vision devices (a 1).…”

Section: Non-linear Optical Propertiesmentioning

confidence: 99%

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Synthesis, characterization and studies on the third-order optical non-linearities of novel charge-transfer heteropoly complexes (C8H12N2)5H7PMo12O40 and (C8H12N2)3H3PMo12O40·5H2O

Wang

Zhou

Zuoping

et al. 1996

Transition Met Chem

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Two novel charge-transfer (CT) heteropoly complexes, (C8HlzN2)5H7PMo1204o (i) and (Cs]rI12N2)3H 3-PMOlaO4o'5H:O (2), prepared by reacting pMezNC6H4NH 2 with the four-electron heteropoly blue HTPMo 12040 '12H20 and heteropoly acid H3PMo1204o . xH20, respectively, were characterized by elemental analysis, and u.v., i.r., XPS and e.s.r, spectroscopies. A sizable electron-transfer interaction occurs within the product molecules and the heteropoly anions retain their Keggin structure. Their third-order optical non-linearity coefficients were measured using the Z-scan technique ~)

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Section: Xps Spectrasupporting

confidence: 49%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Xps Spectramentioning

confidence: 99%

Section: Non-linear Optical Propertiesmentioning

confidence: 99%

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Synthesis, characterization and studies on the third-order optical non-linearities of novel charge-transfer heteropoly complexes (C8H12N2)5H7PMo12O40 and (C8H12N2)3H3PMo12O40·5H2O

Wang

Zhou

Zuoping

et al. 1996

Transition Met Chem

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A Reversible Redox Reaction in a Keggin Polyoxometalate Crystal Driven by Visible Light: A Programmable Solid‐State Photochromic Switch

Tandekar

Garai

Supriya

2018

Chemistry A European J

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The colourless crystals of (PPh ) [PW O ]⋅3 C H NO (1) are converted to the dark blue crystals of {(PPh ) [PW O ]⋅3C H NO} {(PPh ) (C H NO) [PW W O ] ⋅2C H NO)} (2) upon irradiation with visible light in an interesting single crystal to single crystal transformation. This photochromic conversion is accompanied by the reduction of concerned Keggin anion from {PW } to {PW W }. This redox conversion is characterized by various spectroscopic techniques including single crystal X-ray diffraction studies. The photochromic properties of compound 1 can be controlled reversibly through the dimethylformamide (DMF) molecule as a function of temperature and proton exposure in a gas-solid reaction. The present work can be described as a new concept of programmable photochromism with the formation of photochromic pockets in crystalline 1 host (solid state), wherein a solvent can be plugged at a time to show light induced coloration.

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A New Organic‐Inorganic Charge‐transfer Salt [C₁₅H₁₇N₄]₄[Mo₈O₂₆] — Synthesis, Properties and Crystal Structure

Zhang

2005

Zeitschrift anorg allge chemie

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A new organic donor 3-amino-6-dimethylamino-2methyl-phenazine was introduced to charge-transfer complex with polyoxometalate. The complex [C 15 H 17 N 4 ] 4 [Mo 8 O 26 ] (1) was synthesized by hydrothermal reaction of neutral red chloride (3-amino-6-dimethylamino-2-methyl-phenazine hydrochloride) and (NH 4 ) 6 -Polyoxometalates (POMs) have been proved to be an interesting subject in chemistry owing to their structural variation and wide applications in catalysis, magnetism, photochemistry, analysis chemistry, medicine, material chemistry and nanotechnology [1, 2]. As electron-accepting moieties in charge-transfer salts, POMs have a lot of advantages such as the good solubility in both aqueous and nonaqueous solvents; the variety ofshapes, sizes and charges which can induce new organic packings and new band structure; the ability to be reduced by one or several electrons that enable coexistence of delocalized electrons in the organic networks and the inorganic clusters; the possibility of containing magnetic and electronic properties by introducing magnetically active metal ions to POMs [2]. Since French researcher Ouahab and his coworkers synthesized first charge-transfer salts based on polyoxometalates, (TTF) 6 [PW 12 O 40 ]·(Et 4 N) (TTF ϭ tetrathiafulvene) [3], the research about this type of complexes have been a focus in molecular-based materials due to their abundant physical properties and potential applications. Organic donors used in these complexes include substituted amides [4], aromatic amines [5] and electron-rich substrates such as TTFs [2], decamethylferrocenes [2] and so on. The planar conjugated π structures of these donors stabilize the positive charge and reduced energy band gap. Many organic dyes have large planar conjugated π systems but few charge-transfer complexes using dyes as donors have been reported. Considering the potential electric and optic properties of the complexes based on dyes, our group tried to introduce different organic dyes to complexes with polyoxometalates. We have synthesized and reported a charge-transfer complex of dye cations of tri-(p-aminophenyl)carbonium and Keggin type polyoxoanions, [(C 19 H 18 N 3 ) 2 H][PMo 12 O 40 ] [6]. Here we report the synthesis and characterization of a new charge-transfer complex of monoprotonated 3-amino-6-dimethylamino-2-methylphenazine and β-[Mo 8 O 26 ] 4Ϫ , [C 15 H 17 N 4 ] 4 [Mo 8 O 26 ]. Results and DiscussionThe single crystal diffraction shows the complex 1 consists of β-[Mo 8 O 26 ] 4Ϫ anions and two types of crystallographically indepen-645 [Mo 7 O 24 ] · 4H 2 O and was characterized by EPR, element analysis and single crystal x-ray diffraction.

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Photochemistry, spectroscopy, and X-ray structure of an intermolecular charge-transfer complex between an organic substrate and a polyoxometallate, α-H₃PMo₁₂O₄₀·6(tetramethylurea)

Cited by 49 publications

References 0 publications

Synthesis, characterization and studies on the third-order optical non-linearities of novel charge-transfer heteropoly complexes (C8H12N2)5H7PMo12O40 and (C8H12N2)3H3PMo12O40·5H2O

Synthesis, characterization and studies on the third-order optical non-linearities of novel charge-transfer heteropoly complexes (C8H12N2)5H7PMo12O40 and (C8H12N2)3H3PMo12O40·5H2O

A Reversible Redox Reaction in a Keggin Polyoxometalate Crystal Driven by Visible Light: A Programmable Solid‐State Photochromic Switch

A New Organic‐Inorganic Charge‐transfer Salt [C₁₅H₁₇N₄]₄[Mo₈O₂₆] — Synthesis, Properties and Crystal Structure

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Photochemistry, spectroscopy, and X-ray structure of an intermolecular charge-transfer complex between an organic substrate and a polyoxometallate, α-H3PMo12O40·6(tetramethylurea)

Cited by 49 publications

References 0 publications

Synthesis, characterization and studies on the third-order optical non-linearities of novel charge-transfer heteropoly complexes (C8H12N2)5H7PMo12O40 and (C8H12N2)3H3PMo12O40·5H2O

Synthesis, characterization and studies on the third-order optical non-linearities of novel charge-transfer heteropoly complexes (C8H12N2)5H7PMo12O40 and (C8H12N2)3H3PMo12O40·5H2O

A Reversible Redox Reaction in a Keggin Polyoxometalate Crystal Driven by Visible Light: A Programmable Solid‐State Photochromic Switch

A New Organic‐Inorganic Charge‐transfer Salt [C15H17N4]4[Mo8O26] — Synthesis, Properties and Crystal Structure

Contact Info

Product

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About

Photochemistry, spectroscopy, and X-ray structure of an intermolecular charge-transfer complex between an organic substrate and a polyoxometallate, α-H₃PMo₁₂O₄₀·6(tetramethylurea)

A New Organic‐Inorganic Charge‐transfer Salt [C₁₅H₁₇N₄]₄[Mo₈O₂₆] — Synthesis, Properties and Crystal Structure