DMAP-catalyzed esterification of pentaerythritol-derivatized POMs: a new route for the functionalization of polyoxometalates

Wu, Pingfan; Xiao, Zhao; Zhang, Jin; Hao, Jian; Chen, Jiake; Yin, Panchao; Wei, Yujie

doi:10.1039/c1cc10650c

Cited by 59 publications

(19 citation statements)

References 44 publications

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“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14] Especially, their nanosized geometry, unique optical characteritics, electronic properties, and excellent chemical reactivity make POMs more promising for the applications in photocatalysis and photovoltaics. [15][16][17][18][19][20][21] However, one major drawback of POMs for photoelectronic applications is 25 their low or negligible absorption in the visible light region, which poses a limitation for the utilization of solar energy.…”

Section: Introductionmentioning

confidence: 99%

“…[22][23][24][25][26] In addition, the electrical and optical properties of POMs could be dramatically enhanced by the large planar conjugated Π system of organic dyes. Obviously, organic dye-functionalized POM hybrids would 35 show promising applications in functional devices for the photoconversion of light into energy such as artificial photosynthetic devices and photovoltaic cells.…”

Section: Introductionmentioning

confidence: 99%

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Dye-sensitized polyoxometalate for visible-light-driven photoelectrochemical cells

Gao

Miao

et al. 2015

Dalton Trans.

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A simple and facile one-step method for the synthesis of an organic dye-functionalized polyoxometalate (POM) hybrid with visible-light photo-response was reported. The POM hybrid was fully characterized via single crystal XRD, powder XRD, FTIR and elemental analysis. The reaction of the organic dye with inorganic salts gave the dye-functionalized POM (MoBB3), in which the POM cluster was formed in situ. The electronic absorption peak of this hybrid was successfully extended beyond 680 nm. Photoelectrochemical measurement indicated that MoBB3 was photoresponsive under visible-light illumination, suggesting that it is an n-type (electron conductive) semiconducting material. This result might offer a method for the design of novel organic dye-functionalized POMs for photoelectric applications.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Dye-sensitized polyoxometalate for visible-light-driven photoelectrochemical cells

Gao

Miao

et al. 2015

Dalton Trans.

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“…Only few organic post‐functionalization reactions of tris‐ligand functionalized Lindqvist‐type vanadates were reported so far. Examples are reactions of [V 6 O 13 {(OCH 2 ) 3 C‐NH 2 } 2 ] 2− with N ‐hydroxysuccinimide esters or chloromethyl benzoates, [V 6 O 10 {(OCH 2 ) 3 C‐NH 2 } 3 ] 2− with benzoic acid, or [V 6 O 13 {(OCH 2 ) 3 C‐CH 2 OH} 2 ] 2− with carboxylic acid or acid anhydrides …”

Section: Introductionmentioning

confidence: 99%

Versatile Organic Chemistry on Vanadium‐Based Multi‐Electron Reservoirs

Nachtigall

Spandl

2018

Chemistry A European J

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We report the synthesis, post-functionalization, and redox behavior of two organically functionalized aggregates, [V O (OMe) {(OCH ) C-CH N }] and [V O (OMe) {(OCH ) C-NH }]. All twelve μ -oxo groups on the edges of the Lindqvist-type {V O } core were replaced by alkoxo ligands. The absence of a negative charge and the closed organic shell make these neutral mixed-valence compounds very stable towards hydrolysis and well soluble in almost all common organic solvents. These are important advantages over classical POMs. By post-functionalization through copper(I)-catalyzed Huisgen cycloaddition or imine formation, various organic moieties could be introduced. Even a well-soluble trimer composed of three hexanuclear vanadium units connected through an aromatic triimino core was synthesized and studied. The diverse redox behavior, the versatile reactivity, the good stability, and the excellent solubility make our vanadium compounds highly interesting for applications as building blocks in macromolecular chemistry as well as redox labels in biochemistry.

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“…Functionalized pentaerythritol has numerous applications in separations,1 as flame retardants,2 surfactants,3 antioxidants,4 crosslinking agents,5 polyoxometalate derivatives,6 and metal‐containing catalysts 7. The hydroxyl groups are functionalized by reaction with reactive groups such as acyl chlorides8 or anhydrides 9.…”

Section: Introductionmentioning

confidence: 99%

Functionalization of polymer‐supported pentaerythritol as a general synthesis for the preparation of ion‐binding polymers

Alexandratos

Zhu

2012

J of Applied Polymer Sci

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Pentaerythritol bonded to cross-linked poly(vinylbenzyl chloride) beads (PE) provides a scaffold onto which ligands can be attached by reaction with reactive compounds such as phosphoryl halides. To broaden the applicability of PE for the preparation of ion-selective polymers, conditions are reported for the conversion of the hydroxyl group to the bromide, which acts as a better leaving group. The ACH 2 Br moiety thus provides a handle on which an array of ligands can be bound through nucleophilic substitution. In this first in a series of reports, immobilization of diethylamine onto the PE and the ion-binding affinities of the resulting polymer are described.

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DMAP-catalyzed esterification of pentaerythritol-derivatized POMs: a new route for the functionalization of polyoxometalates

Abstract: We have demonstrated that a pentaerythritol-derivatized hexavanadate can be easily esterified with acid anhydrides using 4-(N,N-dimethylamino)pyridine (DMAP) as a catalyst, which provides a convenient method for the functionalization of polyoxometalates.

Cited by 59 publications

References 44 publications

Dye-sensitized polyoxometalate for visible-light-driven photoelectrochemical cells

Dye-sensitized polyoxometalate for visible-light-driven photoelectrochemical cells

Versatile Organic Chemistry on Vanadium‐Based Multi‐Electron Reservoirs

Functionalization of polymer‐supported pentaerythritol as a general synthesis for the preparation of ion‐binding polymers

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