Hybrid Molecular Materials Based on Covalently Linked Inorganic Polyoxometalates and Organic Conjugated Systems

Xu, Bo-Wei; Wei, Yongge; Barnes, Charles L.; Peng, Zhonghua

doi:10.1002/1521-3773(20010618)40:12<2290::aid-anie2290>3.0.co;2-p

Cited by 124 publications

(67 citation statements)

References 6 publications

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“…From the synthetic point of view, the C-Br moiety of this new precursor may be useful as an additional reaction site in this type of cluster for a further functionalization through a carbon-carbon coupling reaction, [8][9][10]13 and, potentially, with nucleophilic species to afford new molecular or polymeric hybrid materials.…”

Section: Discussionmentioning

confidence: 99%

“…2-, a number of new organoimido-derivatives of hexamolybdate, [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] hexatungstate, 20 and pentatu ngstenmolybdate, 21 have been synthesized, spectroscopically characterized and, the majority, structurally authenticated by X-ray diffraction analysis. Very recently, the stability, bonding character, electronic properties, first hyperpolarizabilities of this type of complexes have also been studied by Density Functional Theory (DFT).…”

Section: Marcela Cortésmentioning

confidence: 99%

“…, bromo- 12,18 and iodoareneimido hexamolybdates [7][8][9][10][13][14][15] and iodoareneimido pentatungstenmolybdate 21 seems to be of great importance considering their potential applications as precursors for the synthesis of new organicinorganic hybrids containing additional organic 7,8,10,14,15 or organometallic 13 groups, or two similar clusters linked by an extended π-conjugated organic spacer. [8][9][10]15 These halogenated precursors have successfully been applied for the synthesis of organoimido-hexamolybdates as polymer pendants 5 and main-chain polymers.…”

mentioning

confidence: 97%

“…[8][9][10]15 These halogenated precursors have successfully been applied for the synthesis of organoimido-hexamolybdates as polymer pendants 5 and main-chain polymers. 9,15 In this paper we report the synthesis, spectroscopic characterization, electrochemical studies and the X-ray crystal and molecular structure of the new organic-inorganic hybrid bearing the electron-withdrawal bromo group in a remote position: (n-Bu 4 N) 2 …”

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confidence: 99%

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A NEW LINDQVIST-TYPE HEXAMOLYBDATE CLUSTER FUNCTIONALIZED WITH THE jt-DONOR LIGAND 4-BROMO-2,6-DIMETHYLPHENYLIMIDO: SPECTROSCOPIC, ELECTROCHEMICAL AND STRUCTURAL STUDIES

Cortés

Fuentealba

Manzur

et al. 2008

J. Chil. Chem. Soc.

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A new ionic organic-inorganic hybrid complex of formula (n-Bu 4 N) 2 [Mo 6 O 18 (NR)]⋅½Me 2 CO, R = -C 6 H 2 -2,6-Me 2 -4-Br, (n-Bu 4 N) 2 [1]⋅½Me 2 CO, has been prepared in acetonitrile by reacting tetrabutylammonium α-octamolybdate, (n-Bu 4 N) 4 [α-Mo 8 O 26 ], with 2,6-dimethyl-4-bromoaniline hydrochloride, 2,6-Me 2 -4-Br-C 6 H 2 NH 2 ⋅HCl, using N,N'-dicyclohexylcarbodiimide, (C 6 H 11 )N=C=N(C 6 H 11 ), as dehydrating agent. This complex, formulated as (n-Bu 4 N) 2 [1]⋅½Me 2 CO, contains a C-Br group which can be functionalized for constructing novel hybrid materials. The complex was fully characterized by IR, UV-Vis, 1 H-and 13 C-NMR spectroscopies, and authenticated by single crystal X-ray diffraction analysis. The asymmetric unit contains two crystallographically independent anions, [1] 2-, differing by the orientation of the phenyl ring relative to the hexamolybdate skeleton, and one molecule of acetone. Both molecules differ in the angles Mo(1)-N(1)-C(1)= 172.2(6) and Mo(7)-N(2)-C(9)= 175.6(6)°. These angles, near to 180°, indicate the presence of a Mo≡N triple bond.

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Section: Discussionmentioning

confidence: 99%

Section: Marcela Cortésmentioning

confidence: 99%

mentioning

confidence: 97%

mentioning

confidence: 99%

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A NEW LINDQVIST-TYPE HEXAMOLYBDATE CLUSTER FUNCTIONALIZED WITH THE jt-DONOR LIGAND 4-BROMO-2,6-DIMETHYLPHENYLIMIDO: SPECTROSCOPIC, ELECTROCHEMICAL AND STRUCTURAL STUDIES

Cortés

Fuentealba

Manzur

et al. 2008

J. Chil. Chem. Soc.

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“…Combination applications of routine synthetic methods and various new synthetic methods will continually impregnate new vital force and energy for POMs chemistry [7][8][9][10][11] . In the fields of designing and assembling molecule-based materials with structures constructed by the so-called anion-cation salts or host-guest solids, POMs act as inorganic building blocks with novel structures and benign performances due to their surface bridging or terminal oxygen atoms possessing the strong coordination and bonding capability [12][13][14][15][16][17][18] .…”

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confidence: 99%

Synthesis, crystal structure and characterization of a 2-D network organic-inorganic hybrid polymer with [α-BW12O40]5− as building blocks

2006

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A two-dimensional network compound [Ce(DMF) 4 (H 2 O)][α-BW 12 O 40 ]·H 2 O·(HDMA) 2 (HDMA = protoned dimethylamine, DMF = N,N-dimethylformamide) was synthesized from α-H 5 BW 12 O 40 ·nH 2 O, Ce(NO 3 ) 3 ·6H 2 O and DMF and characterized by IR, UV spectra and TG-DTA. The result of the X-ray single crystal diffraction indicates that the crystal is monoclinic, space group P2 1 /n, with unit cell dimensional: a = 1.1983(3), b = 2.4216(5), c = 1.9517(4) nm, β = 92.91(3)°, Z = 4, R 1 = 0.07710, wR 2 = 0.1416. Structural analysis indicates that every [Ce(DMF) 4 (H 2 O)] 3+ building block is surrounded by three adjacent [α-BW 12 O 40 ] 5− polyanions, meanwhile, every [α-BW 12 O 40 ] 5− polyanion interconnects with three neighboring [Ce(DMF) 4 (H 2 O)] 3+ subunits, by making use of which two-dimensional network structure can be constructed. The result of thermogravimetric analysis manifests that the title compound has two-stage weight loss and the decomposition temperature of the title polyanionic framework is 560 . The elec ℃ trochemical analysis shows the title polyanion has three-step redox processes in the pH = 4-7 media.Polyoxometalates (POMs) have been attracting extensive interest from scientists owing to the variety of their structure and great potential applications in many fields such as catalysis, medicine, functional material, photochemistry as well as in optical, electric, magnetic and superconductive field as organic-inorganic compound formed by electron acceptor and organic matrix [1][2][3][4][5][6] . Combination applications of routine synthetic methods and various new synthetic methods will continually impregnate new vital force and energy for POMs chemistry [7][8][9][10][11] . In the fields of designing and assembling molecule-based materials with structures constructed by the so-called anion-cation salts or host-guest solids, POMs act as inorganic building blocks with novel structures and benign performances due to their surface bridging or terminal oxygen atoms possessing the strong coordination and bonding capability [12][13][14][15][16][17][18] . Many isolated and 1D crystal structures with saturated Keggin anions as building blocks have been reported [19][20][21][22][23][24][25][26][27][28] , however, 2D and high dimensional structures are relatively rare [29][30][31] . Because saturated borotungstic salts have been less reported as well as have special application in the field of catalysis and medicine [32][33][34] , we synthesized a novel two di-438 Science in China Series B: Chemistry mensional network organic-inorganic hybrid polymer with [α-BW 12 O 40 ] 5− as building blocks and studied its structure and properties. Experimental Materials and physical measurementsThe compound α-H 5 BW 12 O 40 ·nH 2 O was prepared according to the literature [35] and confirmed by IR spectroscopy. Other reagents were obtained from commercial resources and used without further purification.C, H and N element analyses were performed on a Perkin-Elmer 240C elemental analyzer. IR spectra were recorded on a Nicolet...

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Hybrid Molecular Dumbbells: Bridging Polyoxometalate Clusters with an Organic π-Conjugated Rod

Lü

Wei

et al. 2002

Angew. Chem.

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We report the facile synthesis of novel hybrid molecular dumbbells in which two polyoxometalate (POM) clusters are covalently bridged by a rigid, p-conjugated organic rod of controllable length. Hybrid materials based on covalently linked POMs and organic species have been extensively studied in recent years. [1±3] The motivation lies not only in the combinations of ™value-adding properties∫, [4] but also in introducing possible synergistic effects. Among the many organic derivatives of POMs, organoimido derivatives have attracted particular interest because the organic p electrons may extend their conjugation to the inorganic framework and thus dramatically modify the redox properties of the cluster. [4, 5] Moreover, organoimido derivatives of POMs with a remote functionality may be utilized to construct covalently linked POM networks. Here we show that functionalized POM clusters can indeed be utilized to conveniently and efficiently construct POM networks. [3a] Specifically, we report the synthesis of two novel hybrid dumbbells 1 and 2, in which two POM cages are linked through an extended p-conjugated organic bridge. [5c, 6] The hybrid dumbbells were synthesized by the Pd-catalyzed Sonogashira coupling reaction. [7,8] As shown in Scheme 1, direct coupling of the iodo-functionalized hexamolybdate perfluorinated additive OFN, as well as evidence from fluorescence measurements, show that the supramolecular synthon pyrene ± OFN can be used for the association of PEGs in aqueous solution. Experimental SectionDetailed information on synthesis and characterization is published as Supporting Information.3 ± 4 b: Poly(ethylene glycol) (4 mmol) was melted in a flask and stirred under high vacuum. Toluene (100 mL) and 1 or 2 (12 mmol) were added to the polymer and the mixture heated until a clear solution was obtained. Pyridine (1 mL) was added slowly dropwise to the solution followed by stirring at 80 8C for 12 h. The reaction mixture was cooled to RT, the precipitated pyridinium hydrochloride removed by filtration through Celite (Aldrich) and the toluene solution added dropwise to diethyl ether (1 L). The polymer precipitate was collected by filtration, dried under high vacuum, redissolved in a small amount of dichloromethane and reprecipitated into diethyl ether. After recovering the product by filtration the polymer was dried under high vacuum for 24 h.General procedure for the preparation of gels: 4 b (1 equiv) was melted at approximately 60 8C and OFN (2 equiv) dissolved in the melt. The melt was cooled to RT where it solidified. A mixture of deionized water and the desired amount of the solid mixture were sealed in a glass vial and heated in a steam bath under stirring for about 10 min until a homogeneous mixture was obtained. Upon cooling to RT a clear yellow gel or viscous liquid was formed.

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Hybrid Molecular Materials Based on Covalently Linked Inorganic Polyoxometalates and Organic Conjugated Systems

Cited by 124 publications

References 6 publications

A NEW LINDQVIST-TYPE HEXAMOLYBDATE CLUSTER FUNCTIONALIZED WITH THE jt-DONOR LIGAND 4-BROMO-2,6-DIMETHYLPHENYLIMIDO: SPECTROSCOPIC, ELECTROCHEMICAL AND STRUCTURAL STUDIES

A NEW LINDQVIST-TYPE HEXAMOLYBDATE CLUSTER FUNCTIONALIZED WITH THE jt-DONOR LIGAND 4-BROMO-2,6-DIMETHYLPHENYLIMIDO: SPECTROSCOPIC, ELECTROCHEMICAL AND STRUCTURAL STUDIES

Synthesis, crystal structure and characterization of a 2-D network organic-inorganic hybrid polymer with [α-BW12O40]5− as building blocks

Hybrid Molecular Dumbbells: Bridging Polyoxometalate Clusters with an Organic π-Conjugated Rod

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