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Synthesis of Modular “Inorganic–Organic–Inorganic” Polyoxometalates and Their Assembly into Vesicles
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Yin P Pradeep CP Zhang B Li FY Lydon C Rosnes MH Li D Bitterlich E Xu L Cronin L Liu T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(26):8157-8162
An organic-inorganic molecular hybrid containing the Dawson polyoxometalate, ((C(4)H(9))(4)N)(5)H[P(2)V(3)W(15)O(59)(OCH(2))(3)CNHCOC(15)H(31)], was synthesized and its surfactant-like amphiphilic properties, represented by the formation of bilayer vesicles, were studied in polar solvents. The vesicle size decreases with both decreasing hybrid concentration and with increasing polarity of the solvent, independently. The self-assembly behavior of this hybrid can be controlled by introducing different counterions into the acetonitrile solutions. The addition of ZnCl(2) and NaI can cause a gradual decrease and increase of vesicular sizes, respectively. Tetraalkylammonium bromide is found to disassemble the vesicle assemblies. Moreover, the original counterions of the hybrid can be replaced with protons, resulting in pH-dependent formation of vesicles in aqueous solutions. The hybrid surfactant can further form micro-needle structures in aqueous solutions upon addition of Ca(2+) ions. 相似文献
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D Gabb CP Pradeep HN Miras SG Mitchell DL Long L Cronin 《Dalton transactions (Cambridge, England : 2003)》2012,41(33):10000-10005
New polyoxometalate 'sandwiches' have been formed where two [P(2)W(15)O(56)](12-) lacunary Dawson clusters encapsulate two transition metal ions to give clusters with the general formula [M(II)(2)(P(2)W(15)O(56))(2)](20-) (where M = Mn, Co, and Ni respectively), [Fe(III)(2)(P(2)W(15)O(56))(2)](18-), and [Cu(II)(4)(P(2)W(15)O(56))(2)](16-). The Mn, Co, and Ni clusters exhibit a hitherto unseen αββα isomeric geometry and all five compounds are associated with tetrabutylammonium cations which allow for their dissolution in non-aqueous solvent. 相似文献
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Li F Long DL Cameron JM Miras HN Pradeep CP Xu L Cronin L 《Dalton transactions (Cambridge, England : 2003)》2012,41(33):9859-9862
The heteropolyvanadate cluster [(n-C(4)H(9))(4)N](4)[Mn(IV)V(12)O(34)]·2CH(3)CN has been isolated by cation exchange from K(10)[(Mn(IV)V(11)O(32))(2)]·20H(2)O. The structural transformation has been confirmed by X-ray single crystal structure determination and cryospray ionization mass spectrometry measurements. 相似文献
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Rosnes MH Musumeci C Pradeep CP Mathieson JS Long DL Song YF Pignataro B Cogdell R Cronin L 《Journal of the American Chemical Society》2010,132(44):15490-15492
Three organic-inorganic hybrid Mn-Anderson polyoxometalates (POMs), with both symmetrical and asymmetrical appended groups, have been synthesized, identified using electrospray mass spectrometry, and isolated using an approach that allows the three AA, BB, and AB compounds to be structurally characterized. Investigation of the self-assembly of the hybrids on hydrophilic surfaces reveals the formation of nanofibres with characteristics that reflect the nature of the substitution of the POM yielding a route to the programmed assembly of anisotropic hybrid nanostructures. 相似文献
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Chullikkattil P. Pradeep Sabbani Supriya Panthapally S. Zacharias Samar K. Das 《Polyhedron》2006,25(18):3588-3592
A tetra-nuclear copper(II) complex [Cu4(C54H46N4O14)(OH)2] · 10H2O (1) has been synthesized starting from l-tyrosine, NaOH, 2,6-diformyl-4-methylphenol (dfp) and CuSO4 · 5H2O. Compound 1 crystallizes from an ethanol–water mixture in triclinic space group. In the crystal of 1, two binuclear copper units, related by a center of symmetry, are bridged by two hydroxo bridges and results in the formation of a tetra-nuclear {Cu4} structure. Five lattice water molecules, located in the asymmetric unit, interact among themselves and form an unusual form of a water nonamer. In the crystal, the water nonamer is again hydrogen bonded to the next nonamer forming a chainlike polymer. Each {Cu4} complex unit attaches four such water nonamer chains. Variable temperature magnetic data fit to the Bleaney–Bower’s equation with a Curie type of impurity of S = 0.5. The best fit of the magnetic data to this equation yielded 2J = −217, g = 2.019 and a TIP value of 60 × 10−6 cm3 mol−1. 相似文献
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Pradeep CP Long DL Streb C Cronin L 《Journal of the American Chemical Society》2008,130(45):14946-14947
The pH-controlled assembly/disassembly of a nanoscale {P4W52O178}24- cluster at pH 2 to a {P4W44O152}20- cluster at pH 3-5 via a {P3W39O134}19- cluster species at pH 2-3 to finally give {P2W19O69(OH2)}14- at pH 6 is reported. This process can be traced in the solid state crystallographically and in solution using dynamic light scattering studies. 相似文献
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