ISSN 1070?3284, Russian Journal of Coordination Chemistry, 2011, Vol. 37, No. 1, pp. 30–35. © Pleiades Publishing, Ltd., 2011.301INTRODUCTIONDue to their intrinsic aesthetic values and potentialapplications, the construction of supramolecularassemblies from organic and/or inorganic molecularbuilding blocks has evolved rapidly in many areas,such as inorganic chemistry, coordination chemistry,crystal engineering, and materials science [1–3].Notably, metal?Schiff?base ( MSB ) complexes areexcellent organometallic candidates to constructsupramolecular compounds due to their powerfulapplications in some fields [4, 5]. At the same time,polyoxometalates ( POM ) as unique anionic metaloxide clusters with many properties and applicationsare an outstanding class of functional inorganic build?ing blocks in construction of supramolecular com?pounds [6–11]. The introduction of a MSB into thechemistry of POM is currently opening up a newdirection for studies on supramolecular compoundsand hybrid materials. However, up to now the reportsmade on a combination of these two interesting fieldsto prepare new hybrid materials characterized by sin?gle?crystal X?ray diffraction analyses have been farunexplored [12–14]. Usually, in order to prepare thePOM?MSB compound, the MSB complex should besynthesized first. To the best of our knowledge, the insitu preparation of POM?MSB compounds was neverexplored. Here, we report the in situ preparation of aPOM?MSB compound containing Mn 2+ ions, 1,4?bis(4?imidazolyl)?2,3 ?diaza?1,3?butadien ( L ) andKeggin?type [PMo 12 O 40 ] 3– polyanions.1 The article is published in the original.EXPERIMENTALMaterials and Instruments. All organic solventsand materials used for synthesis were of reagent gradeand used without further purification, α ?H 3 PMo 12 O 40 ⋅6H 2 O was prepared according to a literature method[15] and characterized by IR spectra and TG analyses.Ligand was synthesized according to a literaturemethod [16]. Elemental analyses (C, H, and N) werecarried out on a Perkin Elmer 240C analyzer. IR spec?tra were recorded on a VECTOR 22 Bruker spectro?photometer with KBr pellets in the 400–4000 cm –1region at room temperature. Thermogravimetric anal?ysis of compound I was performed on a Perkin?Elmerthermal analyzer under nitrogen at a heating rate of10 ° C/min .Synthesis of compound I. The formation of het?eropolyacid manganese salts was accomplished by theneutralization of the acids α ?H 3 PMo 12 O 40 ⋅ 6H 2 O(40 mg, 0.02 mmol) and adding Mn(NO 3 ) 2 ⋅ 4H 2 O(8 mg, 0.03 mmol) dissolved in water (2 ml). The solu?tion was heated at 80 ° C in a water bath. Yellow crystalswere formed by cooling the saturated solution andslow evaporation at room temperature, and character?ized by the IR spectrum. Compound I was prepared bythe layering method. A buffer layer of a solution(10 ml) methanol/water (1 : 1, v/v) was carefully lay?ered over 4 ml of a DMSO solution of L (12 mg,0.06 mmol), then a methanolic solution (4 ml) ofresultant heteropolyacid manganese salts was carefullylayered over the buffer layer. Black block crystalsA New Supramolecular Compound Based on Mn(II)?Schiff?Base and Keggin?Type [PMo 12 O 40 ] 3– 1M. L. Wei*, P. F. Zhuang, R. P. Sun, and H. H. LiCollege of Chemistry and Environmental Science, Henan Normal University, Xinxiang 453007, P.R. China*e?mail: weimeilin@henannu.edu.cnReceived March 3, 2010Abstract —A new organometallic?inorganic hybrid compound {[Mn(L) 2 ] 2 [PMo 12 O 40 ][NO 3 ] ⋅ 4CH 3 OH ⋅3H 2 O} n ( I ) , where L is 1,4?bis(4?imidazolyl)?2,3 ?diaza?1,3?butadiene) was synthesized in situ from[PMo 12 O 40 ] 3– , Mn 2+ and L reaction in an H 2 O–DMSO–CH 3 OH mixture at room temperature, and theproduct was structurally characterized by elemental analysis, infrared spectroscopy, and single?crystal X?raydiffraction analysis. Compound I is constructed from alternating layers of the metal?Schiff?base cation andKeggin anions based on electrostatic forces and hydrogen bond interactions.DOI: 10.1134/S1070328411010167
