共查询到20条相似文献,搜索用时 687 毫秒
1.
Prof. Dr. Mannar R. Maurya Naveen Kumar Dr. Shailendra K. Maurya Prof. Dr. Fernando Avecilla 《欧洲无机化学杂志》2023,26(3):e202200536
Mono benzoxazine appended N-capped amino bis(disubstitutedphenol) ligands [ II ( a–c )] upon reaction with VVO(OEt)3 in a 1 : 1 molar ratio in EtOH/MeOH give [{VVO}en(3,5-dtbb)3] ( 1 ), [{VVO}en(3-tb,5-mb)3] ( 2 ) and [{VVO}en(3,5-dmb)3] ( 3 ). During the reaction, the benzoxazine ring opens with the loss of methylene group and the newly formed ligands, N,N-bis(2-hydroxy-3,5-disubstitutedbenzyl)-N’-2-hydroxy-3,5-disubstituted benzyledene-1,2-diaminoethane [ III ( a–c )], behave as tribasic pentadentate in these complexes. Under similar conditions, when [MVIO2(acac)2] (M=Mo or W; Hacac=acetylacetone) reacts with II ( a–c ), these ligands retain their identity and form cis-[MVIO2] complexes, [{MoVIO2}{en(3,5-dtbb)2(6,8-dtbbenzox)}] ( 4 ), [{MoVIO2}{en(3-tb,5-mb)2(6-tb,8-mbbenzox)}] ( 5 ) and [{MoVIO2}{en(3,5-dmb)2(6,8-dmbenzox)}] ( 6 ), [{WVIO2}{en(3,5-dtbb)2(6,8-dtbbenzox)}] ( 7 ), and [{WVIO2}{en(3-tb,5-mb)2(6-tb,8-mbbenzox)}] ( 8 ). However, the benzoxazine ring ruptures in case of ligand IIc under these conditions and form [{WVIO2}{en(3,5-dmb)3}] ( 10 ), similar to complexes 1–3 . Complex [{WVIO2}{en(3,5-dmb)2(6,8-dmbenzox)}] ( 9 ), having structure similar to 4–8 , could only be obtained when the reaction was carried out in toluene. Not only 9 , even complexes 4–8 can be isolated in toluene. Rupturing of both benzoxazine rings has also been experienced when ligands 1,2-bis(6,8-disubstitutedbenzo[e][1,3]oxazin-3(4H)-yl)ethane [ I ( a–c )] react with [MVIO2(acac)2] (M=Mo or W) in MeOH and give salan type complexes [(MVIO2)en(3,5-dtbb)2] [M=Mo ( 11 ), M=W ( 14 )], [(MVIO2)en(3-tb,5-mb)4] [M=Mo ( 12 ), M=W ( 15 )] and [(MVIO2)en(3,5-dmb)4] [M=Mo ( 13 ), M=W ( 16 )]. Complexes 1–9 have been used as catalyst for the multicomponent Biginelli reaction for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones (DHPMs) and oxidative bromination of phenol derivatives. 相似文献
2.
Summary A binuclear oxo MoV hypophosphite of composition [Mo2O4(H2PO2)2(H2O)2], is prepared by direct reduction of MoVI oxide hydrate (MoO3·H2O) with hypophosphorus acid in an argon atmosphere, and characterised by i.r., and electronic spectra, magnetic susceptibility and cyclic voltammetry measurements.1H and31Pn.m.r., x-ray diffraction and thermal analysis data contribute to its molecular structure elucidation, and a dioxobridged dioxo MoV with bidentate hypophosphite ion and water molecule completing the octahedral coordination around each Mo atom is proposed. 相似文献
3.
Jiqing Xu Renzhang Wang Chunxiao Guo Guoyu Yang Qingxin Zeng Weiming Bu Ling Ye Yuguo Fan Guangdi Yang 《中国科学:化学(英文版)》2001,44(2):137-146
A nickel-1,10-phenanthroline complex supported on an octamolybdate, [(Ni(phen)2 2(ξ-Mo8O26)], has been hydrothermally synthesized with MoO3, H2MoO4, Ni(OAc)2 6H3O and 1,10-phenathroline (1,10-phen) as raw materials. The crystals of the compound belong to monoclinic P21/n space group,a = 1.2952(2),b = 1.6659(10),c = 1.3956(12) nm, β =106.273(8)°,V = 2.8906(5) nm3,Z = 2. 5604 observable reflections (I >2σ(I)) were used for structure resolution and refinements to converge to finalR 1 = 0.0414,wR 2 = 0.0815. The result of structure determination shows that the compound contains octamolybdate possessing a novel structure type (named as ξ-isomer). The feature of ξ-[Mo8O26]4- is that it is composed of Mo6O6 ring and two MoO6 octahedral located at cap positions on opposite faces. The Mo6O6 ring contains two octahedral and four trigonal-bipyramidal MoVI atoms. Each ξ-[Mo8O26]4- unit is bonded with two [Ni(phen)2]2+ through terminal oxygen atoms of octahedral and neighbouring trigonal-bipyramidal Mo atom in the Mo6O6 ring. IR and UV-Vis spectra of the compound were measured and its electronic structure was studied by EHMO method. 相似文献
4.
Jiqing Xu Renzhang Wang Chunxiao Guo Guoyu Yang Qingxin Zeng Weiming Bu Ling Ye Yuguo Fan Guangdi Yang 《中国科学B辑(英文版)》2001,44(2):137-146
A nickel-1,10-phenanthroline complex supported on an octamolybdate, [(Ni(phen)2
2(ξ-Mo8O26)], has been hydrothermally synthesized with MoO3, H2MoO4, Ni(OAc)2 6H3O and 1,10-phenathroline (1,10-phen) as raw materials. The crystals of the compound belong to monoclinic P21/n space group,a = 1.2952(2),b = 1.6659(10),c = 1.3956(12) nm, β =106.273(8)°,V = 2.8906(5) nm3,Z = 2. 5604 observable reflections (I >2σ(I)) were used for structure resolution and refinements to converge to finalR
1 = 0.0414,wR
2 = 0.0815. The result of structure determination shows that the compound contains octamolybdate possessing a novel structure
type (named as ξ-isomer). The feature of ξ-[Mo8O26]4- is that it is composed of Mo6O6 ring and two MoO6 octahedral located at cap positions on opposite faces. The Mo6O6 ring contains two octahedral and four trigonal-bipyramidal MoVI atoms. Each ξ-[Mo8O26]4- unit is bonded with two [Ni(phen)2]2+ through terminal oxygen atoms of octahedral and neighbouring trigonal-bipyramidal Mo atom in the Mo6O6 ring. IR and UV-Vis spectra of the compound were measured and its electronic structure was studied by EHMO method. 相似文献
5.
A new molybdophosphate (NH4)8{Mo2VO4[(Mo2VIO6)CH3C(O)(PO3)2]2}·14H2O (1), has been synthesized by the reaction of {Mo2VO4(H2O)6}2+ fragments with 1-hydroxyethylidenediphosphonate (hedp HOC(CH3)(PO3H2)2), and it is characterized by 31P NMR, IR, UV, element analysis, TG and single-crystal X-ray analysis. The structure analysis reveals that the polyoxoanion
can be described as two {(Mo2VIO6)(CH3C(O)(PO3)2} units connected by a {Mo2VO4}2+ moiety. In the structure, the six Mo atoms are arranged into a new “W-shaped” structure, which represents a new kind of molybdophosphate. 相似文献
6.
Investigation on the Ternary System V/Mo/O During chemical transport reactions mixtures of pseudo-binary line of intersection V2O5/MoO3 are separated into two phases, the V2O5-(α) phase, which MoO3-content depends on the oxygen partial pressure during the deposition and the MoO3 phase which contains no more than 1% (n/n) V2O5. Ternary compounds do not exist on the pseudo-binary line. V9Mo6O40 is formed by the reaction of V2O5 and MoO3 (3:2) under exclusion of oxygen. The compound may be chemically transported under the own oxygen coexistence pressure. It was shown by total pressure measurements of V2O5/MoO3 starting mixtures that the insertion of MoO3 in the α-phase and the formation of the V9Mo6O40 phase respectively is connected with elimination of oxygen and the reduction of VV to VIV in equivalence of the quantity of incorporated MoO3. 相似文献
7.
8.
Porous Capsules with a Large Number of Active Sites: Nucleation/Growth under Confined Conditions
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Somenath Garai Dr. Mirta Rubčić Dr. Hartmut Bögge Prof. Dr. Pierre Gouzerh Prof. Dr. Achim Müller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(11):4321-4325
This work deals with the generation of large numbers of active sites and with ensuing nucleation/ growth processes on the inside wall of the cavity of porous nanocapsules of the type (pentagon)12(linker)30≡{(MoVI)MoVI5}12{MoV2(ligand)}30. A first example refers to sulfur dioxide capture through displacement of acetate ligands, while the grafted sulfite ligands are able to trap {MoO3H}+ units thereby forming unusual {(O2SO)3MoO3H}5? assemblies. A second example relates to the generation of open coordination sites through release of carbon dioxide upon mild acidification of a carbonate‐type capsule. When the reaction is performed in the presence of heptamolybdate ions, MoO42? ions enter the cavity where they bind to the inside wall while forming new types of polyoxomolybdate architectures, thereby extending the molybdenum oxide skeleton of the capsule. Parallels can be drawn with Mo‐storage proteins and supported MoO3 catalysts, making the results relevant to molybdenum biochemistry and to catalysis. 相似文献
9.
《中国化学快报》2023,34(3):107365
Available online two new Ni8Mo8 bimetallic coordination clusters, [Ni4(TC4A)]2[(Mo5VMo3VIO24)(PO4)] (+Solvent) (Ni8PMo8, H4TC4A= p-tert-butylthiacalix[4]arene) and [Ni4(TC4A)]2[(Mo5VMo3VIO24)(OH)(CO3)] (+Solvent) (Ni8Mo8), were synthesized by solvothermal method and structurally characterized by single-crystal X-ray diffraction, powder X-ray diffraction, FT-IR spectroscopy, and TGA experiments, respectively. The usage of H3PMo12O40 as source for Ni8PMo8 resulted a sandwich like structure built from two Ni4-thiacalix[4]arene units and a Mo8 polyoxometalate with inner spaces of PO43?. Ni8Mo8 with the similar structure to that of Ni8PMo8 is from H2MoO4 starting reagent with OH? and CO32? anions encapsulated in the center. The two clusters can be directly loaded on carbon paper and utilized as working electrodes which showed distinguishable performances for glucose detection and oxidation. This work provides a better understanding of the structure–property relationships in using substituted polyoxometalates for electrochemical applications and is helpful for building calixarene-based or polyoxometalate-based functional materials. 相似文献
10.
Yu. V. Manakin D. A. Kuznetsov I. V. Fedyanin K. A. Lyssenko N. V. Kovaleva A. V. Kulikov T. A. Bazhenova 《Russian Chemical Bulletin》2013,62(8):1843-1851
General conditions for the formation of heterometallic clusters by the simultaneous methanolysis of MoCl5 and MgCl2 were determined. The resultant alkalinity of the reaction solution, the Mg/Mo molar ratio, and the presence of traces of water are key factors responsible for the composition and structure of the mixed magnesium molybdenum methoxides that formed. The new decanuclear mixed-valence MoV,VI Mg oxomethoxide [MoV 4O4(μ3-O)2(μ2-O)2MoVI 2-O4(OMe)2Mg4(MeOH)6(μ3-OMe)6(μ2-OMe)8] (1) was synthesized by the reaction of lowernuclearity magnesium molybdenum oxoalkoxide complexes: NaMoV of the complex Na(MeOH)MoV 2O2(μ2-OMe)3(OMe)4 (2) and MgMoVI of the complex [MoVIO2Mg(MeOH)2-(OMe)4]2 (3). The molecular structure of 1 was determined by X-ray diffraction. 相似文献
11.
Two new organic–inorganic hybrid compounds, [Cu(phen)(prz)]2[PMoV1MoVI7VIV2VV4O42]·4H2O (1) and [Ag2(phen)4]2[PMoV1MoVI7VIV2VV4O42] (2) (phen = 1,10-phenanthroline, prz = pyrazine), have been synthesized and characterized by IR, XPS, XRD, UV–vis, fluorescent spectra analyses, elemental analyses, X-ray diffraction analyses, TG analyses, and cyclic voltammetric measurements. Both compounds are formed by Keggin POM cores and transition metal fragments. Compound 1 exhibits an unprecedented 1-D chain structure constructed from [PMoV1MoVI7VIV2VV4O42]4? and [Cu(phen)(prz)]2+ in the –A–B↑–C–B↓– linking mode. Compound 2 shows a supramolecular structure formed by [PMoV1MoVI7VIV2VV4O42]4? and [Ag2(phen)4]2+. 相似文献
12.
Bin Wang Bao Li Guang-Feng Hou Hao-Long Li Shan Wang Li-Xin Wu Shaylyn Walter Li-Hua Bi 《Journal of Cluster Science》2014,25(3):741-753
An inorganic–organic hybrid compound, (H2bpy)3[AsIIIAs2 VMo15 VIMo3 VO62]·3H2O (bpy: 4,4′-bipyridine) (1) has been synthesized under hydrothermal conditions and characterized by elemental analysis, X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction, IR spectrum, UV–Vis spectrum, thermogravimetric analysis and single-crystal X-ray diffraction. The crystallographic analysis reveals that compound 1 is composed of a Wells–Dawson polyoxoanion [As2 VMo15 VIMo3 VO62]9? with the mixed valence of MoV,VI, which acts as a tetradentate ligand coordinating with the AsIII cation to form the mixed valence AsIII,V containing arsenomolybdate with the single cap structure in a chelate coordination mode. In the solid state, compound 1 shows a 3D supramolecular structure through hydrogen-bonding interactions (C–H···O, N–H···O, N–H···N). In addition, compound 1 exhibits reversible multi-electron redox processes and effective electrocatalytic activities towards the reduction of H2O2, NaNO2 and KBrO3. Moreover, compound 1 is used as a reducing agent of the graphene oxide to prepare graphene by a green chemistry type one-step synthesis method, which is characterized by XPS, Raman spectroscopy, PXRD, IR, scanning electron microscopy and transmission electron microscopy. 相似文献
13.
Yan Wang Li-Na Xiao Hong Ding Zhong-Min Gao Tie-Gang Wang Xiao-Bing Cui Ji-Qing Xu 《Journal of solid state chemistry》2010,183(12):2862-2868
Three new supramolecular compounds based on triethylenediamine and different polyoxometalates [WVI3VV3O19H]{[Cu(HDABCO)]2(H2O)} (1), [P2MoVI18O62][HDABCO]2[H2DABCO]2·12 H2O (2) and [MoVI7.5WVI0.5O27][Cu(HDABCO)]2·2 H3O·2 H2O (3) (DABCO=triethylenediamine) have been synthesized hydrothermally and characterized by IR, TG, XPS and X-ray diffraction analyses. Crystal structure analyses reveal that compound 1 exhibits a face-centered cubic packing motif, compound 2 displays a supramolecular structure constructed form the “chains” arranged hexagonally, compound 3 contains [Mo7.5W0.5O27]∞ chain decorated by [Cu(HDABCO)]2+ cations, which was then packed into a layer structure. These results show that the same organonitrogen combining with the different POMs will yield different supramolecular networks. 相似文献
14.
《Journal of Coordination Chemistry》2012,65(4):627-639
Two polyoxometalate-based inorganic metal-organic hybrid supramolecular complexes [Cu(2,2′-bpy)2]2[VIV 2MoV 5MoVI 7O38(PO4)] (1) (2,2′-bpy?=?2,2′-bipyridine) and [Cu(2,2′-bpy)2]2[MoVMoVI 11O36(PO4)]?·?3H2O (2), have been hydrothermally prepared and structurally characterized by single-crystal X-ray diffraction. Both complexes are constructed from polyoxoanions (the bivanadyl capped α-Keggin polymolybdate anion [VIV 2MoV 5MoVI 7O38(PO4)]4? for 1 and the reduced 12-molybdophosphate anion [MoVMoVI 11O36(PO4)]4? for 2) and copper(II) complex cations [Cu(2,2′-bpy)2]2+, forming two-dimensional (2D) layer network structures, in which the polyoxoanion and the complex fragment cation connect with each other through Cu?···?Opolyoxoanion short contact weak interactions, which mediate ferromagnetic interaction. 相似文献
15.
Cungen Zhang Gerd Rheinwald Vasile Lozan Biao Wu Paul‐Gerhard Lassahn Heinrich Lang Christoph Janiak 《无机化学与普通化学杂志》2002,628(6):1259-1268
Four new molybdenum complexes [MoVIO2(L1)(Him)] ( 1 ), [MoVIO2(L1)(3‐MepzH] ( 2 ), [MoVIO2(L2)(3‐MepzH)] ( 3 ), and [(MoVIO2)2(μ‐L3)(MeOH)2] ( 4 ) were synthesized and characterized by IR, NMR, ESI‐MS, and single‐crystal structure analysis [H2L1 = 2‐(salicylideneamino)‐2‐methyl‐1‐propanol, H2L2 = 2‐(3‐methoxysalicylideneamino)‐2‐methyl‐1‐propanol, H4L3 = 1, 7‐bis(salicylidene)dihydrazide malonic acid, Him = imidazole and 3‐MepzH = 3‐methylpyrazole]. In all four structures the molybdenum atom has a distorted octahedral coordination with the three meridional donor atoms from the Schiff base di‐ or tetraanion (L1, 2)2—/(L3)4— and one oxo group occupying the sites of the equatorial plane. The other oxo group and the azole or methanol molecule occupy the apical sites. In 1—3 two centrosymmetrically related molecules form a hydrogen‐bonded pair through the (azole)N‐H···O(alkoxo) interaction. Additional crystal packing appears to be controlled mostly by π stacking between the aromatic rings of the salicyl moiety. ESI‐MS investigations reveal that the integrity of complexes 1—4 is largely retained in methanol solution. At the same time evidence is provided that di‐ to tetranuclear oligomers of formula [{MoVIO2(L)}x] and [{MoVIO2(L)}x(3‐MepzH)] with L = L1, L2, x = 2, 3, 4 are present simultaneously with 2 and 3 in methanol solution, respectively the tetranuclear species [{(MoVIO2)2(L3)}2] with 4 . 相似文献
16.
Marina Cindri Neven Strukan Tanja Kajfe Gerald Giester Boris Kamenar 《无机化学与普通化学杂志》2001,627(12):2604-2608
The novel dioxomolybdenum(VI) complexes with methyl ( 1 ), ethyl ( 2 ), n‐propyl ( 3 ), i‐propyl ( 4 ), n‐butyl ( 5 ) and cyclohexyl ( 6 ) ester of 2‐mercaptonicotinic acid have been prepared in the reactions of MoO2Cl2 and MoO2(acac)2 (acac = 2,4‐pentandionate) with mercaptonicotinic acid in corresponding alcohol. The esterification reaction was catalyzed by MoV originated from the reduction of MoVI with mercaptonicotinic ‐SH group with simultaneous formation of S–S bond resulting from the condensation of two 2‐mercaptonicotinic molecules. The presence of MoV was proved by ESR spectra. The molecular and crystal structures of 1 , 2 , 3 and 4 as well as of the by‐products 1,1′‐dithio‐2,2′‐n‐butylnicotinoate ( 7 ) and tetramethylammonium hexachloromolybdate(V) ( 8 ) have been determined by a X‐ray single crystal diffraction. The complexes 1 – 4 contain MoO22+ core with octahedral coordination of each molybdenum atom complexed by two 2‐mercaptonicotinato N and S donor atoms. 相似文献
17.
André Leclaire Vincent Caignaert Bernard Raveau 《Journal of solid state chemistry》2007,180(7):2044-2052
The single crystal structure of a series of nine isotypic Mo(V) diphosphates was determined from crystals with composition A2+(MoO)10(P2O7)8 (A=Ba, Sr, Ca, Cd, Pb) and A+(MoO)5(P2O7)4 (A=Ag, Li, Na, K). The structure of those phosphates, built up of corner sharing MoO6 octahedra, MoO5 tetragonal pyramids and P2O7 diphosphates groups, forms eight-sided tunnels as described by Lii et al. for A=Ag. New features are evidenced: (1) existence of two orientations, up and down along b for the MoO5 pyramids; (2) maximum insertion rate of the divalent cations which is twice less than that of the univalent cations; (3) different behavior of the series “Pb, Sr, Ba, Li, Na, K” which exhibits only one kind of site for the inserted cation, compared to the “Cd, Ca, Ag” series for which two kinds of sites are observed; (4) off-centering of the A-site cations with respect to the tunnel axis; and (5) unusually high thermal factors along the tunnel axis, but absence of ionic conductivity. 相似文献
18.
The aim of this study is to investigate the influence of some monovalent counter-ions (NH4
+, K+ and Cs+) on thermal behavior of polyoxometalates derived from H3PMo12O40 (HPM) and H4PVMo11O40 (HPVM) by replacing the protons. The IR and UV-VIS-DRS spectra of some acid and neutral NH4
+, K+, Cs+ salts, which derived from HPM and HPVM, confirmed the preservation of Keggin units (KU) structure. The X-ray diffraction
spectra clearly showed the presence of a cubic structure. The non-isothermal decomposition of studied polyoxometalates proceeds
by a series of processes: the loss of crystallization water; the loss of O2 accompanying with a reduction of V5+→V4+ and Mo6+→Mo5+; the loss of constitution water started at 360°C for HPVM salts and 420°C for HPM salts; the decomposition of ammonium ion
over 420°C with NH3, N2 and H2O elimination and simultaneous processes of reduction (V5+→ V4+ and Mo6+→ Mo5+ or Mo4+) associating with endothermic effects; reoxidation of Mo5+, Mo4+ and V4+with a strong exothermic effect; destruction of KU to the oxides: P2O5, MoO3 and V2O5 and the crystallization of MoO3.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
19.
Room‐Temperature and Aqueous‐Phase Synthesis of Plasmonic Molybdenum Oxide Nanoparticles for Visible‐Light‐Enhanced Hydrogen Generation
下载免费PDF全文
![点击此处可从《化学:亚洲杂志》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Jiayuan Shi Dr. Yasutaka Kuwahara Dr. Meicheng Wen Dr. Miriam Navlani‐García Dr. Kohsuke Mori Prof. Taicheng An Prof. Hiromi Yamashita 《化学:亚洲杂志》2016,11(17):2377-2381
A straightforward aqueous synthesis of MoO3?x nanoparticles at room temperature was developed by using (NH4)6Mo7O24?4 H2O and MoCl5 as precursors in the absence of reductants, inert gas, and organic solvents. SEM and TEM images indicate the as‐prepared products are nanoparticles with diameters of 90–180 nm. The diffuse reflectance UV‐visible‐near‐IR spectra of the samples indicate localized surface plasmon resonance (LSPR) properties generated by the introduction of oxygen vacancies. Owing to its strong plasmonic absorption in the visible‐light and near‐infrared region, such nanostructures exhibit an enhancement of activity toward visible‐light catalytic hydrogen generation. MoO3?x nanoparticles synthesized with a molar ratio of MoVI/MoV 1:1 show the highest yield of H2 evolution. The cycling catalytic performance has been investigated to indicate the structural and chemical stability of the as‐prepared plasmonic MoO3?x nanoparticles, which reveals its potential application in visible‐light catalytic hydrogen production. 相似文献
20.
M. Nieves Corella‐Ochoa Dr. Haralampos N. Miras Dr. De‐Liang Long Prof. Leroy Cronin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(43):13743-13754
Five mixed‐metal mixed‐valence Mo/V polyoxoanions, templated by the pyramidal SeO32? heteroanion have been isolated: K10[MoVI12VV10O58(SeO3)8]?18 H2O ( 1 ), K7[MoVI11VV5VIV2O52(SeO3)]?31 H2O ( 2 ), (NH4)7K3[MoVI11VV5VIV2O52(SeO3)(MoV6VV‐ O22)]?40 H2O ( 3 ), (NH4)19K3[MoVI20VV12VIV4O99(SeO3)10]?36 H2O ( 4 ) and [Na3(H2O)5{Mo18?xVxO52(SeO3)} {Mo9?yVyO24(SeO3)4}] ( 5 ). All five compounds were characterised by single‐crystal X‐ray structure analysis, TGA, UV/Vis and FT‐IR spectroscopy, redox titrations, and elemental and flame atomic absorption spectroscopy (FAAS) analysis. X‐ray studies revealed two novel coordination modes for the selenite anion in compounds 1 and 4 showing η,μ and μ,μ coordination motifs. Compounds 1 and 2 were characterised in solution by using high‐resolution ESI‐MS. The ESI‐MS spectra of these compounds revealed characteristic patterns showing distribution envelopes corresponding to 2? and 3? anionic charge states. Also, the isolation of these compounds shows that it may be possible to direct the self‐assembly process of the mixed‐metal systems by controlling the interplay between the cation “shrink‐wrapping” effect, the non‐conventional geometry of the selenite anion and fine adjustment of the experimental variables. Also a detailed IR spectroscopic analysis unveiled a simple way to identify the type of coordination mode of the selenite anions present in POM‐based architectures. 相似文献