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By virtue of combining an in‐situ assembly process with a stepwise synthesis in conventional aqueous solution, two series of unique organic–inorganic hybrid heteropolyoxomolybdates were constructed from plenary Keggin germanomolybdates and Cu–Ln heterometallic units and fully characterized: [H2INA]2H8[LnCu(INA)4(H2O)6]2[α‐GeMo12O40]3⋅52 H2O (Ln=La3+ (1), Ce3+ (2), Pr3+ (3), Nd3+ (4), Sm3+ (5), Eu3+ (6); HINA=isonicotinic acid) and (NH4)[Cu(PA)2][Cu(PA)2Ln(H2O)8][α‐GeMo12O40]⋅10 H2O (Ln=Nd3+ (7), Sm3+ (8), Eu3+ (9); HPA=picolinic acid). The most remarkable structural characteristic of compounds 1–6 was that their molecular units were defined by three discrete plenary Keggin [α‐GeMo12O40]4− polyoxoanions and two organic–inorganic hybrid heterometallic [LnCu(INA)4(H2O)6]+ moieties, whereas compounds 7–9 exhibited a nice‐looking 1D chain‐like structure that was built from plenary [α‐GeMo12O40]4− polyoxoanions, pendent [Cu(PA)2] complexes, and bridging {[Cu(PA)2][Ln(H2O)8]}3+ heterometallic groups. Notably, two different pyridine carboxylic acid ligands led to the discrepancy between the two structure types. To the best of our knowledge, compounds 1–9 constitute the first examples of plenary Keggin heterometallic germanomolybdates that include Cu–Ln–organic subunits. Further studies revealed that compounds 3 and 8 exhibited fast adsorption capacity for cationic dyes methylene blue (MB) and rhodamine B (RhB) in water. Moreover, compounds 3 and 8 could quickly and selectively adsorb MB from a mixture of MB/methyl orange (MO) or MB/azophloxine (Apo). Ge whizz: Two series of Cu–Ln heterometallic Keggin‐type germanomolybdate hybrids have been synthesized and their adsorption performance of dyes has been intensively probed. [ABSTRACT FROM AUTHOR]

Abstract: In the presence of the larger [H2N(CH3)2]+ and K+ counter cations as structure‐stabilizing agents, a class of unprecedented selenium and lanthanide (Ln) simultaneously bridging tetra‐vacant Dawson‐like selenotungstate aggregates [H2N(CH3)2]2Na9K2H19{[Ln4W4 Se4O22(H2O)5](Se2W14O52)2}2⋅60 H2O [Ln=TbIII (1), DyIII (2), HoIII (3), ErIII (4), TmIII (5), YbIII (6)] have been obtained by the one‐pot assembly reaction of Na2WO4⋅2 H2O, Ln(NO3)3⋅6 H2O, and Na2SeO3 under moderately acidic aqueous conditions and the complexes were structurally characterized by elemental analyses, IR spectra, single‐crystal X‐ray diffraction, powder X‐ray diffraction (PXRD), and thermogravimetric (TG) analyses. It should be noted that the appropriate molar ratio of Se/W is extremely important in the formation of 1–6 and can effectively ameliorate the yield of 1–6. Moreover, dimethylamine hydrochloride is also indispensable and plays a considerably important role in improving the solubility of Ln ions and stabilizing the structures of 1–6. The main polyoxoanion skeletons of 1–6 are constructed from two sandwich‐type tetra‐vacant Dawson‐like {[Ln4W4Se4O22(H2O)5](Se2W14O52)2}16− half‐units linked through two W‐O‐Ln bridges. The sandwich‐type half‐unit comprises two tetra‐vacant Dawson‐like [Se2W14O52]12− fragments encapsulating a unique dodecanuclear Se‐Ln‐W [Ln4W4Se4O22(H2O)5]8+ oxo cluster. Their solid‐state visible and NIR fluorescent properties and lifetime decay behaviors were measured and their solid‐state luminescent spectra mainly demonstrate the characteristic emission bands of Ln3+ ions. Moreover, the dominant wavelengths, the color purity, and correlated color temperatures of 1–5 have been also calculated. In addition, the luminous flux values of 1–5 are 2031, 6992, 3071, 921, and 477 lumen, respectively. [ABSTRACT FROM AUTHOR]

Abstract: The exploration of high nuclearity molecular metal oxide clusters and their reactivity is a challenge for chemistry and materials science. Herein, we report an unprecedented giant molecular cerium–bismuth tungstate superstructure formed by self‐assembly from simple metal oxide precursors in aqueous solution. The compound, {[W14CeIV6O61]([W3Bi6CeIII3(H2O)3O14][B‐α‐BiW9O33]3)2}34− was identified by single‐crystal X‐ray diffraction and features 104 metal centers, a relative molar mass of ca. 24 000 and is ca. 3.0×2.0×1.7 nm3 in size. The cluster anion is assembled around a central {Ce6} octahedron which is stabilized by several molecular metal oxide shells. Six trilacunary Keggin anions ([B‐α‐BiW9O33]9−) cap the superstructure and limit its growth. In the crystal lattice, water‐filled channels with diameters of ca. 0.5 nm are observed, and electrochemical impedance spectroscopy shows pronounced proton conductivity even at low temperature. [ABSTRACT FROM AUTHOR]

A trizirconium(IV)-substituted sandwich-type polyoxotungstate, K7.5H6.5[Zr3(µ2-OH)2(µ2-O)(A-α-GeW9O34)(1,4,9-α-P2W15O56)] ·16.5H2O ( 1), was hydrothermally synthesized and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, powder X-ray diffraction, energy-dispersive X-ray spectroscopy, and single-crystal X-ray diffraction. The structural unit of 1 consists of trilacunary Dawson-type phosphotungstate and trilacunary Keggin-type germanotungstate units that are linked by a trizirconium(IV) cluster. [ABSTRACT FROM AUTHOR]

Three types of serine-decorated rare- earth-containing arsenotungstate [H2N(CH3)2]6NaH[RE2 W4O10(H2O)8(Ser)2(B-α-AsW9O33)2]⋅30 H2O (RE3+=Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, and Y3+; 1), [H2N(CH3)2]6Na6− xRE xH4−2 x[RE4W8O19(H2O)10+ y(OH)2(Ser)2(B-α-AsW9O33)4]⋅ n H2O (RE3+=Tb3+, x=1, y=2, n=36; RE3+=Dy3+, Ho3+, Er3+, Yb3+, Y3+, x=0, y=0, n=38; RE3+= Tm3+, x=1, y=0, n=38; Ser=serine; 2), and [H2N(CH3)2]6−2 xNa2+3 xRE xH10−6 x+ y[RE4W8O19(H2O)8(OH)2(Ser)4(B-α-AsW9O33)4]⋅Cl y⋅ n H2O (RE3+=Ce3+, Pr3+, x=1, y=0, n=65; RE3+=Nd3+, Sm3+, x=0, y=0, n=65; RE3+=Eu3+, Gd3+, x=1, y=2, n=45; 3) were synthesized with the participation of the organic solubilizers dimethylamine hydrochloride and l-serine and were structurally characterized. The use of different amounts of rare-earth salts results in the structural transformation from dimerization to tetramerization of types 1- 3. Type 1 is a dimeric sandwich-type assembly of a dual-Ser-participating [RE2W4O10(H2O)8(Ser)2]10+ entity sandwiched by two [B-α-AsW9O33]9− moieties, whereas types 2 and 3 have a tetrameric square structure formed by four [B-α-AsW9O33]9− moieties that anchor a dual/tetra- Ser-participating [RE4W8O19(H2O)10+ y(OH)2(Ser)2]20+ or [RE4W8O19(H2O)8(OH)2(Ser)4]20+ core. The solid-state luminescence properties and lifetime-decay behaviors of these compounds were investigated. The chromaticity coordinates, dominant wavelengths, color purities, and correlated color temperatures were also calculated. [ABSTRACT FROM AUTHOR]

Under hydrothermal conditions, replacement of the water molecules in the [MnIII4MnII2O4(H2O)4]8+ cluster of mixed-valent Mn6 sandwiched silicotungstate [(B-α-SiW9O34)2MnIII4MnII2O4(H2O)4]12− ( 1 a) with organic N ligands led to the isolation of five organic-inorganic hybrid, Mn6-substituted polyoxometalates (POMs) 2- 6. They were all structurally characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, diffuse-reflectance spectroscopy, and powder and single-crystal X-ray diffraction. Compounds 2- 6 represent the first series of mixed-valent {MnIII4MnII2O4(H2O)4− n(L) n} sandwiched POMs covalently functionalized by organic ligands. The preparation of 1- 6 not only indicates that the double-cubane {MnIII4MnII2O4(H2O)4− n(L) n} clusters are very stable fragments in both conventional aqueous solution and hydrothermal systems and that organic functionalization of the [MnIII4MnII2O4(H2O)4]8+ cluster by substitution reactions is feasible, but also demonstrates that hydrothermal environments can promote and facilitate the occurrence of this substitution reaction. This work confirms that hydrothermal synthesis is effective for making novel mixed-valent POMs substituted with transition-metal (TM) clusters by combining lacunary Keggin precursors with TM cations and tunable organic ligands. Furthermore, magnetic measurements reveal that 3 and 6 exhibit single-molecule magnet behavior. [ABSTRACT FROM AUTHOR]

With the rapid development of science and technology and the trend of multidisciplinary pervasion, POM-based TM–RE heterometallic chemistry (POM = polyoxometalate, TM = transition-metal, RE = rare-earth) has become one of the most rapidly growing and challengeable areas of inorganic chemistry due to the impressive structural diversities, various chemical compositions and potential applications of these materials in magnetism, optics, electrochemistry, electrocatalysis and materials science. Over the past several years, continuous interest and persisting efforts have been dedicated to the preparation and exploration of POM-based TM–RE heterometallic derived materials (PTRHDMs), which have led to more than two hundred PTRHDMs. In this review, we summarize the structural types of reported PTRHDMs together with synthetic strategies, structural motifs and relevant functional applications. The exciting array of this emerging research theme presages continuous growth and great vitality. In the last section, some prospects of this branch are also presented and possible guidance for future work is outlined. [ABSTRACT FROM AUTHOR]

A novel 3-connected SrSi2-type 3D chiral framework constructed from hexa-NiII-cluster-substituted polyoxometalate (POM) units [Ni(enMe)2]3[WO4]3[Ni6(enMe)3(OH)3PW9O34]2⋅9H2O ( 1) (enMe=1,2-diaminopropane) has been made from a hydrothermal synthetic method. This POM represents the first 3D framework based on {Ni6PW9} units and {WO4} connectors. [ABSTRACT FROM AUTHOR]

Three novel hexa-Ni-substituted Dawson phosphortungstates [Ni6(en)3(H2O)6(μ3-OH)3(H3P2W15O56)] ⋅14 H2O ( 1), [Ni(enMe)2(H2O)][Ni6(enMe)3(μ3-OH)3(H2O)6(HP2W15O56)] ⋅ 10 H2O ( 2), and [Ni(enMe)2]3[Ni(enMe)2(H2O)][Ni(enMe)(H2O)2][Ni6(enMe)3(μ3-OH)3(Ac)2(H2O)(P2W15O56)]2 ⋅6 H2O ( 3) (en=ethylenediamine, enMe=1, 2-diaminopropane, Ac=CH3COO−) have been made under hydrothermal conditions and were characterized by IR spectroscopy, elemental analysis, diffuse reflectance spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. The common structural features of compounds 1- 3 contain the similar hexa-Ni-substituted Dawson polyoxometalate (POM) units that can be viewed as a [Ni6(μ3-OH)3]9+ cluster capping on a [P2W15O56]12− fragment. Compounds 1 and 2 are two isolated clusters, whereas compound 3 is the first 3D POM framework constructed from hexa-Ni-substituted Dawson POM units and Ni(enMe) complex bridges. The preparations of compounds 1- 3 not only indicate that triangle coplanar Ni6 clusters are very stable fragments in both trivacant Keggin and trivacant Dawson POM systems, but also offer that the hydrothermal technique can act as an effective strategy for making novel Dawson-type high-nuclear transition-metal cluster substituted POMs by combination of lacunary Dawson precusors with transition-metal cations in the tunable role of organic ligands. In addition, magnetic measurements illustrate that there exist overall ferromagnetic interactions in compound 3. [ABSTRACT FROM AUTHOR]

Two Co-substituted sandwich-type polyoxometalates (Hen)[Co(HO)(PWO)]{[Co(HO)][Co(HO)(PWO)]}·18HO ( 1) and (Hen)[Co(HO)(HGeWO)]{[Co(HO)][Co(HO)(HGeWO)]}·16HO ( 2) (en = ethylenediamine) have been hydrothermally synthesized and characterized by IR spectra, elemental analyses, thermogravimetric analyses, powder X-ray diffraction and single-crystal X-ray diffraction. Single-crystal structure analysis reveals that the molecules of 1 and 2 contain two Co-substituted sandwich-type polyoxoanions. This type of a molecular unit containing double polyoxoanions is very rare. From the viewpoint of supramolecular chemistry, the sandwich-type polyoxoanions in 1 and 2 can be further extended to 3-D frameworks via extensive hydrogen-bonding interactions. [ABSTRACT FROM AUTHOR]

Two unique organic–inorganichybrid heteropolymolybdateswith copper–aminoacid complexes [Cu(arg)2]2[(CuO6)Mo6O18(As3O3)2]·4 H2O (1) and[Cu(arg)2]3[TeMo6O24]·8H2O (2) (arg = l-arginine) have been preparedunder the 110 °C hydrothermal environments and structurally characterizedby elemental analyses, IR spectra, thermogravimetric (TG) analyses,and single-crystal X-ray diffraction. 1stands for thefirst one-dimensional (1D) chain organic–inorganic hybrid arsenomolybdateconstructed from lantern-shaped [(CuO6)Mo6O18(As3O3)2]4–units through dinuclear [Cu2(arg)4]4+connectors, whereas 2represents an unprecedented 1Dchain organic–inorganic hybrid telluromolybdate built by Anderson-type[TeMo6O24]6–fragments viatrinuclear [Cu3(arg)6]6+bridges.Variable-temperature magnetic susceptibilities of 1and 2have been investigated and both illustrate the weak antiferromagneticcoupling within copper centers mediated by the carboxyl groups ofarg ligands. Moreover, the solid-state electrochemical and electrocatalyticproperties of 1have been carried out in 1 mol L–1H2SO4aqueous solution by entrappingit in a carbon paste electrode. 1displays apparent electrocatalyticactivities toward the reduction of nitrite and bromate. [ABSTRACT FROM AUTHOR]

A tetra-Co substituted sandwich-type polyoxotungstate (HTED)Cs[Co(HO)(B- α-HPWO)]·28HO (TED = triethylenediamine) has been hydrothermally synthesized and characterized by IR spectrum, elemental analysis, thermogravimetric analysis, powder X-ray diffraction and single-crystal X-ray diffraction, respectively. Single-crystal structure analysis reveals that the tetra-Co substituted sandwich-type phosphotungstate units [Co(HO)(B- α-PWO)] are combined together by Cs cations giving rise to the 3D framework with the 'sqc876' 3D net. [ABSTRACT FROM AUTHOR]

Two new organic-inorganic hybrid carboxylate-bridging copper-lanthanide heterometallic polyoxotungstates K[Cu(en)(HO)]{[Cu(en)][Ce(GeWO)(HO)](CO)}·11HO ( 1) and K [Cu(en)(HO)]{[Cu(en)(HO)][Tb(PWO)(CHCOO)(HO)]}·15HO ( 2) (en = 1,2-ethylenediamine) have been prepared under hydrothermal conditions and characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD), thermogravimetric (TG) analyses and X-ray single-crystal diffraction. X-ray structural analyses reveal that 1 exhibits the 1D zigzag chain architecture formed by dimeric oxalate-bridging {[Cu(en)][Ce(GeWO)(HO)](CO)} units and [Cu(en)] linkers whereas 2 displays a typical hybrid acetate-bridging dimeric structure [(α-PWO)Tb(HO)(η,μ-1,1)-CHCOO] modified by [Cu(en)(HO)] fragments. Notably, both contain 2:2-type carboxylate-bridging monolanthanide-substituted Keggin-type dimeric moieties and two types of organic ligands. 1 represents the rare 1D Cu-Ln heterometallic germanotungstate containing mixed ligands of en and oxalate whereas 2 represents the rare dimeric organic-inorganic hybrid Keggin-type phosphotungstate containing both Cu-Ln heterometals and mixed ligands of en and acetate. Graphical Abstract: Two new organic-inorganic hybrid copper-lanthanide heterometallic polyoxotungstates containing mixed organic ligands of en and carboxylate were successfully separated under hydrothermal conditions. 1 exhibits the 1D zigzag chain architecture formed by dimeric oxalate-bridging {[Cu(en)][Ce(GeWO)(HO)](CO)} units by [Cu(en)] linkers, whereas 2 displays a typical hybrid acetate-bridging dimeric structure [(α-PWO)Tb(HO)(η,μ-1,1)-CHCOO] modified by [Cu(en)(HO)] fragments.[Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Two unique organic-inorganic hybrid polyoxometalates constructed from Preyssler-type [Na(H2O)P5W30O110]14− ({P5W30}) subunits and TM/Ln-carboxylate-Ln connectors (TM=transition metal, Ln=lanthanide), KNa7[{Sm6Mn(μ-H2O)2(OCH2COO)7(H2O)18}{Na(H2O)P5W30O110}] ⋅22 H2O ( 1) and K4[{Sm4Cu2(gly)2(ox)(H2O)24}{NaP5W30O110}]Cl2 ⋅25 H2O ( 2; gly=glycine, ox=oxalate) have been hydrothermally synthesized and characterized by elemental analyses, IR spectra, UV/Vis-NIR spectra, thermogravimetric analyses, power X-ray diffraction, and single-crystal X-ray diffraction. Compound 1 displays one interesting 3D framework built by three types of subunits, {P5W30}, [Sm2Mn(μ-H2O)2(OCH2COO)2(H2O)5]4+, and [Sm4(OCH2COO)5 (H2O)13]2+, whereas 2 also manifests the other intriguing 3D architecture created by three types of subunits, {P5W30}, [SmCu(gly)(H2O)8]4+, and [Sm2(ox)(H2O)8]4+. To our knowledge, 1 and 2 are the first 3D frameworks that contain {P5W30} units and TM/Ln-carboxylate-Ln connectors. The fluorescent properties of 1 and 2 have been investigated. [ABSTRACT FROM AUTHOR]

Three novel polyoxometalates (POMs) containing [Ni6(μ3-OH)3]9− and [P2W15O56]12− units were first made, showing the first hexa-nuclearity transition-metal substituted POMs (TMSPs) based on monomeric lacunary Dawson fragments, which further indicates that the hydrothermal technique can offer an effective way for making new TMSPs through lacunary POM fragments incorporated with high-nuclear TM clusters. [ABSTRACT FROM AUTHOR]

Abstract: Three new sandwich-type polyoxotungstates (POTs) decorated by nickel-2,2′-bpy complexes [{Ni(2,2′-bpy)2(H2O)}2{Ni(2,2′-bpy)}2 {Ni4(H2O)2(B-α-XW9O34)2}]n− (X=PV, n=4 for 1; X=AsV, n=4 for 2; X=GeIV, n=4 for 3) (2,2′-bpy=2,2′-bipyridine) were successfully synthesized under hydrothermal conditions and structurally characterized by elemental analyses, IR spectroscopy, single-crystal X-ray diffraction, and magnetic properties. Single-crystal structural analyses indicate that 1 and 2 are isostructural and both crystallize in the monoclinic space group C2/c, whereas 3 belongs to the triclinic space group . To our knowledge, 1, 2 and 3 represent rare examples of the organic–inorganic hybrid sandwich-type polyoxometalates functionalized by multiple nickel-aromatic amine complexes. Magnetic measurements of 1 exhibit the presence of ferromagnetic interactions within the rhombic tetranuclear-NiII cluster. [Copyright &y& Elsevier]

Abstract: Two new Dawson-based phosphotungstates (H2en)0.5H[Cu(en)2(H2O)]2{[Cu(en)2](α 1-P2W17CuO61)}·8H2O (1) (en=ethylenediamine) and [4,4′-H2bpy]2{[Cu(4,4′-bpy)3][Cu(4,4′-bpy)4(H2O)2]2[Cu(4,4′-bpy)][α-P2W18O62]2}·6H2O (2) (4,4′-bpy=4,4′-bipyridine) have been hydrothermally synthesized and structurally characterized. 1 crystallizes in the triclinic space group P−1 with a=11.7626(17), b=13.246(2), c=29.350(5)Å, α=87.355(5), β=79.583(5), γ=66.993(3)°, V=4138.3(11)Å3, Z=2, GOF=1.089, R 1=0.0563 and wR 2=0.1505, whereas 2 belongs to the orthorhombic space group Iba2 with a=22.277(8), b=47.04(2), c=22.153(8)Å, V=23215(17)Å3, Z=4, GOF=1.051, R 1=0.0627 and wR 2=0.1477. 1 consists of a 1-D linear chain structure constructed from monocopperII-substituted Dawson polyoxoanions, while 2 represents the first 2-D sheet-like structure with a (4,4)-connected topological net built up from plenary Dawson-type polyoxoanions and CuII-4,4′-bpy complex cations in polyoxometalate chemistry. [Copyright &y& Elsevier]

Abstract: Three inorganic–organic composite sandwich-type phosphotungstates [Ni(tepa)(H2O)]4H2[Ni4(H2O)2(α-B-PW9O34)2]·8H2O (1), (enH2)3[Ni2(H2O)10][Ni4(H2O)2(α-B-PW9O34)2]·en·8H2O (2) and (enH2)10[Mn4(H2O)2(α-B-PW9O34)2]2·20H2O (3) (tepa=tetraethylenepentamine and en=ethylenediamine) have been synthesized by the hydrothermal reaction of the trivacant Keggin polyoxoanion [α-A-PW9O34]9− with Ni2+ or Mn2+ ions in the presence of tepa or en and structurally characterized by IR spectra, elemental analysis, thermogravimetric analysis and variable temperature magnetic susceptibility. X-ray crystallographic analyses indicate that they all contain the classical tetra-M sandwiched polyoxoanions [M 4(H2O)2(α-B-PW9O34)2]10− (M=Ni2+ or Mn2+) and nickel-organoamine cations or organoamine cations work as the charge balance ions. The tetra-M clusters in 1, 2 and 3 exhibit the familiar structural type of a β-junction at the sites of metal incorporation. The study of magnetic property of 1 is indicative of a typical ferromagnetic coupling between Ni2+ cations. [Copyright &y& Elsevier]

A new B-Anderson-type heteropoly compound [Cu 2 (phen) 2 (CH 3 COO) 2 (H 2 O) 2 ] [HAl(OH) 6 (Mo 6 O 18 )]  ·  2.5H 2 O containing binuclear copper(II) coordination ions has been synthesized by reaction of AlCl 3   ·  6H 2 O, Na 2 MoO 4   ·  2H 2 O, glacial acetic acid, 1,10-phenanthroline and CuCl 2   ·  2H 2 O in methanol--water mixed solution and characterized by IR, UV-Vis spectra, TG-DTA analysis and X-ray crystallography. From X-ray single-crystal structural analysis, the title compound crystallizes in a triclinic lattice, P space group, with a   =  13.379(3), b   =  17.388(4), c   =  18.063(4)  Å, α  =  85.97(3), β  =  69.79(3), γ  =  69.22(3)°, V   =  3680.4(13)  Å 3 , Z   =  2, R 1   =  0.0797, wR 2   =  0.1787. In the title compound, the two Cu 2+ coordination cations are combined with each other through two acetate bridges and have five-coordinate, distorted square-pyramid geometry with N2O3 bonding at each metal. In addition, there are also two crystallographically independent ‘one-half  ’ Anderson-type polyanions in the title compound lattice. [ABSTRACT FROM AUTHOR]

The reaction of the mono-lacunary silicotungstate ligand α-K8SiW11O39 · 13H2O with praseodymiumIII cation results in a new Keggin-type derivative K3[(Pr(H2O)4SiW11O39)(NaPr2(H2O)12)(Pr(H2O)4SiW11O39)] · 13.5H2O (1), whose polyanion consists of two crystallographically distinct [Pr(H2O)4SiW11O39]5- building block units and one [NaPr2(H2O)12]7+ subunit, which are connected by alternating praseodymium and sodium centers via the terminal and bridging oxygen atoms from the precursor [α-SiW11O39]8- to construct a 1D infinitely chainlike structure. [Copyright &y& Elsevier]

Polyoxometalates A series of mixed‐valence Mn6‐sandwiched polyoxometalates (POMs) with SMM behavior have been hydrothermally made, in which the covalently functionalized Mn6 cluster via organic ligands are first observed in POMs. For more details, see the Full Paper by J.‐W. Zhao, G.‐Y. Yang, H.‐S. Liu et al. on page 12322 ff. [ABSTRACT FROM AUTHOR]

Review: [267 refs. [ABSTRACT FROM AUTHOR]

Polyoxometalates In their Full Paper on page 17324 ff., G. ‐ Y. Yang et al. describe the synthesis of three novel organic – inorganic hybrids, Ni6 ‐ substituted trivacant Dawson ‐ type transition ‐ metal ‐ substituted polyoxometalates (TMSPs), obtained under hydrothermal conditions and characterized by various methods. Two of the compounds are made up of two isolated clusters, whereas the third one is the first extended architecture based on Ni6 ‐ substituted Dawson segments and [Ni(enMe)2]2+ bridges. The key points of the synthetic procedures have been discussed. [ABSTRACT FROM AUTHOR]