Two series of novel organic–inorganic hybrid carboxylated rare-earth-substituted monolacunary Dawson-type phosphotungstate monomers [Hdap]4[RE(H2O)(Hpic)3][RE(Hpic)2 (α2-P2W17O61)]·21H2O [RE = GdIII (1), TbIII (2), DyIII (3), HoIII (4), ErIII (5), TmIII (6), YbIII (7), YIII (8); Hpic = 2-picolinic acid, dap = 1,2-diaminopropane] and dimers [H2dap]8[RE2(H2ox)2(ox)(α2-P2W17O61)2]·25H2O [RE = HoIII (9), ErIII (10), TmIII (11), YbIII (12), YIII (13); H2ox = oxalic acid] have been hydrothermally synthesized and characterized by elemental analyses, IR spectra, thermogravimetric measurements, and X-ray single-crystal diffraction. The monomeric polyoxoanion skeleton of isomorphic 1–8 is constructed from a monolacunary Dawson-type phosphotungstate implanted by a [RE1(Hpic)2]3+ cation in the polar position and supported by the other [RE2(H2O)(Hpic)3]3+ cation on the equatorial belt. Interestingly, two kinds of RE cations separately coordinate to two or three Hpic ligands in the form of N–C–C–O–RE containing five-membered ring fashion. The dimeric polyoxoanion backbone of isomorphic 9–13 is built by two mono-RE substituted Dawson-type phosphotungstate fragments [RE(H2ox)(α2-P2W17O61)]7– joined together by an ox2– linker. The visible photoluminescence spectra of solid-state 2, 3, 5, and 10 and the NIR photoluminescence properties for solid-state 5, 10, 7, and 12 at ambient temperature have been carried out, which are mainly derived from the RE3+ f–f electron transitions. Magnetic susceptibility measurements and fitting results of 3 demonstrate that 3 is a single-molecule magnet.

A family of unprecedented tellurotungstate-based organotin–rare-earth (RE) heterometallic hybrids [H2N(CH3)2]6H12Na2 {[Sn(CH3)W2O4(IN)][(B-α-TeW8O31)RE(H2O) (Ac)]2}2·25H2O [RE = CeIII (1), PrIII (2), NdIII (3), SmIII (4), EuIII (5), GdIII (6), TbIII (7); HIN = isonicotinic acid, HAc = acetic acid] were synthesized and characterized by elemental analyses, IR spectra, UV spectra, thermogravimetric analyses, powder X-ray diffraction, and single-crystal X-ray diffraction. The polyoxoanionic skeletons {[Sn(CH3)W2O4(IN)][(B-α-TeW8O31)RE(H2O) (Ac)]2}220– of 1–7 are constructed from two symmetrical units {[Sn(CH3)W2O4(IN)][(B-α-TeW8O31)RE(H2O) (Ac)]2}10– linked by two acetate connectors, which not only represent the first inorganic–organic hybrid RE-substituted tellurotungstates involving three different organic ligands, but also stand for the first samples of organotin–RE heterometallic polyoxometalate derivatives. The solid-state luminescent emission properties of 2–5 mainly display the characteristic emission bands of REIII cations, whereas during the emission procedure of 7, [B-α-TeW8O31]10– segments make a nonignorable contribution to the PL behavior of 7 accompanying by the occurrence of the intramolecular energy transfer from O→W LMCT energy to Tb3+ centers. Furthermore, 4@CTAB composites with peanutlike and honeycombed morphologies were prepared by a surfactant cetyltrimethylammonium bromide (CTAB). The time-resolved emission spectra of the 4@CTAB composite with CTAB/4 = 0.033/0.05 consolidate the energy transfer from CTAB to REIII centers. Variable-temperature magnetic susceptibility measurements for 2, 3, and 4 were performed.

•Rare-earth containing docosatungstates•The hendecatungstate [W11O38H]9 − subunit•Solid-state luminescence propertiesThree rare-earth containing docosatungstates Na3H2[RE(H2O)4][RE(H2O)5]2[W22O74H2]·36H2O [RE = DyIII (1), HoIII (2), YIII (3)] have been synthesized by reaction of Na2WO4·2H2O, dimethylamine hydrochloride (DMAHC) and RE(NO3)3·6H2O in the aqueous solution and characterized by elemental analyses, IR spectra, thermogravimetric (TG) analysis, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. 1–3 are isomorphous and each molecular unit consists of a S-shaped docosatungstate [W22O74H2]14 − polyoxoanion with two supporting [RE(H2O)5]3 + cations and one disordered [RE(H2O)4]3 + cation. The [W22O74H2]14 − polyoxoanion can be viewed as combination of two hendecatungstate [W11O38H]9 − subunits in the staggered fashion by sharing two μ2-O atoms. The TG curves of 1–3 reveal the one-step weight loss between 25 °C to 700 °C. Moreover, both 1 and 2 demonstrate the characteristic luminescence emission behaviors of the corresponding RE3 + ions and their lifetime decay curves can be well fitted to the double exponential function. In addition, the CIE chromaticity coordinates of 1 and 2 have been obtained based on their corresponding emission spectra, and their dominant wavelengths and color purities have been also calculated.Three rare-earth containing docosatungstates Na3H2[RE(H2O)4][Ln(H2O)5]2[W22O74H2]·36H2O [Ln = DyIII, HoIII, YIII] were synthesized and their photoluminescence properties were investigated.Download high-res image (109KB)Download full-size image

•lanthanide-incorporated arsenotungstates.•duplicate {AsO2(OH)}-bridging lanthanide(Ln)-incorporated arsenotungstates.•the solid-state photoluminescence properties.Two {AsO2(OH)}-bridging lanthanide(Ln)-incorporated arsenotungstates (ATs) [H2N(CH3)2]8LnNa5 {[W3Ln2(H2O)8AsO8(OH)][B-α-AsW9O33]2}2·65H2O [Ln = ErIII (1), YbIII (2)] were synthesized by reaction of Na2WO4·2H2O, Ln(NO3)3·6H2O and NaAsO2 in the presence of dimethylamine hydrochloride. The common structural features of 1 and 2 are that the AsIII ions not only act as heteroatoms of the AT fragments but also function as the bridging groups to link two identical {[W3Ln2(H2O)8AsO8(OH)][B-α-AsW9O33]2} half-units. The results of TG analyses indicate that 1 and 2 undergo the similar three-step weight loss procedure between 25 and 800 °C. The first-step weight loss is attributable to the liberation of sixty-five lattice water molecules, the second-step weight loss corresponds to the release of sixteen coordination water molecules, ten protons as well as eight dimethylamine groups, and the third-step weight loss can be assigned to the sublimation of three As2O3 molecules. In addition, the solid-state photoluminescence properties of 1 and 2 have been investigated and mainly demonstrate the characteristic emission behaviors of ErIII ions and YbIII ions.Two {AsO2(OH)}-bridging lanthanide-incorporated arsenotungstates were synthesized and photoluminescence properties of the ErIII-containing species were intensively investigated.Download high-res image (464KB)Download full-size image

•Rare-earth-containing polyoxometalate•Lanthanide-containing Keggin silicomolybdate•Isonicotinic acid•Electrochemical propertiesTwo rare-earth–isonicotinic-acid containing silicomolybdates [NH4]6[RE(INA)2(HINA)(H2O)3]2[α-SiMo12O40]2·6H2O [RE = NdIII (1), ErIII (2); HINA = isonicotinic acid] have been synthesized in the conventional aqueous solution and characterized by elemental analyses, IR spectra, UV spectra and single-crystal X-ray diffraction. Both 1 and 2 crystallize in the triclinic P–1 space group and consist of two typical Keggin [α-SiMo12O40]4 − polyanions, one isolated rare-earth-isonicotinic-acid [RE(INA)2(HINA)(H2O)3]22 + dimeric complex cation, six NH4+ ions and six lattice water molecules. Interestingly, two rare-earth ions are linked by four INA− ligands in the [Ln(INA)2(HINA)(H2O)3]22 + complex cation, which is very rare in polyoxometalate chemistry. The UV spectral measurements of 1 indicate that 1 is stable in aqueous solution in the pH range of 4.49–9.39. Furthermore, the electrochemical and electrocatalytic properties of 1 have been measured by cyclic voltammetry in 0.5 mol·L− 1 Na2SO4 + H2SO4 aqueous solution at the scan rate of 100 mV·s− 1.Two rare-earth–isonicotinic-acid containing silicomolybdates have been synthesized and characterized.Download high-res image (282KB)Download full-size image

Two classes of rare-earth-organic-containing Waugh-type manganomolybdates (NH4)8{[RE(Hina)(ina)(H2O)2][MnIVMo9O32]}2·12H2O [RE = La3+ (1), Pr3+ (2), Nd3+ (3)] and (NH4)3[RE(Hina)2(H2O)6][MnIVMo9O32]·7H2O [RE = Sm3+ (4), Eu3+ (5), Gd3+ (6), Tb3+ (7), Dy3+ (8), Ho3+ (9), Er3+ (10), Tm3+ (11), Yb3+ (12), Y3+ (13)] (Hina = isonicotinic acid) were prepared by means of a step-by-step synthetic strategy and further characterized by IR spectroscopy, elemental analyses, UV-visible spectroscopy and single-crystal X-ray diffraction. X-ray diffraction indicates that 1–3 consist of an organic–inorganic hybrid dimeric {[RE(Hina)(ina)(H2O)2][MnIVMo9O32]}28− core constituted by two [MnMo9O32]6− units linked via a dinuclear {[RE(Hina)(ina)(H2O)2]2}4+ cation whereas 4–13 are composed of an organic–inorganic hybrid [RE(Hina)2(H2O)6]3+ fragment and one [MnMo9O32]6− polyoxoanion. It should be pointed out that the nature of RE cations controls these two structure types. As far as we know, 1–13 represent the first examples of Waugh-type manganomolybdates including rare-earth-organic subunits so far. Furthermore, their photocatalytic activities for the degradation of azophloxine were probed in aqueous medium and 3 and 8 as representatives were systematically investigated involving the influence of the optimal pH, catalyst dosage and the doping amount of VK-TA18 nanometer titanium dioxide on the photocatalytic activities. The solid-state photoluminescence properties and lifetime decay behaviors of 3, 4 and 5 in UV-visible or near-infrared regions were also examined at ambient temperature.

A neoteric 1-D sinusoidal tungstoantimonate (TA) Na2H4{[Mn(H2O)3]3[Mn(H2O)2]2[Mn(H2O)][Mn(C2O4)]3[B-α-SbW9O33]2}·31H2O (1) was synthesized from the reaction of Na9[B-α-SbW9O33]·19.5H2O with MnCl2·4H2O with the assistance of oxalic acid and structurally characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction, powder X-ray diffraction and thermal analyses. In 1, an unprecedented oxalate-bridging nona-MnII {[Mn(H2O)3]3[Mn(H2O)2]2[Mn(H2O)][Mn(C2O4)]3}12+ cluster is clamped by two trivacant Keggin [B-α-SbW9O33]9− fragments forming a unique nona-MnII-encapsulated sandwich-type species. In the sandwich belt, the internal hexa-MnII {[Mn(H2O)2]2[Mn(H2O)][Mn(C2O4)]3}6+ ring is alternately concatenated with three [Mn(H2O)3]2+ ions situated at three vertices of an equicrural triangle through oxalate linkers, completing an approximately coplanar nona-MnII core. More interestingly, adjacent nona-MnII-sandwiched TA units are interconnected by double MnII–C2O4 linkages, giving rise to the first inorganic–organic hybrid 1-D chain high-nuclear Mn-sandwiched TA. Furthermore, the zero-field-cooling/field-cooled magnetization and alternating current magnetic susceptibility measurements reveal the occurrence of long-range ferromagnetic ordering and spin-glass behavior in 1, which are further consolidated by the fitting of the Arrhenius law and the conventional critical scaling law of spin dynamics.

The one-pot assembly reaction of Na2WO4·2H2O, RE(NO3)3·6H2O, and NaAsO2 in the participation of dimethylamine hydrochloride as an organic solubilizing agent in the acidic aqueous solution led to a class of trigonal pyramidal {AsO2(OH)} bridging rare-earth substituted arsenotungstate (AT) aggregates [H2N(CH3)2]8Na8{[W3RE2(H2O)8AsO8(OH)][B-α-AsW9O33]2}2·65H2O [RE = EuIII (1), GdIII (2), TbIII (3), DyIII (4), HoIII (5), YIII (6)], which were structurally characterized by elemental analyses, IR spectra, single-crystal X-ray diffraction, and thermogravimetric (TG) analyses. The common structural feature of 1–6 is that their polyoxoanions consist of a novel tetrameric unit [(W3RE2(H2O)8AsO8(OH))(B-α-AsW9O33)2]216– constituted by four trivacant Keggin [α-AsW9O33]9– fragments linked through an unseen elliptical [W6RE4(H2O)16As2O16(OH)2]20+ moiety. Their polyoxoanionic infrastructures can also be described as a fusion of two equivalent dimeric subunits [(W3RE2(H2O)8O7)(B-α-AsW9O33)2]8– bridged via two μ2-{AsO2(OH)} linkers. To the best of our knowledge, such a linking mode with trigonal pyramidal {AsO2(OH)} groups as linkers connecting adjacent RE containing polyoxometalate moieties together is very rare. The thermal stability of 1–6 was also investigated on the crystalline samples, and the thermal decomposition processes of 1, 4, and 6 were comparatively deeply studied. The fluorescent properties and decay times of 1, 3, and 4 were measured, and they exhibit the characteristic emissions of RE centers. The lifetimes of 1 and 3 mainly originate from the contribution of RE ions whereas the overall lifetime of 4 is contributed by the synergistic interactions of AT fragments and Dy3+ ions.

Heterometallic polyoxotungstates (HMPOTs) are still a challenging and attractive materials in polyoxometalate chemistry despite having generated remarkable interest in recent years not only on account of a variety of new structures and topologies but also because of their multiple potential applications in catalysis, magnetism, nanoscience, electrochemistry and photochemistry. This brief highlight article is principally focused on an overview of four types of HMPOTs: polyoxotungstate-based main-group (MG) and transition-metal (TM) heterometallic derivatives (PMGTMHDs), polyoxotungstate-based TM and TM heterometallic derivatives (PTMTMHDs), polyoxotungstate-based rare-earth (RE) and TM heterometallic derivatives (PRETMHDs) and polyoxotungstate-based RE and RE heterometallic derivatives (PREREHDs), and gives a summary of some representative examples involving their syntheses, structures and related properties. In addition, an outlook on these materials is also provided.

Currently, transition-metal substituted polyoxotungstates (TMSPTs) have developed as a fast growing and challengeable subfamily of polyoxoxmetalates (POMs). Before 2005, the number of TM cores in TMSPTs was mostly lower than five. Since 2005, numerous inorganic or organic–inorganic TMSPTs with more than five TM cores (denoted as high-nuclear TMSPTs) have continuously been excavated and investigated. In this perspective, we endeavor to discuss the synthetic methodologies, structural diversities and relevant properties of the high-nuclear TMSPTs reported in the past decade. Future perspectives and opportunities on TMSPTs are included in the last section. This review is meant to provide fodder and guidance for further exploration and discovery of more high-nuclear TMSPTs with innovative architectures and remarkable functionality.

Three types of new lanthanoid(Ln)-containing isopolyoxotungstates [H2N(CH3)2]6Na6[Ln4(H2O)22W28O94H2]2·113H2O [Ln = Pr3+ (1), Nd3+ (2), Sm3+ (3)], Na2[Eu(H2O)7]2[Eu(H2O)5]2[W22O74H2]·20H2O (4), and Na3H2[Ln(H2O)4][Ln (H2O)5]2[W22O74H2]·36H2O [Ln = Gd3+ (5), Tb3+ (6), Er3+ (7), Tm3+ (8), Yb3+ (9), Lu3+ (10)] have been obtained by reacting Na2WO4·2H2O with Ln(NO3)3·6H2O in the presence of dimethylamine hydrochloride in the acidic aqueous solution and structurally characterized by elemental analyses, IR spectroscopy, UV spectroscopy, electrospray ionization mass spectrometry (ESI–MS), thermogravimetric (TG) analyses, and single-crystal X-ray diffraction. 1, 2, and 3 are isostructural and display a one-dimensional (1-D) chain-like alignment built by hexameric Ln8-comprising [Ln4(H2O)22W28O94H2]212– entities via [Ln(H2O)5]3+ connectors. The [Ln4(H2O)22W28O94H2]212– entity consists of two [Ln4(H2O)22W28O94H2]6– subunits connected by two W–O–Ln–O–W linkers. Intriguingly, the rare λ-shaped octacosatungstate [W28O94H2]18– moiety observed in the [Ln4(H2O)22W28O94H2]6– subunit is composed of two undecatungstate [W11O38H]9– fragments joined through a hexatungstate [W6O22]8– fragment by sharing four μ2-O atoms. In 4, 22-isopolytungstate [W22O74H2]14– anions are interlinked together by four W–O–Eu1–O–W linkers giving rise to the 1-D chain motif, and then adjacent 1-D chains are further bridged through multiple W–O–Eu2–O–W connectors to engender the two-dimensional extended sheet structure with the 4-connected topology. The isomorphic 5–10 demonstrate the discrete structure consisting of a [Ln(H2O)4][Ln (H2O)5]2[W22O74H2]8– unit. The pH ranges in which 3, 4, and 9 are stable in aqueous solution have been examined by virtue of UV and ESI–MS spectra. The solid-state luminescent properties of 3, 4, and 6 have been probed at room temperature. 3 displays the pink emission derived from characteristic emission bands of the Sm3+ cations that correspond to transitions from the 4G5/2 excited-state to lower 6HJ (J = 5/2, 7/2, 9/2, 11/2) levels, 4 emits the red light that mainly results from the 5D0 → 7F2 transition of the Eu3+ cations, and 6 manifests the green luminescence mainly originating from the 5D4 → 7F5 transition of the Tb3+ cations. Their lifetime decay curves all conform to the single exponential function, affording their lifetimes of 8094.19 ns, 149.00 μs and 384.89 μs, respectively.

•Polyoxometalate-based copper–lanthanide heterometallic derivatives.•Inorganic–organic hybrid copper–lanthanide heterometal comprising germanotungstates.•The photoluminescence properties of the Eu3+ ions.The hydrothermal reaction of K8Na2[A-α-GeW9O34]·25H2O, Cu(CH3COO)2·H2O, Ln(NO3)·6H2O and ethylenediamine (en) has led to a series of inorganic–organic hybrid copper–lanthanide heterometal comprising germanotungstates (GTs) [Cu(en)2(H2O)]6[Ln(H2O)(CH3COO)(α-GeW11O39)]2·8H2O [Ln = Nd3+ (1), Sm3+ (2), Eu3+ (3), Gd3+ (4), Dy3+ (5), Ho3+ (6)], which have been characterized by elemental analyses, IR spectra, thermogravimetric (TG) analyses and single-crystal X-ray diffraction. Their common feature of 1–6 is that they all comprise a CH3COO-bridging mono-Ln substituted dimeric GT fragment [Ln(H2O)(CH3COO)(α-GeW11O39)]212− with six supporting [Cu(en)2(H2O)]2+ complex cations. To the best of our knowledge, such monovacant Keggin-type GTs containing both Cu–Ln heterometal centers and mixed en and acetate ligands are very rare. The luminescence properties and the lifetime decay behavior of the solid sample of 3 have been intensively investigated at room temperature.A series of inorganic–organic hybrid copper–lanthanide heterometal comprising germanotungstates were synthesized. Photoluminescence properties of the Eu-containing species were intensively investigated.

•Inorganic–organic hybrids with mixed organic components•Copper-2-picolinic-acid germanomolybdates•1,3-bis[tris(hydroxymethyl)methylamino]propane•Electrochemical propertiesTwo inorganic–organic hybrids based on saturated α-Keggin-type germanomolybdates with mixed organic components [H2DAP]2[Cu(PA)2][α-GeMo12O40]·8H2O (1) and [NH4]2[H8L] [Cu(PA)2][α-GeMo12O40]·8H2O (2) (DAP = 1.2-diaminopropane, HPA = 2-picolinic acid, H6L = 1,3-bis[tris(hydroxymethyl)methylamino]propane) have been obtained via the conventional aqueous solution method and structurally characterized by elemental analysis, IR spectra, thermogravimetric (TG) analysis and single-crystal X-ray diffraction. 1 stands for an one-dimensional linear organic–inorganic hybrid germanomolybdate chain constructed from classical Keggin [α-GeMo12O40]4 − units supported by [Cu(PA)2] linkers, whereas 2 represents the first hybrid germanomolybdate containing the H6L component and consists of a saturated α-Keggin polyanion [α-GeMo12O40]4 −, a diprotonated [H8L]2 + cation, a copper coordination complex [Cu(PA)2], two ammonium cations [NH4]+ and eight lattice water molecules. Furthermore, the electrochemical and electrocatalytic properties of 1 and 2 have also been investigated in detail.Two inorganic–organic hybrids based on saturated α-Keggin-type germanomolybdates with mixed organic components have been synthesized and their electrochemical properties have been probed.

•1-D and 2-D inorganic–organic hybrid polyoxomolybdates•Organic–inorganic hybrid octamolybdates•The photocatalytic degradation towards rhodamine-BTwo new 1-D and 2-D inorganic–organic hybrid polyoxomolybdates [H2dap]2[x-Mo8O26]·2H2O (1) and [Cu(dap)2]2[β-Mo8O26] (2) (dap = 1,2-propanediamine) have been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectra, powder X-ray diffraction and single-crystal X-ray diffraction. The most remarkable structural differences between them are that 1 displays a 1-D chain constructed from [x-Mo8O26]4 − clusters through two terminal O atoms from adjacent [x-Mo8O26]4 − clusters whereas 2 demonstrates the 2-D extended layer made up of [β-Mo8O26]4 − clusters via [Cu(dap)2]2 + connectors. To our knowledge, the [x-Mo8O26]4 − cluster in 1 is reported for the first time. The thermogravimetric (TG) curve of 1 shows a two-step weight loss whereas the TG decomposition of 2 only proceeds in one stage. Additionally, their electrochemical behaviors and their photocatalytic degradation properties towards rhodamine-B are also investigated.Two 1-D and 2-D inorganic–organic hybrid polyoxomolybdates [H2dap]2[x-Mo8O26]·2H2O (1) and [Cu(dap)2]2[β-Mo8O26] (2) (dap = 1,2-propanediamine) have been hydrothermally synthesized and structurally characterized.

•Inorganic–organic hybrid CuIICeIII heterometallic germanotungstate•1-D CuIICeIII heterometallic chain architecture•Solid-state electrochemical and electrocatalytic propertiesA new 1:2-type inorganic–organic hybrid CuIICeIII heterometallic germanotungstate (GT) derivative KNa2H9[enH2]2 [Cu(en)2(H2O)]2[Cu(en)2]2{Cu(en)2[Ce(α-GeW11O39)2]2}·14H2O (1) (en = ethylenediamine) was obtained by simultaneously introducing Cu2 + and Ce4 + cations to the trivacant Keggin-type [A-α-GeW9O34]10 − system in the help of extra Na2WO4·2H2O and en ligand under hydrothermal conditions and was further characterized by elemental analyses, IR spectrum, thermogravimetric (TG) analysis and single-crystal X-ray diffraction. 1 exhibits a 1-D CuIICeIII heterometallic chain architecture by tetrameric {Cu(en)2[Ce(α-GeW11O39)2]2}24 − units via K+ cations. Moreover, its solid-state electrochemical and electrocatalytic properties have been measured in 0.5 mol L− 1 Na2SO4 + H2SO4 aqueous solution by entrapping them in a carbon paste electrode, indicating that 1 displays apparent electrocatalytic activities for nitrite, bromate and hydrogen peroxide reduction.A 1:2-type inorganic–organic hybrid CuIICeIII heterometallic germanotungstate derivative has been synthesized and the electrochemical properties of 1 have been studied.

Owing to their unique and abundant structures and potential multi-fold applications in various fields such as luminescence, magnetism, catalysis, etc., rare-earth-containing polyoxometalates (RECPs) play an important role in the development of polyoxometalate chemistry. In this article, the major progress in RECPs made in the past decade involving synthetic strategies, structural characteristics and some significant properties related to optics, catalysis and magnetism is highlighted and discussed. The final section is committed to looking forward to some future perspectives in this field and providing some personal insights or viewpoints for the ongoing trends in the future.

•Organic–inorganic hybrid octamolybdates•Octamolybdate-based hybrids functionalized by 1,3-bis[tris(hydroxymethyl)methylamino]propane ligand•Electrocatalytic reduction of bromateTwo octamolybdate-based organic–inorganic hybrids functionalized by 1,3-bis[tris(hydroxymethyl)methylamino]propane (H6bthmap) Na2H4[γ-Mo8O26(H5bthmap)2]·2H2O (1) and [NH4]6{[Cu(H3bthmap)]2(β-Mo8O26)} (2) have been synthesized through the aqueous synthetic method and structurally characterized by elemental analyses, IR spectra, UV spectra, thermogravimetric (TG) analysis and single-crystal X-ray diffraction. X-ray crystallography reveals that 1 consists of a classic [γ-Mo8O26]4 − polyoxoanion decorated by two flexible [H5bthmap]− ligands through two O atoms from two [H5bthmap]− ligands and 2 contains a [β-Mo8O26]4 − polyoxoanion with bisupporting [Cu(H3bthmap)]− anions via two terminal O atoms from the [β-Mo8O26]4 − polyoxoanion. As far as we know, 1 and 2 represent the first octamolybdate-based hybrids with 1,3-bis[tris(hydroxymethyl)methylamino]propane ligands. The TG curves of 1 and 2 indicate two steps of weight loss and three steps of weight between 25 and 980 °C, respectively. Furthermore, the electrochemical and electrocatalytic properties of 1 and 2 have been investigated.Two octamolybdate-based hybrids functionalized by 1,3-bis[tris(hydroxymethyl)methylamino]propane (H6bthmap) Na2H4[γ-Mo8O26(H5bthmap)2]·2H2O and [NH4]6{[Cu(H3bthmap)]2(β-Mo8O26)} were synthesized and characterized.

•Organic–inorganic hybrid silicotungstate•Organic–inorganic hybrid independent 1-D double-chain structure•Electrochemistry•MagnetismA novel organic–inorganic hybrid independent 1-D double-chain silicotungstate [Cu(biim)2][Cu(4,4′-bpy)(biim) (H2O)][α-SiW12O40]·3H2O (1, biim = 2,2′-biimidazole, 4,4′-bpy = 4,4′-dipyridine) has been successfully synthesized by reaction of Na10[A-α-SiW9O34]·18H2O, CuCl2·2H2O, EuCl3, biim and 4,4′-bpy under 160 °C hydrothermal environment and characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction. The most remarkable structural feature of 1 is that two types of independent 1-D chains are paralleling and one is constructed from plenary Keggin [α-SiW12O40]4 − units and [Cu(biim)2]2 + linkers while the other is based on [Cu(biim)(H2O)]2 + cations and 4,4′-bpy connectors. The variable-temperature magnetic susceptibility of 1 shows the weak antiferromagnetic exchange interactions within CuII centers. Furthermore, the solid-state electrochemical properties of 1 have been also measured in 0.5 mol·L− 1 Na2SO4 + H2SO4 aqueous solution by entrapping it in a carbon paste electrode.An organic−inorganic hybrid independent 1-D double-chain Keggin-type silicotungstate with mixed ligands has been synthesized and characterized.

•The mono-SmIII substituted phosphotungstate.•Organic–inorganic hybrid mono-lanthanide substituted polyoxometalates with amino acids.•IR spectra and UV spectra of 1:2-type [Sm(α-PW11O39)2]11− containing polyoxotungstates.•Solid-state photoluminescence of mono-SmIII substituted phosphotungstate.•Polyoxometalate-based ferroelectric material.An organic–inorganic hybrid mono-SmIII substituted phosphotungstate KNa3[HPro]7[Sm(α-PW11O39)2]·Pro·18H2O (1) (Pro = d-proline) has been synthesized in the conventional aqueous solution and structurally characterized by elemental analyses, inductively coupled plasma atomic emission spectrometry (ICP-AES) analyses, IR spectra, UV spectra, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) and single-crystal X-ray diffraction. The molecule of 1 consists of a classical 1:2-type [Sm(α-PW11O39)2]11− fragment and free d-proline components. It should be pointed out that the synergistic action between the in-situ formed chiral [Sm(α-PW11O39)2]11− fragment and chiral d-proline components results in the formation of the chiral 1. The luminescence emission of 1 reveals three characteristic bands that derive from the 4G5/2 → 6H5/2, 4G5/2 → 6H7/2 and 4G5/2 → 6H9/2 transitions of the SmIII cation as well as the synergistic contribution of the O → W transitions of [α-PW11O39]7− moieties and a π*–n or π*–π transitions of Pro. Its ferroelectric behavior has been measured.Graphical abstractAn organic–inorganic hybrid mono-SmIII substituted phosphotungstate with amino acids has been synthesized and IR, UV spectra, the photoluminescence spectra and ferroelectric behavior have been studied.

By the routine aqueous solution method, a series of transition-metal–lanthanide heterometallic tungstoantimonates [Ln(H2O)8]2[Fe4(H2O)8(thr)2][B-β-SbW9O33]2·22H2O [Ln = PrIII (1), NdIII (2), SmIII (3), EuIII (4), GdIII (5), DyIII (6), LuIII (7), thr = threonine] were prepared and structurally characterized by multiple testing techniques. The common structural characteristic of 1–7 is that they are isomorphous and all consist of a [Fe4(H2O)8(thr)2(B-β-SbW9O33)2]6– subunit with two supporting [Ln(H2O)8]3+ cations on both sides. It should be pointed out that two thr ligands in the [Fe4(H2O)8(thr)2(B-β-SbW9O33)2]6– subunit substitute for two water ligands in the classical [Fe4(H2O)10(B-β-SbW9O33)2]6– polyoxoanion. As far as we know, 1–7 represents the first organic–inorganic tungstoantimonate hybrids consisting of transition metal and lanthanide cations and amino acid components. The fluorescence behavior of 4 has been measured and manifests the remarkable fluorescence feature resulting from the emission signature of EuIII cations. Furthermore, the solid-state electrochemistry and electrocatalytic performances of 1 have been measured in 0.5 mol L–1 Na2SO4+H2SO4 aqueous solution, and the results show that 1 illustrates comparatively apparent catalytic activities toward the BrO3– and H2O2 reduction. The magnetic properties of 3 and 6 have been studied.

Two unique organic–inorganic hybrid heteropolymolybdates with 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 prepared under the 110 °C hydrothermal environments and structurally characterized by elemental analyses, IR spectra, thermogravimetric (TG) analyses, and single-crystal X-ray diffraction. 1 stands for the first one-dimensional (1D) chain organic–inorganic hybrid arsenomolybdate constructed from lantern-shaped [(CuO6)Mo6O18(As3O3)2]4– units through dinuclear [Cu2(arg)4]4+ connectors, whereas 2 represents an unprecedented 1D chain organic–inorganic hybrid telluromolybdate built by Anderson-type [TeMo6O24]6– fragments via trinuclear [Cu3(arg)6]6+ bridges. Variable-temperature magnetic susceptibilities of 1 and 2 have been investigated and both illustrate the weak antiferromagnetic coupling within copper centers mediated by the carboxyl groups of arg ligands. Moreover, the solid-state electrochemical and electrocatalytic properties of 1 have been carried out in 1 mol L–1 H2SO4 aqueous solution by entrapping it in a carbon paste electrode. 1 displays apparent electrocatalytic activities toward the reduction of nitrite and bromate.

Two types of unique oxalate-connective lanthanide-substituted isopolyoxotungstates, Na10[Ln2(C2O4)(H2O)4(OH)W4O16]2·30H2O (1) and K4Na16[Ln(C2O4)W5O18]4·60H2O (2) (Ln = EuIII, HoIII, ErIII, or TbIII), have been synthesized under conventional aqueous solution conditions and structurally characterized by elemental analyses, IR spectra, single-crystal X-ray diffraction, and thermogravimetric analyses. It should be pointed out that the utilization of different alkaline cations leads to the formation of two structural types. When only Na+ ions are present in the system, type 1 was obtained, while when Na+ and K+ ions are used, type 2 was found. Complex 1 is a double-oxalate-bridging di-Ln substituted Lindqvist dimer with a rectangle tetra-Ln cluster, whereas 2 is a single-oxalate-connective mono-LnIII Lindqvist tetramer with square tetra-Ln cluster. As far as we know, such di-Ln substituted Lindqvist fragment in 1 is observed for the first time. Moreover, 2 represents the first organic–inorganic hybrid square Ln-substituted isopolyoxotungstate. The solid-state luminescent properties of 1-Eu, 1-Tb, 2-Eu, and 2-Tb have been measured. 1-Eu and 2-Eu display intense, sharp, and narrow emission bands in the orange visible region that originate from the characteristic 5D0 → 7FJ transitions, and their fluorescence lifetimes are 1.18 and 1.20 ms, respectively. 1-Tb and 2-Tb exhibit green photoluminescence mainly derived from 5D4 → 7F5 transitions. The decay behavior of 1-Tb can be fitted to a biexponential function with lifetimes of τ1 = 0.43 ms and τ2 = 1.25 ms, whereas the decay behavior of 2-Tb can be fitted to single exponential function with the lifetime of 1.03 ms. Magnetic susceptibilities of 1 and 2 have been measured, and the decline of χMT upon cooling for 1 and 2 is mostly related to the progressive thermal depopulation of the excited state of Ln cations.

As an important ramification of polyoxometalates, germanotungstate (GT) chemistry has gradually developed as a new research focus and a challenging area, and has made great progress in the past decade due to a wide range of potential applications in various areas such as catalysis, magnetism, photochemistry and materials science. In this review, we mainly focus on three categories of metal-functionalized GTs: transition metal (TM)-substituted GTs (TMSGTs), rare earth (RE)-substituted GTs (RESGTs) and GT-based TM–RE heterometallic derivatives (GTTRHDs). We discuss their synthetic strategies, structural features and some properties involving magnetism, electrochemistry and catalysis. Finally, some perspectives on this field are also provided and some possible directions for future work are outlined.

•Organic–inorganic hybrid CuII–LnIII heterometallic polyoxometalates.•2D organic–inorganic hybrid phosphotungstates.•2D 5-conneted polyoxometalate-based CuII–LnIII heterometallic network.Reactions of the trivacant polyoxotungstate Na9[A-α-PW9O34]·7H2O with CuCl2·2H2O and LnCl3 (Ln = SmIII, ErIII) in the presence of 1,2-diaminopropane (dap) have led to two organic–inorganic hybrid Cu–Ln heterometallic polyoxotungstates [Cu(dap)2(H2O)][Cu(dap)2]4.5[Sm(α-PW11O39)2]·5H2O (1) and [Cu(dap)2(H2O)][Cu(dap)2]4.5[Er(α-PW11O39)2]·4H2O (2). 1 and 2 are isomorphic and display the 2D 5-connected sheet constructed from alternating bis(undecatungstophosphate)lanthanate [Ln(α-PW11O39)2]11− units and [Cu(dap)2]2+ connectors, in which the [Ln(α-PW11O39)2]11– subunits act as 5-connected nodes and adjacent 2D sheets show the –AAA– packing mode. Furthermore, their thermogravimetric analyses and magnetic susceptibilities have been investigated.Two 2D Cu–Ln heterometallic polyoxometalate aggregates 1 and 2 have been prepared and characterized by elemental analyses, IR spectra, X-ray diffraction, thermogravimetric analyses and magnetic susceptibility.

•Organic–inorganic hybrid sandwich-type germanotungstate.•Germanotungstate with discrete polyoxoanions and 1-D chains.•Ferromagnetic tetra-FeIII sandwiched germanotungstate.A novel organic–inorganic hybrid sandwich-type germanotungstate [enH2]8[Fe4(en)(α-GeW9O34)2] [Fe4(en)2(α-GeW9O34)2]·en·14H2O has been synthesized by reaction of K8Na2[A-α-GeW9O34]·25 H2O, FeCl3, Ce(NH4)4(SO4)4·4H2O and en (en = ethylenediamine) under hydrothermal conditions and characterized by elemental analyses, IR spectrum, powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS) and single-crystal X-ray diffraction. To our knowledge, 1 represents the first organic–inorganic hybrid sandwich-type germanotungstate with discrete [Fe4(en)2(α-GeW9O34)2]8 − polyoxoanions and 1-D [Fe4(en)(α-GeW9O34)2]n8n − polymeric chains in polyoxometalate chemistry. Thermogravimetric curve of 1 between 25 and 700 °C indicates two steps of weight loss. Variable-temperature magnetic susceptibilities of 1 exhibit the ferromagnetic interactions within the belt-like tetra-FeIII clusters mediated by the oxygen bridges.The first sandwich-type germanotungstate hybrid with discrete [Fe4(en)2(α-GeW9O34)2]8 − polyoxoanions and 1-D [Fe4(en)(α-GeW9O34)2]n8n − polymeric chains has been synthesized, which exhibits the ferromagnetic interactions within the belt-like tetra-FeIII clusters.

•Copper–lanthanide heterometallic germanotungstate.•IR spectra of copper–lanthanide heterometallic germanotungstates.•Photoluminescence spectra of germanotungstates.•The electrocatalytic activity for nitrite reduction.Two organic–inorganic hybrid copper–lanthanide heterometallic germanotungstates KNa2H7[enH2]3[Cu(en)2(H2O)]2[Cu(en)2]2{Cu(en)2[Eu(α-GeW11O39)2]2}·13H2O (1) and Na2H4[Cu(en)2(H2O)]2[Cu(en)2]6[Cu(en)2]{Cu(en)2[La(α-GeW11O39)2]2}·12H2O (2) have been hydrothermally synthesized by reaction of K8Na2[A-α-GeW9O34]·25H2O with CuCl2·2H2O and EuCl3/LaCl3 in the presence of en (en = ethylenediamine) and structurally characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction. 1 exhibits the 1D chain motif built by tetrameric {[Cu(en)2(H2O)]2[Cu(en)2]2{Cu(en)2[Eu(α-GeW11O39)2]2}}16− moieties through square antiprismatic K+ cations while 2 displays the 1D architecture made by tetrameric [[Cu(en)2]6[Cu(en)2]{Cu(en)2[La(α-GeW11O39)2]2}]10− units via octahedral [Cu(en)2]2+ cations. Furthermore, the solid-state electrochemical and electrocatalytic properties of 1 have been investigated and 1 indicates the good electrocatalytic activity for nitrite reduction. In addition, the photoluminescence property of 1 has been investigated.Two 1-D copper–lanthanide heterometallic germanotungstate hybrids have been synthesized and IR spectra, the photoluminescence spectra and the electrocatalytic activity for nitrite reduction of 1 have been studied.

•Copper–lanthanide heterometallic coordination polymers containing 2,2′-bipyridyl-5,5′-dicarboxylic acid.•IR spectra of copper–lanthanide heterometallic coordination polymers.•X-ray photoelectron spectroscopy of copper and lanthanide cations.•Solid-state photoluminescence of copper–lanthanide heterometallic coordination polymers.Three new two-dimensional CuI–LnIII heterometallic coordination polymers [LnIIICu2I(Hbpdc)4]·Cl·xH2O [LnIII = LaIII, x = 8 (1); LnIII = PrIII, x = 9 (2); LnIII = EuIII, x = 8 (3)] (H2bpdc = 2,2′-bipyridyl-5,5′-dicarboxylic acid) have been prepared under hydrothermal conditions and structurally characterized by elemental analyses, inductively coupled plasma atomic emission spectrometry (ICP–AES) analyses, IR spectra, X-ray photoelectron spectroscopy (XPS) and single-crystal X-ray diffraction. X-ray diffraction indicates that the isomorphic 1–3 display the two-dimensional sheet structure constructed from [CuI(Hbpdc)2]– fragments through Ln3+ connectors. Moreover, the solid-state photoluminescence measurements of 3 indicate that the EuIII ions, Hbpdc– ligands and CuI cations make contributions to its luminescent properties simultaneously.Three two-dimensional CuI–LnIII heterometallic coordination polymers based on 2,2′-dipyridyl-5,5′-dicarboxylate ligands have been synthesized and IR spectra, XPS spectra and the photoluminescence spectra have been studied.

A novel organic–inorganic hybrid hexa-NiII sandwiched germanotungstate [enH2]2[Ni(en)2]2{[Ni6(en)2(H2O)2] [B-α-GeW9O34]2}·14H2O (1) has been hydrothermally synthesized and structurally characterized. 1 consists of a hexa-nickel sandwiched polyoxoanion {[Ni6(en)2(H2O)2][B-α-GeW9O34]2}8 −, two discrete [Ni(en)2]2 + cations, two free diprotonated [enH2]2 + cations and fourteen lattice water molecules. Notably, the sandwich-type polyoxoanion {[Ni6(en)2(H2O)2][B-α-GeW9O34]2}8 − is constructed from two trivacant [B-α-GeW9O34]10 − Keggin moieties in a staggered fashion linked via a belt hexa-nickel cluster [Ni6(en)2(H2O)2]12 +. To our knowledge, 1 represents the first hexa-NiII substituted sandwich-type germanotungstate. 1 shows the occurrence of ferromagnetic interactions within nickel centers. The photocatalytic property of 1 has been investigated.An organic–inorganic hybrid hexa-nickel sandwiched germanotungstate has been hydrothermally synthesized and structurally characterized. The magnetic and photocatalytic properties have been investigated.Highlights► Sandwich-type Keggin germanotungstate. ► The hexa-nickel substituted sandwich-type germanotungstate. ► The ferromagnetic interactions within nickel centers. ► The photocatalytic property of germanotungstate.

A novel organic–inorganic hybrid 3D framework based on neodymium oxalate–selenites [Nd2(SeO3)2(C2O4) (H2O)2]·2H2O (1) has been successfully synthesized under hydrothermal conditions and further characterized by elemental analyses, inductively coupled plasma atomic emission spectrometry (ICP-AES), X-ray powder diffraction (XRPD), IR spectrum, thermal analysis, and X-ray single-crystal diffraction. X-ray structural analysis reveals that 1 features a square ring composed of two {Nd2O4C2} subunits bridged by two {SeO3}2− anions via the corner-sharing mode. Interesting, the rhombic {Nd2O2} units interconnected with each other generating the 1D zigzag chain structure, whereas adjacent 1D chains are bridged by {SeO3}2− groups forming the 2D network architecture, which are further linked together through oxalate ligands leading to the 3D framework. The magnetic behavior of 1 is mainly due to the splitting of the 10-fold degenerate 4I9/2 ground state affected by the crystal field perturbation and the progressive depopulation of the higher energy state upon cooling.Graphical abstractA novel organic–inorganic hybrid based on neodymium oxalate–selenite [Nd2(SeO3)2(C2O4) (H2O)2]·2H2O (1) has been hydrothermally synthesized, which displays the 3-D porous framework constructed from {SeO3}2− groups and oxalate ligands.Highlights► The organic–inorganic hybrid 3D porous framework. ► Neodymium oxalate–selenites. ► Lanthanide(Ln)-containing selenites. ► The neodymium magnetism.

An organic–inorganic hybrid paratungstate [enH2]2[Cu(en)2]3[H2W12O42]·6H2O (1) (en = ethylenediamine) has been hydrothermally synthesized by reaction of Na2WO4·2H2O with CuCl2·2H2O in the presence of en and structurally characterized by elemental analyses, IR spectroscopy, UV spectrum, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) and X-ray single-crystal diffraction. It is worth pointing out that 1 exhibits the 6-connected 3-D framework with the long topological (O'Keeffe) vertex symbol 4·4·64·4·4·4·4·64·4·4·4·64·4·4·4 for the [Cu(en)2]3[H2W12O42]4 − node, which gives the short vertex (Schläfli) symbol of 41263. To the best of our knowledge, such 6-connected 3-D open-framework constructed from paratungstate clusters is for the first time observed in polyoxometalate chemistry.An organic–inorganic hybrid paratungstate [enH2]2[Cu(en)2]3[H2W12O42]·6H2O has been synthesized and displays the first six-connected 3-D architecture constructed from paratungstate-based polyoxometalate units and [Cu(en)2]2 + connectors.Highlights► The paratungstate-based polyoxometalate units ► The organic–inorganic hybrid paratungstate ► Six-connected 3-D framework constructed from paratungstate-based polyoxometalate units and [Cu(en)2]2 + connectors

The hydrothermal reactions of Na8[A-α-HAsW9O34]·11H2O with CuCl2·2H2O, LnCl3 in the presence of ethylenediamine (en) lead to three novel 2D organic–inorganic hybrid CuII–LnIII heterometallic arsenotungstates Na3[Cu(en)2(H2O)][Cu(en)2]1.5[H3Ln(α-AsW11O39)2]·xH2O (Ln = DyIII, x = 5 (1); Ln = GdIII, x = 4 (2); Ln = LaIII, x = 5.5 (3)), which have been characterized by elemental analyses, IR spectra, optical diffuse reflectance spectra, thermogravimetric analyses and single-crystal X-ray diffraction. 1–3 are isomorphic and exhibit the unique 2D honeycomb (6,3)-network topology constructed from sandwich-type [H3Ln(α-AsW11O39)2]8− units through [Cu(en)2]2+ linkers. To the best of our knowledge, 1–3 represent rare 2D organic–inorganic hybrid CuII–LnIII heterometallic arsenotungstates. The photocatalytic measurements show that 1–3 can to some extent inhibit the photodegradation of rhodamine-B. Moreover, magnetic measurements demonstrate that there are the weak ferromagnetic behaviors in 1 and 2.Graphical abstractThree novel 2D organic–inorganic hybrid CuII–LnIII heterometallic arsenotungstates have been hydrothermally synthesized and structurally characterized. The photocatalytic, photoluminescence and magnetism preperties have been investigated.Highlights► CuII–LnIII heterometallic polyoxometalates. ► 2D organic–inorganic hybrid arsenotungstates. ► 2D (6,3)-network topology consisting of sandwich-type units. ► The photodegradation of rhodamine-B. ► The photoluminescence of the DyIII ion. ► Magnetism.

Three organic–inorganic hybrid monolacunary Keggin silicotungstate-based 3d–4f heterometallic derivatives NaH[Cu(dap)2(H2O)][Cu(dap)2]4.5[Ln(α-SiW11O39)2]·7H2O (Ln = SmIII for 1, DyIII for 2, GdIII for 3) have been prepared by the hydrothermal reaction of Na10[A-α-SiW9O34]·18H2O, CuCl2·2H2O, LnCl3 and dap (dap = 1,2-diaminopropane) and characterized by elemental analyses, IR spectra and X-ray single-crystal diffraction. 1–3 display the novel 3D CuII–LnIII heterometallic frameworks with the scarce 5-connected (46·64) topology and their common features are that they all consist of 1:2-type [Ln(α-SiW11O39)2]13− subunits and [Cu(dap)2]2+ connectors. To the best of our knowledge, 1–3 represent the rare 3D organic–inorganic hybrid Keggin silicotungstate-based 3d–4f heterometallic derivatives. In addition, the photoluminescence properties of 1 and 2 have been investigated and the magnetic susceptibilities of 1–3 have been measured.Graphical abstractThree organic–inorganic hybrid monolacunary Keggin silicotungstate 3d–4f heterometallic derivatives have been synthesized and characterized. The photoluminescence and magnetic properties have been investigated.Highlights► Organic–inorganic hybrid polyoxometalate-based 3d–4f heterometallic derivatives. ► 3D organic–inorganic hybrid 3d–4f heterometallic silicotungstates. ► The photoluminescence properties of the Sm and DyIII ions. ► The magnetism of Cu–Ln heterometallic silicotungstates.

Currently, transition-metal substituted polyoxotungstates (TMSPTs) have developed as a fast growing and challengeable subfamily of polyoxoxmetalates (POMs). Before 2005, the number of TM cores in TMSPTs was mostly lower than five. Since 2005, numerous inorganic or organic–inorganic TMSPTs with more than five TM cores (denoted as high-nuclear TMSPTs) have continuously been excavated and investigated. In this perspective, we endeavor to discuss the synthetic methodologies, structural diversities and relevant properties of the high-nuclear TMSPTs reported in the past decade. Future perspectives and opportunities on TMSPTs are included in the last section. This review is meant to provide fodder and guidance for further exploration and discovery of more high-nuclear TMSPTs with innovative architectures and remarkable functionality.

A neoteric 1-D sinusoidal tungstoantimonate (TA) Na2H4{[Mn(H2O)3]3[Mn(H2O)2]2[Mn(H2O)][Mn(C2O4)]3[B-α-SbW9O33]2}·31H2O (1) was synthesized from the reaction of Na9[B-α-SbW9O33]·19.5H2O with MnCl2·4H2O with the assistance of oxalic acid and structurally characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction, powder X-ray diffraction and thermal analyses. In 1, an unprecedented oxalate-bridging nona-MnII {[Mn(H2O)3]3[Mn(H2O)2]2[Mn(H2O)][Mn(C2O4)]3}12+ cluster is clamped by two trivacant Keggin [B-α-SbW9O33]9− fragments forming a unique nona-MnII-encapsulated sandwich-type species. In the sandwich belt, the internal hexa-MnII {[Mn(H2O)2]2[Mn(H2O)][Mn(C2O4)]3}6+ ring is alternately concatenated with three [Mn(H2O)3]2+ ions situated at three vertices of an equicrural triangle through oxalate linkers, completing an approximately coplanar nona-MnII core. More interestingly, adjacent nona-MnII-sandwiched TA units are interconnected by double MnII–C2O4 linkages, giving rise to the first inorganic–organic hybrid 1-D chain high-nuclear Mn-sandwiched TA. Furthermore, the zero-field-cooling/field-cooled magnetization and alternating current magnetic susceptibility measurements reveal the occurrence of long-range ferromagnetic ordering and spin-glass behavior in 1, which are further consolidated by the fitting of the Arrhenius law and the conventional critical scaling law of spin dynamics.