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The detection of ascorbic acid (AA), dopamine (DA), and uric acid (UA) is not only of great significance in the areas of biomedicine and neurochemistry but also helpful in disease diagnosis and pathology research. Due to their diverse structures, designability, and large specific surface areas, metal-organic frameworks (MOFs) have recently caught considerable attention in the electrochemical field. Herein, a family of heterometallic MOFs with amino modification, MIL-125(Ti-Al)-xNH2 (x = 0%, 25%, 50%, 75%, and 100%), were synthesized and employed as electrochemical sensors for the detection of AA, DA, and UA. Among them, MIL-125(Ti-Al)-75%NH2 exhibited the most promising electrochemical behavior with 40% doping of carbon black in 0.1 M PBS (pH = 7.10), which displayed individual detection performance with wide linear detection ranges (1.0-6.5 mM for AA, 5-100 μM for DA and 5-120 μM for UA) and low limits of detection (0.215 mM for AA, 0.086 μM for DA, and 0.876 μM for UA, S/N = 3). Furthermore, the as-prepared MIL-125(Ti-Al)-75%NH2/GCE provided a promising platform for future application in real sample analysis, owing to its excellent anti-interference performance and good stability. [ABSTRACT FROM AUTHOR]

Two tetra-nuclear YbIII-incorporated selenotungstate clusters, Keggin (C2H8N)6Na14[Yb4Se6W44O160(H2O)12]·40H2O (1) and Wells--Dawson (C2H8N)4Na14[Yb4Se6W45O159(OH)6(H2O)11]·38H2O (2), have been isolated through a pH-controlled assembly, which exhibit the first YbIII-containing polyoxotungstates with selenium heteroatoms. Their assemblies rely on the structure-directing effects of SeO32- anion templates to give rise to available Se-containing Keggin-/Wells--Dawson-type motifs. Both compounds were characterized by single-crystal X-ray diffraction, IR spectroscopy, power X-ray diffraction (XRD), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) as well as electrospray ionization mass spectrometry (ESI-MS). Furthermore, systematic magnetic studies revealed that 1 exhibits field-induced single-molecule magnetic behavior with a pre-exponential factor of τ0 = 6.60(7) x 10-8 s and a relaxation energy barrier of ΔE/kB = 39.44(2) K,while 2 only displays antiferromagnetic interactions between the ytterbium centers. [ABSTRACT FROM AUTHOR]

Recently, the well-known phenalenyl radical π-dimer with its fascinating 2-electron/12-center (2e/12c) bond has attracted our attention. In this work, we designed two molecules, Li3O...C13H9 (1a) and BeF3...C13H9 (1b). Interestingly, owing to the inductive effect of superatoms, an electron is transferred from Li3O to phenalenyl in 1a, while an electron is transferred from phenalenyl to BeF3 in 1b. Further, we employed 1a and 1b as building blocks to assemble two novel molecules with 2e/12c bonds: Li3O... (C13H9)2...BeF3 (2a) and Li3O...(C13H9)2...BeF3 (2b). Remarkably, 2a and 2b with novel 2e/12c bonds exhibit a dramatic interlayer charge-transfer character, which results in a significant difference of dipole moments (Δµ: 2.6804 for 2a and 3.8019 Debye for 2b) between the ground state and the crucial excited state. As a result, the static first hyperpolarizabilities (βo: 5154 for 2a and 12500 au for 2b) are considerably larger than the values of 347 for 1a and 328 au for 1b. It is our expectation that the results of the present work might provide beneficial information for further theoretical and experimental studies on the fascinating properties of molecules with interlayer charge-transfer character. [ABSTRACT FROM AUTHOR]

The article discusses the self assembly of an all-thiol-stabilized high-nuclearity luminescent nanocluster with a crab like shape in a compound that has been synthesized using silver tertiary alkenethiolates with Trifluoroacetic acid, triethylamine and potassium bromide in methanol. Topics discussed include single crystal X-ray analysis of crab shaped compound, the composition of cationic cluster of silver thiolate and solvency of organometallic cluster in organic solvents.

A new 3D extended heteropoly blue Ba4[SiWV 4WVI 8O40]·H2O (1) composed of twelve-coordinated a-Keggin anions [SiWV 4WVI 8O40]8- and eight-coordinated Ba sites {BaO8} has been hydrothermally synthesized and fully characterized by elemental analysis, IR spectroscopy, XPS, single crystal X-ray and X-ray powder (XRPD) diffraction. 1 represents the first inorganic 3D framework constructed from four-electron reduced a-Keggin anions linked by alkaline earth metals. The photocatalytic activity of 1 has been evaluated for rhodamine B (RhB) degradation. 1 exhibits excellent catalytic activity for the degradation of RhB in the presence of H2O2and the involvement of visible light makes a more complete degradation. The results of the current study suggest that multi-electron reduced polyoxometalates can catalyze efficient degradation of an organic dye with H2O2. [ABSTRACT FROM AUTHOR]

A new organic-inorganic hybrid titaniobate compound, [Cu(en)2]-[Cu(en)2(H2O)2]3[Ti2Nb8O28]·8H2O (1) (en = ethylenediamine), was successfully synthesized, characterized by single-crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis (TGA) and UV-Vis diffuse reflectance spectroscopy and its photoluminescence studied. [ABSTRACT FROM AUTHOR]

Recently, a new sulfide cluster fullerene, Sc2S@Cs (10528)-C72 containing two pairs of fused pentagons has been isolated and characterized (Chen et al., J. Am. Chem. Soc., 2012, 134, 7851). Inspired by this investigation, we propose a question: what properties will be influenced by the interaction between the encapsulated V-shaped polar molecule and C72 To answer this question, four encapsulated metallic fullerenes (EMFs) M2N@C72 (M = Sc or Y, N = S or O) along with pristine Cs-C72 (10528) were investigated by quantum chemistry methods. The results show that the Egap (3.01-3.14 eV) of M2N@C72 are significantly greater than that of pristine Cs-C72 (10528) (2.34 eV). This indicates that the stabilities of these EMFs increase by encapsulating the V-shaped polar molecule into the fullerene. Furthermore, the natural bond orbital (NBO) charge analysis indicates electron transfer from M2N to C72 cage, which plays a crucial role in enhancing first hyperpolarizability (βtot). The βtot follows the order of 1174 au (Y2O@C72) 1179 au (Sc2O@C72) > 886 au (Y2S@C72) 864 au (Sc2S@C72) > 355 au (C72). This indicates that the ßtot of M2N@C72 is more remarkable than that of pristine Cs-C72 (10528) due to the induction effect of the encapsulated molecule. Compared with sulfide cluster fullerenes (Y2S@C72 and Sc2S@C72), oxide cluster fullerenes (Sc2O@C72 and Y2O@C72) show much larger βtot due to the small ionic radius and the large electronegativity of oxygen. In contrast, the metal element (scandium and yttrium) has a slight influence on the tot. Thus, oxide cluster fullerenes are candidates to become promising nonlinear optical materials with higher performance. [ABSTRACT FROM AUTHOR]

The rotary motion based on metallacarboranes around a molecular axis can be controlled by simple electron transfer processes, which provides a basis for the structure-property relationship for the nonlinear optical (NLO) switching. However, this phenomenon has not been previously reported in the development of NLO properties of metallacarboranes. In this work, the metallacarboranes [NIIII/IV(C2B9H11)2]-/0 and their C-,B-functionalized derivatives are studied by the density functional theory (DFT) method. By calculating relative energies, we obtained the stable states before and after rotation controlled by simple electron transfer. Then, the static and frequency-dependent second-order NLO properties were calculated by several DFT functionals. According to the TDDFT results, the large NLO responses of the studied compounds are mainly caused by substituent group-to-carborane cage charge transfer (L'LCT) and substituent group-to-metal charge transfer (L'MCT) processes. The order of first hyperpolarizabilities (β values) illustrates that the NLO response can be enhanced by introducing a strong electron-donating group. Significantly, the geometric interconversions resulting from the redox reaction of 1C/1T-6C/6T allow the NLO responses to be switched "ON" or "OFF". The B(9,9')-methoxyphenyl-functionalized derivative of nickelacarborane, having low energetic cost and large different NLO responses between two states (from 0 to 20 998 a.u.), can be an excellent switchable NLO material. [ABSTRACT FROM AUTHOR]

Recently, two isomeric thiophene-fused benzocarborane derivatives Tb1 and Tb2 with different locations of sulfur atoms, labeled as 1, 4 and 6, 9 of the thiophene were synthesized by Morisaki (Chem.-Eur. J., 2012, 18, 11251-11257) and Barrere (Macromolecules, 2009, 42, 2981-2987), respectively. In the present work, natural bond orbital (NBO) analysis shows that after doping one lithium atom into the isomeric structures Tb1 and Tb2, the electrons transfer to different regions in Tb1 and Tb2. For Tb1-Li, the transferred electrons mainly locate at S1, C2, C3, and S4, but for Tb2-Li, the transferred electrons mainly locate at C2, C3, C7, and C8. Significantly, the charge distribution is a crucial factor influencing the static first hyperpolarizabilities for Tb1-Li and Tb2-Li. Furthermore, the βtot value of Tb1-Li is 6222 au, which is about 160 times larger than that of Tb1 (39 au). However, the βtot value of Tb2-Li (498 au) is only about 5 times larger than that of the corresponding Tb2 (91 au). It is our expectation that this work could provide useful information for the development of nonlinear optical materials based on carboranes. [ABSTRACT FROM AUTHOR]

Two Anderson-type heteropolyanion-supported copper phenanthroline redox couples have been successfully introduced into dye-sensitized solar cells, which can significantly increase the shortcircuit photocurrent, open-circuit voltage and the conversion efficiency by 2.2 times, 26.8% and 3.93 times respectively, compared to the pristine copper phenanthroline redox couple. [ABSTRACT FROM AUTHOR]

The electronic structures and photophysical properties of eight Pt-complexes with different N-heterocyclic carbene ligands and potential to serve as light emitting diode materials were investigated by density functional theory and time-dependent density functional theory, employing the BP86 functional for geometry optimisations, SAOP potential for excited state calculations and all-electron TZ2P basis set throughout. Non-radiative and radiative decay rate constants were determined for each system through analyses of the geometric relaxations, d-orbital splitting and spin–orbit couplings at the optimised S0and T1geometries. Three Pt-systems bound to two N-heterocyclic carbenes were shown to be nonemissive, while a fourth was shown to be emissive from the T1excited state. Similar T1-initated emission was observed for three other Pt-systems investigated, each bound to four N-heterocyclic carbenes, while a fourth similarly tetra-ligated system showed T2-initation of emission. The results highlight the coupling of ligand-identity to photophysical properties and more importantly, the potential for rational optimisation and tuning of emission wavelengths and phosphorescent efficiencies. Encouragingly, two of the tetra-N-heterocyclic carbene ligated systems show strong potential to serve as highly-efficient blue and green light emitting materials, respectively. [ABSTRACT FROM AUTHOR]

With the bottom-up design principle, we use metal-ions to bridge the predesigned tectons (1[(H2L1)2(Mo8O26)]·4H2O and 3[(H2L2)(L2)0.5(Mo8O26)0.5]·H2O) so that two higher dimensional γ-octamolybdate based inorganic–organic hybrid compounds 2[CuI2(L1)3(Mo8O26)0.5] and 4[Ni(L2)2(HL2)2(Mo8O26)]·4H2O are successfully obtained. [ABSTRACT FROM AUTHOR]

Three cationic iridium complexes containing 4,7-bis(3,6-di-tert-butyl-9H-carbazol-9-yl)-1,10-phenanthroline (L1) and 4,7-bis(3′,6′-di-tert-butyl-6-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3,9′-bi(9H-carbazol)-9-yl)-1,10-phenanthroline (L2) as the ancillary ligands, namely, [Ir(ppy)2(L1)]PF6(1), [Ir(ppy)2(L2)]PF6(2) and [Ir(oxd)2(L2)]PF6(3) (ppy is 2-phenylpyridine, oxd is 2,5-diphenyl-1,3,4-oxadiazole), have been designed and prepared. With more intramolecular rotational units on the ancillary ligand (L2), 2and 3possess a unique aggregation-induced phosphorescent emission (AIPE) property. This phenomenon was unprecedentedly observed in the cationic iridium(iii) complexes. In order to investigate the underlying mechanism of this AIPE behavior, their photophysical, temperature-dependent aggregation properties as well as theoretical calculations, were performed. The results suggest that restricted intramolecular rotation is responsible for the AIPE of cationic complexes. Moreover, photoluminescent quantum yields in the neat film, thermal stabilities and off/on luminescence switching of 2were investigated, revealing its potential application as a candidate for LECs and organic vapor sensing. [ABSTRACT FROM AUTHOR]

High-valent transition-metal-substituted Keggin-type polyoxometalates (POMs) are active and robust oxidation catalyst. The important oxidized intermediates of these POM complexes are very difficult to be characterized by using the experimental method, and thus no detail information is available on such species. In the present paper, density functional theory (DFT) calculations have been carried out to characterize the electronic structures of a series of mono-ruthenium-substituted Keggin-type POMs. We find that the aquaruthenium(ii/iii/iv) species possess dxy2dxz2dyz2, dxy2dxz2dyz1, and dxy2dxz1dyz1electronic configuration, respectively, and hydroxyl/oxoruthenium(iv/v/vi) species possess dxy2dxz1π*yz1, dxy2π*xz1π*yz1, dxy1π*xz1π*yz1, and dxy1π*xz1π*yz0electronic configuration, respectively. Mulliken spin population shows that spin density is localized on the ruthenium center in aquaruthenium(ii/iii/iv) POM complexes, and the RuOaunit in hydroxyl/oxoruthenium(iv/v/vi) POM complexes. The Oaatom has substantial radical character in oxoruthenium(iv/v) species, and the radical character of the Oaatom are significantly weakened in the oxoruthenium(vi) species. The relevant energy of the important Ru–Oaπ*-antibonding unoccupied orbitals with high RuOacompositions of oxoruthenium(iv/v/vi) POM complexes decrease in the order: oxoruthenium(iv) > oxoruthenium(v) > oxoruthenium(vi). The pH-independent multiple reduction energies for Ru(iii/ii), Ru(v/iv), and Ru(vi/v) couples are calculated, which is in agreement with the experimental data. [ABSTRACT FROM AUTHOR]

The complexes AlQ3and Ir(ppy)3(Q = 8-hydroxyquinolate; ppy = 2-phenylpyridyl) are typical green emitting fluorescence and phosphorescence materials, respectively. Here we hybridize Ir(ppy)3with AlQ3to investigate the optoelectronic properties of the Ir(iii)-centred derivatives including (ppy)2IrQ, (ppy)IrQ2and IrQ3by using density functional methods. Our calculations show that the derivative Ir(iii) complexes are red emitting phosphorescence materials. The characters of the lowest triplet excited states for these Ir(iii) complexes are mainly dominated by the 8-hydroxyquinolate ligand. IrQ3and (ppy)2IrQ possess good electron transfer performance, while (ppy)IrQ2might have hole transport properties. [ABSTRACT FROM AUTHOR]

The second-order nonlinear optical (NLO) properties of porphyrin–metal–polyoxometalate (por–metal–POM) sandwich structures [(por)M(PW11O39)]5−(por = TPP, TPyP, TPPF20, M = Hf; por = TPP, M = Zr) and [(TPP)Hf(XW11O36)]6−(X = Si, Ge) are investigated by time-dependent density functional theory (TDDFT). The character of charge-transfer transition indicates that the porphyrin ligand acts as an electron acceptor and the lacunary Keggin-type POM acts as an electron donor. Our results show that this kind of organic–inorganic hybrid compound possesses remarkably large molecular second-order NLO polarizability, ∼100 × 10−30esu, and might be an excellent second-order NLO material. Furthermore, the NLO response can be tuned by the element substituents. The computed β0values increase with the auxiliary electron-accepting group on the porphyrin ring (TPPF20> TPyP > TPP) and a heavy central heteroatom (Ge > Si > P). The present investigation provides important insight into the NLO properties of this class of por–metal–POM sandwich compound. [ABSTRACT FROM AUTHOR]

Two POM-pillared 3D porous compounds, [CuICuII(CuIIfcz)2(H2O)5(PMoVI10MoV2O40)]·6H2O (1) and [CuI2(CuIIfcz)2(H2O)2(PMoVI8VV3VIV3O42)]·6H2O (2) (Hfcz = fluconazole, (1-(2,4-difluorophenyl)-1,1-bis[(1H-1,2,4-triazol-1-yl)methyl]benzyl alcohol) have been constructed based on different polyanions, (Cufcz)22+ macrocations and copper cations by the hydrothermal method. The (Cufcz)22+ macrocations link Cu cations to generate a 2D wavelike cationic sheet. Then the POM anions act as pillars to the cationic sheet to form different POM-pillared 3D frameworks. In compound 1, the polyanion exhibits a rare coordination mode and acts as a penta-dentate ligand, which acts as to pillars to the cationic sheet to form an unprecedented 3D (3,4,5,6)-connected open framework with (3·6·7)(32·6·73)(33·4·62·73·8)(34·42·62·76·8)(32·62·76·84·10) topology. In compound 2, polyanions covalently link cationic sheets to extend to an unusual 3D (3,4,6)-connected framework with the (52·6)(52·62·7·9)(54·64·74·93) topology. To the best of our knowledge, it is the first time that POM-pillared 3D metal–organic frameworks have been realized by combining POMs with deliberately designed macrocations and transition-metal ions, using a rational approach for synthesis of POM-based open metal–organic frameworks. In addition, the electrochemical behaviors of compounds 1 and 2 have been investigated. [ABSTRACT FROM AUTHOR]

A series of mixed-ligand coordination complexes, namely [Zn(L1)(oba)] (1), [Cd(L1)(oba)] (2), [Zn2(L2)(oba)2]·8H2O (3), [Cd2(L2)(oba)2]·2H2O (4), [Zn3(L3)(oba)3] (5), [Cd2(L3)(oba)2]·(L3) (6), [Cd(L4)(oba)]·H2O (7) and [Cd(L5)(oba)]·3H2O (8), where L1= 2-(2-pyridyl)imidazole, L2= 1,4-bis[2-(2-pyridyl)imidazol-1-yl]butane, L3= 1,4-bis[2-(2-pyridyl)imidazol-1-ylmethyl]benzene, L4= 1,3-bis[2-(2-pyridyl)imidazol-1-ylmethyl]benzene, L5= 1,2-bis[2-(2-pyridyl)imidazol-1-ylmethyl]benzene and H2oba = 4,4′-oxydibenzoic acid, have been synthesized under hydrothermal conditions. Their structures have been determined by single crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric (TG) analyses. In compounds 1and 2, oba2−, L1ligand and ZnIIor CdIIions assemble to form the parallel chains or parallel sheets which are linked by the weak hydrogen bonding and ππ stacking interactions to give the 2D supramolecular sheet or 3D supramolecular net, respectively. For 3, L2ligands connect [Zn(oba)] chains to generate a unusual (10,3)-b topological structure which is the first example for eight-fold interpenetrating framework based on the (10,3)-b net. In 4, L2ligands link [Cd(oba)] double-chains to give a 2D sheet which is assembled by ππ stacking interactions to obtain a 3D supramolecular net. In 5, L3ligands link ZnIIions from α-Po net formed by ZnIIions and oba2−anions to show a novel 3D 8-connected self-penetrating framework with the unreported (416·611·8) topological structure. In 6, the double-chains constructed by CdIIand oba2−anions are linked by one kind of L3ligand to form a layer-like structure which is assembled by ππ stacking interactions to show a 3D supramolecular structure. In 7, oba2−anions coordinate to CdIIcations to form chains which are connected by L4to form a four-fold interpenetrating diamond network. In 8, the weak hydrogen bonding and ππ stacking interactions connect the [Cd(L5)(oba)] chains to give a 2D supramolecular sheet. By careful inspections of the structures of 1–8, we believe that the different flexible and angular neutral ligands, coordination geometries of metal centers and weak interactions (hydrogen bonds and ππ stacking interactions) are crucial factors for the formation of the different structures. The photoluminescent properties of 1–8have been studied in the solid state at room temperature. [ABSTRACT FROM AUTHOR]

In this paper, ten new silver compounds, namely [Ag(bipy)](L1)·H2O (1), [Ag(bipy)](L2)·2H2O (2), [Ag2(bipy)2(H2O)2](L3)·H2O (3), [Ag(L4)(bipy)]·H2O (4), [Ag(L5)(bipy)] (5), [Ag(L6)(bipy)]·0.5CH3CN (6), [Ag3(L7)2(bipy)2]·2(H2O) (7), [Ag2(L8)(bipy)1.5(H2O)]·H2O (8), [Ag2(L9)(bipy)2(H2O)2] (9) and [Ag3(L10)(bipy)2][(bipy)(H2O)2]·(H2O)3.5 (10) (where bipy = 4,4′-bipyridine, L1 = 6-amino-1-naphthalenesulfonate anion, L2 = 2-naphthalenesulfonate anion, L3 = sulfosalicylate anion, L4 = p-aminobenzenesulfonate anion, L5 = 4-dimethyaminoazobenzenen-4′-sulfonate anion, L6 = 2,5-dichloro-4-amino-benzenesulfonate anion, L7 = 8-hydroxyquinoline-5-sulfonate anion, L8 = 2-nitroso-1-naphthol-4-sulfonate anion, L9 = 2,6-naphthalenedisulfonate anion and L10 = 1,3,5-naphthalenetrisulfonate anion), have been synthesized and characterized by elemental analyses, IR spectroscopy and X-ray crystallography. In compounds 1–6, Ag(i) centers are linked by bipy ligands to form 1D Ag–bipy chain structures, in which the sulfonate anions of compounds 1–3 act as counter ions. The sulfonate anions of compounds 4 and 5 connect Ag–bipy chains to form 1D double chain structures, respectively. The sulfonate anions of compound 6 connect Ag–bipy chains to form a 2D layer structure. Unexpectedly, compound 7 shows a hinged chain structure, and these chains interlace with each other through hydrogen bonds and π–π interactions to generate a 3D structure with channels along the c axis. Compounds 8 and 9 show 1D ladder-like structures. In compound 10, the Ag–bipy chains are connected by sulfonate anions to generate a 3D poly-threaded network, in which an isolated Ag–bipy chain is inserted. The results indicate that the anionic sulfonate-containing co-ligands play an important role in the final structures of the Ag(i) complexes. Additionally, the luminescent properties of these compounds were also studied. [ABSTRACT FROM AUTHOR]

Five POM-based hybrid materials have been designed and synthesized based on different metal ions under hydrothermal conditions, namely, [Zn(Hfcz)(H2O)3](H3fcz)(SiMo12O40)·3H2O (1), [Cd2(Hfcz)6(H2O)2](SiMo12O40)·H2O (2), [Co2(Hfcz)2(SiW12O40)](H3fcz)2(SiW12O40)·10H2O (3), [Ni2(Hfcz)4(H2O)2](SiW12O40)·5H2O (4) and [Ag4(Hfcz)2(SiMo12O40)] (5), where Hfcz is fluconazole [2-(2,4-difluorophenyl)-1,3-di(1H-1,2,4-triazol-1-yl)propan-2-ol]. Their crystal structures have been determined by X-ray diffraction, elemental analyses, IR spectra, and thermogravimetric analyses (TGA). There are 1D mono and double chain-like metal–organic units in compounds 1 and 2, respectively. Polyoxometalates and metal–organic units co-crystallize through hydrogen bonds. In compound 3, metal–organic sheets are pillared by one kind of polyanion through covalent connections to generate a sandwich double-sheet. The other kind of polyanion acts as a counter-ion and lies in two adjacent sandwich double-sheets through non-covalent interactions. Polyanions covalently link metal–organic sheets to extend to an unusual 3D 5-connected framework with the (44·66) topology in 4. In compound 5, polyanions link metal–organic chains to form a sheet through covalent connections. It is interesting that compound 5 shows an intricate (4,5,10)-connected framework with (44·62)4(48·62)2(414·619·812) topology based on two kinds of Ag cations as four-connected and five-connected nodes, and polyanions as ten-connected nodes, when Ag⋯O interactions are considered. It represents the highest connected network topology presently known for polyoxometalate systems. The structural differences among 1–5 indicate the importance of different metal–organic units, coordination modes of polyanions for framework formation, and the interactions between polyanions and metal–organic units. In addition, the luminescent properties of compounds 1, 2 and 5, and electrochemical behaviours of compounds 1–5 have been investigated. [ABSTRACT FROM AUTHOR]

Inorganic–organic hybrid materials based on Keggin polyoxometalate building blocks combined with CuII/CuI and flexible fluconazole ligand [1-(2,4-difluorophenyl)-1,1-bis[(1H-1,2,4-triazol-1-yl)methyl]methanol] (Hfcz) have been obtained by hydrothermal methods, namely, [CuII2(Hfcz)4(SiW12O40)]·3H2O (1), [CuII4(fcz)4(H2O)4(SiMo12O40)]·6H2O (2), [CuII2(fcz)2][CuII4(fcz)4(SiW12O40)][CuII2(fcz)2(H2O)2(SiW12O40)]·6H2O (3), (Et3NH)2[CuI2(Hfcz)2(SiW12O40)]·2H2O (4), (Et3NH)2[CuI2(Hfcz)2(SiW12O40)]·H2O (5) and [CuI4(Hfcz)4(SiMo12O40)] (6). Their structures have been determined by single-crystal X-ray diffraction analyses, and the compounds are further characterized by elemental analyses, IR spectra and thermogravimetric (TG) analyses. In 1, Cu(ii) cations are bridged by fluconazole ligands to form a 3D lvt coordination polymeric network, which is connected by (SiW12O40)4− anions to form a complicated 3D (4,6)-connected framework with the topology of (42·64)(46·67·82)2. In 2, two fcz− anions chelate two Cu2+ cations to form a [Cu(fcz)]22+ dimer, which is bridged by (SiW12O40)4− polyanions to generate a 2D (4,4) grid. Compound 3 is formed by three types of co-crystallizing subunits including a dimer [Cu(fcz)]22+, a dumbbell molecule [Cu4(fcz)4(SiW12O40)] and an infinite chain {[Cu2(fcz)2(H2O)2(SiW12O40)]2−}∞. In compounds 4 and 5, Hfcz ligands link Cu+ cations to generate 1D coordination polymeric units, and (SiW12O40)4− polyanions connect these metal–organic units to form two types of (63) sheets which are topological isomerism. In compound 6, (SiMo12O40)4− polyanions fixed in CuI–Hfcz square rings are further extended into a 2D sheet via linking CuI atoms of different rings. By carefully inspection of the structures of 1–6, it is believed that various transition-metal organic units and Keggin polyanions with different coordination modes are important for the formation of the different structures. In addition, electrochemical behaviors of compounds 1, 2, 5 and 6 have been investigated. [ABSTRACT FROM AUTHOR]