Crystal-to-crystal polymerisation of monosubstituted [PW11O39Cu(H2O)]5- Keggin-type anions.

The reaction between neutral bis(picolinate)copper(II) complexes and copper(II)-monosubstituted Keggin-type phosphotungstate anions formed in situ leads to the formation of the hybrid [C(NH2)3]10[{PW11O39Cu(H2O)}2{Cu(pic)2}]·10H2O compound (1, pic = picolinate) in the presence of structure-directing guanidinium cations. Single-crystal X-ray diffraction studies demonstrate that 1 contains dimeric {PW11O39Cu(H2O)}2{Cu(pic)2} molecular species constituted by two Keggin-type anions linked by one {Cu(pic)2} octahedral complex through axial coordination to their terminal oxygen atoms. The extensive hydrogen-bonding network established by guanidium cations and Keggin clusters plays a key role in retaining the crystallinity of the system throughout dehydration to allow a single-crystal-to-single-crystal (SCSC) transformation into the anhydrous [C(NH2)3]10[{PW11O39Cu}2{Cu(pic)2}] (2a) at 170 °C. Structural modifications involve the re-orientation, shifting in ca. 1.5 Å and condensation of all the {PW11O39Cu} units to result in {PW11O39Cu}n chains in an unprecedented solid-state polymerisation. This phase transition also implies the cleavage of Cu-O bonds induced by the rotation and translation of Keggin-type anions, in such a way that hybrid dimeric units in 1 are dismantled and {Cu(pic)2} complexes become square planar. The irreversibility of the phase transition has been confirmed by combined thermal and diffractometric analyses, which evidence that the anhydrous phase adsorbs only one water molecule per cluster to become the [C(NH2)3]10[{PW11O39Cu}2{Cu(pic)2}]·2H2O (2h) hydrated derivative without any significant alteration in its cell parameters, nor in its crystalline structure. Phase transformations have been monitored by electron paramagnetic resonance spectroscopy.

Systematic Approach to the Synthesis of Cobalt-Containing Polyoxometalates for Their Application as Energy Storage Materials.

New energy storage materials are an object of study within the framework of the global energy transition. The development of renewable sources is being boosted thanks to stationary energy storage systems such as redox flow batteries (RFBs). This work reports the synthesis of the cobalt-containing Keggin-type polyoxometalates [CoW12O40]6- (CoW12) and [Co(H2O)SiW11O39]6- (CoSiW11), which have previously been shown to have applicability in RFBs. These procedures were reassessed to meet the strict requirements associated with the further implementation of RFBs, including fast and affordable synthetic procedures with high reaction yields. In contrast to the lengthy and complicated synthetic approaches published to date, the optimized synthesis reported in this work enables the isolation of the pure crystalline salt of the CoW12 anion with a 75% reduction of the time of the whole reaction procedure, eliminating tedious steps such as the recrystallization and including a 20% increased yield. The control of the stoichiometry, fine-tuning of reaction conditions, and the identification of intermediate species, as well as the acidic equilibria taking place during the process, were monitored via thermal, spectroscopic, and structural analyses. In the case of the CoSiW11 anion, its preparation was based on a simple and highly efficient procedure. Moreover, promising electrochemical properties were observed with the use of the one-pot synthetic approach, in which the stoichiometric amounts of the starting reagents are dissolved in the supporting electrolyte to be directly implemented as the electrolyte for a RFB.

Consecutive Single-Crystal-to-Single-Crystal Isomerization of Novel Octamolybdate Anions within a Microporous Hybrid Framework with Robust Water Sorption Properties.

The 3D hybrid framework [{Cu(cyclam)}3 (κ-Mo8 O27 )] ⋅ 14H2 O (1) (cyclam=1,4,8,11-tetraazacyclotetradecane) undergoes sequential single-crystal-to-single-crystal transformations upon heating to afford two different anhydrous phases (2 a and 3 a). These transitions modify the framework dimensionality and enable the isomerization of κ-octamolybdate (κ-Mo8 ) anions into λ (2 a) and µ (3 a) forms through metal migration. Hydration of 3 a involves condensation of one water molecule to the cluster to afford the γ-Mo8 isomer in 4, which dehydrates back into 3 a through the 6 a intermediate. In contrast, 2 a reversibly hydrates to form 5, exhibiting the same Mo8 cluster as that of 1. It is remarkable that three of the Mo8 clusters (κ, λ and µ) are new and that up to three different microporous phases can be isolated from 1 (2 a, 3 a, and 6 a). Water vapor sorption analyses show high recyclability and the highest uptake values for POM-based systems. The isotherms display an abrupt step at low humidity level desirable for humidity control devices or water harvesting in drylands.

Combined experimental and theoretical investigation on the magnetic properties derived from the coordination of 6-methyl-2-oxonicotinate to 3d-metal ions.

Five new compounds are reported herein starting from 2-hydroxy-6-methylnicotinic acid (H2h6mnic) and first-row transition metal ions, although H2h6mnic shows a prototropy in solution to lead to the 6-methyl-2-oxonicotinate (6m2onic) ligand that is the molecule eventually present in the compounds. The structural and chemical characterization reveals the following chemical formulae: {[MnNa(µ3-6m2onic)2(µ-6m2onic)(MeOH)]·H2O·MeOH}n (1Mn), {[M2Na2(µ3-6m2onic)2(µ-6m2onic)2(µ-H2O)(H2O)6](NO3)2}n [MII = Co (2Co) and Ni (3Ni)], 2[Cu2(6m2onic)3(µ-6m2onic)(MeOH)]·[Cu2(6m2onic)2(µ-6m2onic)2]·2[Cu(6m2onic)2(MeOH)]·32H2O (4Cu) and {[Cu(µ-6m2onic)2]·6H2O}n (5Cu) (where 6m2onic = 6-methyl-2-oxonicotinate). An unusual structural diversity is observed for the compounds, ranging from isolated complexes (in 4Cu), 1D arrays (in 1Mn and 5Cu) and 3D frameworks (in 2Co and 3Ni). Magnetic properties have been studied for all compounds. Analysis of the magnetic dc susceptibility and magnetization data for 4Cu and 5Cu suggests the occurrence of ferromagnetic exchange, which is well explained by broken-symmetry and CASSCF calculations. The sizeable easy-plane magnetic anisotropy present in compound 2Co allows for a field-induced magnet behaviour with an experimental effective energy barrier of 16.2 cm-1, although the slow relaxation seems to be best described through Raman and direct processes in agreement with the results of ab initio calculations.

New phosphotetradecavanadate hybrids: crystal structure, DFT analysis, stability and binding interactions with bio-macromolecules.

Two novel bicapped Keggin polyoxidovanadates with organic cations, (C6H8N)5[H4PV14O42]·5H2O (1) and (C6H14N4)2(NH4)[H4PV14O42]·11H2O (2), (PV14O426- = PV14, C6H7N = 3-picoline and C6H12N4 = methenamine) were synthesized. These compounds were isolated and characterized in the solid state and in solution by elemental analysis, powder X-ray diffraction, FTIR, UV-vis, 51V, 31P, 13C and 1H NMR, and fluorescence spectroscopy. Further confirmation of the PV14 structures was obtained by single-crystal X-ray diffraction studies of 1 and 2. The Hirshfeld surface analysis was performed to confirm that within the intermolecular interactions occurring in the two crystals, the O⋯H/H⋯O, O⋯O and H⋯H interactions dominate. The protonation and one-electron reduction of the PV14 moiety were also analysed by means of DFT calculations; besides confirming the protonation sites and correctly predicting the pKa values, the DFT results also indicate that molecular reduction is energetically more favourable in protonated PV14 anions. Upon the addition of PV14 anions to bovine serum albumin (BSA) up to a ratio of 1 : 1, the fluorescence decreased by 45% for both 1 and 2, indicating that the interaction of vanadium-containing species with this protein takes place; log(KSV) values of ca. 5.5 were obtained in both systems. Upon the addition of 1 or 2 to solutions of calf-thymus DNA (ctDNA), changes were observed in the UV-vis absorption and circular dichroism spectra. The significance of the changes observed is discussed considering the several V-containing species that form in the solution.

The Chemistry of Zirconium/Carboxylate Clustering Process: Acidic Conditions to Promote Carboxylate-Unsaturated Octahedral Hexamers and Pentanuclear Species.

Clustering chemistry is a key point in the design and synthesis of the secondary building units that comprise metal-organic frameworks (MOFs) based on group IV metals. In this work, the first stages of the zirconium-carboxylate clustering process in alcohol/water mixtures are studied in detail using the monocarboxylic benzoic and hydroxybenzoic acids to avoid the polymerization. Mass spectroscopy measurements performed on the reactions revealed the presence of hexa- and pentanuclear species even at low pH values and also evidenced the acid-base nature and pH dependence of the transformation between both species. The control on the chemistry governing the equilibria between these species has allowed us to isolate six new compounds in the solid state. The single-crystal X-ray diffraction analysis revealed that they are closely related to the well-known [Zr6(O)4(OH)4(OOC)12] secondary building unit found in many MOFs by removing carboxylic ligands in the case of the hexameric species ([Zr6(O)4(OH)4(OOC)8(H2O)8]4+) or by additionally removing one of the metal centers in the case of the pentameric entities ([Zr5(O)2(OH)6(OOC)4(H2O)11(alcohol)]6+). Going in detail, the unsaturated hexameric clusters exhibit different dispositions of their eight carboxylate ligands in such a way that the remaining four carboxylate-free positions are arranged according to a square planar or tetrahedral symmetry. It should be highlighted that the pentameric complexes imply an unprecedented core nuclearity in zirconium clusters and thus their isolation provides a novel building block for the design of metal-organic materials.

Slow Magnetic Relaxation and Luminescent Properties of Mononuclear Lanthanide-Substituted Keggin-Type Polyoxotungstates with Compartmental Organic Ligands.

The reaction of mid to late lanthanide ions with the N,N'-dimethyl-N,N'-bis(2-hydroxy-3-formyl-5-bromobenzyl)ethylene-diamine organic ligand and monolacunary Keggin type [α-SiW11O39]8- anion affords a series of isostructural compounds, namely, K5[LnIII(α-SiW11O39)(C20H22Br2N2O4)]·14H2O (1-Ln, Ln = Sm to Lu). The molecular structure of these sandwich-type complexes is formed by the LnIII ion in a biaugmented trigonal prismatic geometry, which occupies the external O4 site of the organic ligand and the vacant site of the lacunary polyoxometalate (POM) unit. The empty N2O2 coordination site of the organic ligand allows its unprecedented folding, which displays a relative perpendicular arrangement of aromatic groups. Weak Br···Br and π-π interactions established between adjacent molecular units govern the crystal packing, which results in the formation of assemblies containing six hybrid species assembled in a chairlike conformation. 1-Gd and 1-Yb display slow relaxation of the magnetization after the application of an external magnetic field with maxima in the out-of-phase magnetic susceptibility plots below ∼5-6 K, which is ascribed to the presence of various relaxation mechanisms. Moreover, photoluminescent emission is sensitized for 1-Sm and 1-Eu in the visible region and 1-Er and 1-Yb in the NIR. In contrast, the quenching of metal-centered luminescence in the 1-Tb derivative has been attributed to the out-of-pocket coordination mode of the lanthanide center within the POM fragment. It is demonstrated that the 1-Yb dual magneto-luminescent material represents the first lanthanide-containing POM reported to date with simultaneous slow magnetic relaxation and NIR emission. Solution stability of the hybrid molecular species in water is also confirmed by ESI-mass spectrometry experiments carried out for 1-Tb and 1-Tm.

Single-Crystal-to-Single-Crystal Cluster Transformation in a Microporous Molybdoarsenate(V)-Metalorganic Framework.

The hybrid compound [Cu(cyclam)(H2O)2]0.5[{Cu(cyclam)}1.5{B-H2As2Mo6O26(H2O)}]·9H2O (1) (cyclam = 1,4,8,11-tetraazacyclotetradecane) was synthesized in aqueous solution by reacting the {Cu(cyclam)}2+ complex with a mixture of heptamolybdate and an arsenate(V) source. Crystal packing of 1 exhibits a supramolecular open-framework built of discrete covalent molybdoarsenate/metalorganic units and additional [Cu(cyclam)(H2O)2]2+ cations, the stacking of which generates squarelike channels parallel to the z axis with an approximate cross section of 10 × 11 Å2 where all the hydration water molecules are hosted. Thermal evacuation of solvent molecules yields a new anhydrous crystalline phase, but compound 1 does not preserve its single-crystalline nature upon heating. However, when crystals are dehydrated under vacuum, they undergo a structural transformation that proceeds via a single-crystal-to-single-crystal pathway, leading to the anhydrous phase [{Cu(cyclam)}2(A-H2As2Mo6O26)] (2). Total dehydration results in important modifications within the inorganic cluster skeleton which reveals an unprecedented solid-state B to A isomerization of the polyoxoanion. This transition also involves changes in the CuII bonding scheme that lead to covalent cluster/metalorganic layers by retaining the open-framework nature of 1. Compound 2 adsorbs ambient moisture upon air exposure, but it does not revert back to 1, and the hydrated phase [{Cu(cyclam)}2(A-H2As2Mo6O26)]·6H2O (2h) is obtained instead. Structural variations between 1 and 2 are reflected in electron paramagnetic resonance spectroscopy measurements, and the permanent microporosity of 2 provides interesting functionalities to the system such as the selective adsorption of gaseous CO2 over N2.

Isolation of the Elusive Heptavanadate Anion with Trisalkoxide Ligands.

The unprecedented heptavanadate cluster has been isolated from reactions between trisalkoxide ligands and vanadate in water at pH = 2 as a series of alkylammonium [HxV7O18(H2O)((OCH2)3CR)](4-x)- salts (1-3, R = CH2OH; 4, R = CH3). Their structures have been determined and the partial stability of 4 in water assessed by a combination of multinuclear NMR spectroscopy and ESI-MS. The heptavanadate unit reported herein could represent an intermediate species in the formation of decavanadate that is blocked by attachment of tripodal ligands.

Mechanism of action of nitrification inhibitors based on dimethylpyrazole: A matter of chelation.

In agriculture, the applied nitrogen (N) can be lost in the environment in different forms because of microbial transformations. It is of special concern the nitrate (NO3-) leaching and the nitrous oxide (N2O) emissions, due to their negative environmental impacts. Nitrification inhibitors (NIs) based on dimethylpyrazole (DMP) are applied worldwide in order to reduce N losses. These compounds delay ammonium (NH4+) oxidation by inhibiting ammonia-oxidizing bacteria (AOB) growth. However, their mechanism of action has not been demonstrated, which represent an important lack of knowledge to use them correctly. In this work, through chemical and biological analysis, we unveil the mechanism of action of the commonly applied 3,4-dimethyl-1H-pyrazole dihydrogen phosphate (DMPP) and the new DMP-based NI, 2-(3,4-dimethyl-1H-pyrazol-1-yl)-succinic acid (DMPSA). Our results show that DMP and DMPSA form complexes with copper (Cu2+) cations, an indispensable cofactor in the nitrification pathway. Three coordination compounds namely [Cu(DMP)4Cl2] (CuDMP1), [Cu(DMP)4SO4]n (CuDMP2) and [Cu(DMPSA)2]·H2O (CuDMPSA) have been synthesized and chemical and structurally characterized. The CuDMPSA complex is more stable than those containing DMP ligands; however, both NIs show the same nitrification inhibition efficiency in soils with different Cu contents, suggesting that the active specie in both cases is DMP. Our soil experiment reveals that the usual application dose is enough to inhibit nitrification within the range of Cu and Zn contents present in agricultural soils, although their effects vary depending on the content of these elements. As a result of AOB inhibition by these NIs, N2O-reducing bacteria seem to be beneficed in Cu-limited soils due to a reduction in the competence. This opens up the possibility to induce N2O reduction to N2 through Cu fertilization. On the other hand, when fertilizing with micronutrients such as Cu and Zn, the use of NIs could be beneficial to counteract the increase of nitrification derived from their application.

Structural Characterization of Mono and Dihydroxylated Umbelliferone Derivatives.

Coumarin derivatives are a class of compounds with a pronounced wide range of applications, especially in biological activities, in the medicine, pharmacology, cosmetics, coatings and food industry. Their potential applications are highly dependent on the nature of the substituents attached to their nucleus. These substituents modulate their photochemical and photophysical properties, as well as their interactions in their crystalline form, which largely determines the final field of application. Therefore, in this work a series of mono and dihydroxylated coumarin derivatives with different chemical substituents were synthesized and characterized by UV-Visible spectroscopy, thermal analysis (differential scanning calorimetry (DSC) and TGA), 1H NMR and X-Ray Diffraction to identify limitations and possibilities as a function of the molecular structure for expanding their applications in polymer science.

Toward Advanced Functional Systems: Honeycomb-Like Polymeric Surfaces Incorporating Polyoxovanadates with Surface-Appended Copper-Cyclam Complexes.

In this work the immobilization of hybrid polyoxometalates (POMs) onto functional polymeric surfaces is exposed and discussed. Thus, various hybrid polymer‒inorganic films were prepared by anchoring selected hybrid POMs onto tailored polymeric surfaces that consisted of breath figures (BFs) made of polystyrene-b-poly(acrylic acid)/polystyrene (PS-b-PAA/PS) blends. Functionalization of the BF films was performed by selective arrangement of acrylic acid groups of the amphiphilic block copolymer on the surface pores because of their affinition for the water condensed during breath figure formation. These carboxylic acid functional groups contained within the PAA blocks were then employed to anchor [Cu(cyclam)][{Cu(cyclam)}2(V10O28)]·10H2O (1-CuV10) and [{Cu(cyclam)}(VO3)2]·5H2O (1-CuV1), hybrid POMs by immersing the films into aqueous solutions of the in situ formed hybrid clusters, resulting in the hybrid films BF1 and BF2, respectively. Superficial analysis of these hybrid polymeric films was carried out by the sophisticated ion beam-based technique time-of-flight secondary ion mass spectrometry (ToF-SIMS) that was revealed to be an excellent method for the superficial compositional mapping of patterned surfaces.

Structural Transformations in the Thermal Dehydration of [Cu2(bpa)(btec)(H2O)4]n Coordination Polymer.

Reactions between pyridinic ligands such as 1,2-bis(4-pyridyl)ethane (bpa) and transition metal cations are a very widespread technique to produce extended coordination polymers such as Metal-Organic Frameworks. In combination with a second ligand these systems could present different topologies and behaviors. In this context, the use of 1,2,4,5-benzenetetracarboxylic acid (H4btec) gave us a novel 2D compound, [Cu2(bpa)(btec)(H2O)4]n (1), which was prepared by microwave-assisted synthesis and structurally characterized by means of single crystal X-ray diffraction. Its thermal behavior was analyzed through thermogravimetric analysis and variable temperature powder X-ray diffraction, concluding that thermal stability is influenced by the coordination water molecules, allowing two sequential thermochromic phase transformations to take place. These transformations were monitored by electronic paramagnetic resonance spectroscopy and magnetic susceptibility measurements. In addition, the crystal structure of the anhydrous compound [Cu2(bpa)(btec)]n (1.ah) was determined. Finally, a topological study was carried out for the bpa ligand considering all the structures deposited in the Cambridge Structural Databased. More than 1000 structures were analyzed and classified into 17 different topologies, according to the role of the ligand.

Chitosan nanogels as nanocarriers of polyoxometalates for breast cancer therapies.

Polyoxometalates (POMs) have been revealed as interesting antitumor agents inhibiting the action of Sox2 transcription factor, which reduces the risk of metastasis during hormonal therapies. However, they have shown serious concerns to be incorporated into the cells due to their cytotoxicity. Taking this into consideration, this study aims to develop polyoxometalate-based nanocarriers to be potentially applied as new forms of anticancer therapies. Thus, the Wells-Dawson type [P2Mo18O62]6- phosphomolybdate was physically loaded into covalently crosslinked chitosan nanogels that can act as nanocarriers for local delivery. The obtained nanocomposites were extensively characterized by 31P-NMR, TEM microscopy, DLS and zeta potential measurements. This work revealed that selected chitosan nanocarriers would present great potential for POM delivery into tumoral cells due to their pH-triggered deliverability that inhibits cytotoxic drug release at physiological pH. Furthermore, the high uptakes values reported herein make prepared nanocomposites interesting candidates for future breast antitumoral treatments.

Thermostructural Behavior in a Series of Lanthanide-Containing Polyoxotungstate Hybrids with Copper(II) Complexes of the Tetraazamacrocycle Cyclam: A Single-Crystal-to-Single-Crystal Transformation Study.

A series of 14 isostructural [Cu(cyclam)]2[{Cu(cyclam)}4{(α-GeW11O39)Ln(H2O)(OAc)}2]·18H2O (1-Ln, where Ln = La-Lu; cyclam = 1,4,8,11-tetraazacyclotetradecane) polyoxometalate-based hybrids reported herein represent (i) the first example of a two-dimensional covalent hybrid lattice involving the [{(α-XW11O39)Ln(H2O)(OAc)}2] n- archetype and (ii) the first structural characterization of such a dimeric polyoxotungste for Ln = La and Pr as well as for the combination of X = Ge and Ln = Ce, Nd, Sm, or Lu. Compounds 1-Ln have been characterized by elemental analyses, infrared spectroscopy, and thermogravimetric analysis, and their thermostructural behavior has been monitored by powder and single-crystal X-ray diffraction. The title compounds undergo two single-crystal-to-single-crystal transformations triggered by thermal dehydration leading to the [{Cu(cyclam)}6{(α-GeW11O39)Ln(H2O)(OAc)}2]·4H2O intermediate (2-Ln, where Ln = Eu or Er) and [Cu(cyclam)]0.5[{Cu(cyclam)}5.5{(α-GeW11O39)Ln(OAc)}2] (3-Ln, where Ln = Ce or Eu) final anhydrous phases, the latter evidencing a coordinatively unsaturated derivative of the dimeric archetype for the first time. These transitions involve formation and disruption of Cu-OPOM bonds that result in different {Cu(cyclam)}2+ moieties grafting onto and being released from Keggin surfaces, which reduces the dimensionality of 1-Ln to one-dimensional covalent assemblies for 2-Ln and 3-Ln. While all 3-Ln phases rehydrate fully upon exposure to air for 24 h, the kinetics governing the crystal transitions back toward 1-Ln through 2-Ln depend on the nature of Ln. Under ambient moisture, the anhydrous structures fully revert back to the parent framework for Ln = La-Sm, while the samples containing Eu to Lu afford mixtures of 1-Ln and 2-Ln and require immersion in water for the structural reversion to reach completion. Single-crystal X-ray diffraction analyses of the rehydrated 1R-Ln samples (Ln = Ce, Eu, and Er) support these observations.

Six tris-(bipyrid-yl)iron(II) complexes with 2-substituted 1,1,3,3-tetra-cyano-propenide, perchlorate and tetra-fluorido-borate anions; order versus disorder, hydrogen bonding and C-N⋯π inter-actions.

Structures are reported for six closely related salts of tris-(bipyrid-yl)iron(II) cations, namely tris-(2,2'-bi-pyridine)-iron(II) bis-(1,1,3,3-tetra-cyano-2-meth-oxy-propenide) 0.776-hydrate, [Fe(C10H8N2)3](C8H3N4O)2.0.776H2O, (I), tris-(2,2'-bi-pyridine)-iron(II) 1,1,3,3-tetra-cyano-2-(propyl-sulfan-yl)propenide perchlor-ate, [Fe(C10H8N2)3](C10H7N4S)(ClO4), (II), tris-(5,5'-dimethyl-2,2'-bi-pyridine)-iron(II) 1,1,3,3-tetra-cyano-2-meth-oxy-propenide tetra-fluorido-borate ethanol 0.926-solvate, [Fe(C12H12N2)3](C8H3N4O)(BF4).0.926C2H2O, (III), tris-(5,5'-dimethyl-2,2'-bi-pyridine)-iron(II) 1,1,3,3-tetra-cyano-2-eth-oxy-propenide tetra-fluorido-borate, [Fe(C12H12N2)3](C9H5N4O)(BF4), (IV), tris-(5,5'-dimethyl-2,2'-bi-pyridine)-iron(II) 1,1,3,3-tetra-cyano-2-(ethyl-sufanyl)propenide tetra-fluorido-borate, [Fe(C12H12N2)3](C9H5N4S)(BF4), (V), and tris-(5,5'-dimethyl-2,2'-bi-pyri-dine)-iron(II) 1,1,3,3-tetra-cyano-2-prop-oxypropenide tetra-fluorido-borate, [Fe(C12H12N2)3](C10H7N4O)(BF4), (VI). In compound (I), one of the anions is disordered over two sets of atomic sites with equal occupancies while, in the second anion, just one of the C(CN)2 units is disordered, again over two sets of atomic sites with equal occupancies: the anionic components are linked by multiple C-H⋯N hydrogen bonds to form a three-dimensional framework. In compound (II), the polynitrile anion is disordered over two sets of atomic sites with occupancies in the approximate ratio 3:1, while the perchlorate anion is disordered over three sets of atomic sites: there are C-N⋯π inter-actions between the cations and the polynitrile anion. The polynitrile anion in compound (III) is fully ordered, but the tetra-fluorido-borate anion is disordered over two sets of atomic sites with occupancies 0.671 (4) and 0.329 (4): the cations and the tetra-fluorido-borate anions are linked by C-H⋯F inter-actions to form an inter-rupted chain. Compounds (IV) and (V) are isostructural and all of the ionic components are fully ordered in both of them: the cations and tetra-fluorido-borate anions are linked into C 2 2(12) chains. The polynitrile anion in compound (VI) is disordered over two sets of atomic sites with approximately equal occupancies, and here the chains formed by the cations and the tetra-fluorido-borate anions are of the C 2 2(13) type.

A Charge-Transfer Salt Based on Ferrocene/Ferrocenium Pairs and Keggin-Type Polyoxometalates.

A new hybrid inorganic-organometallic salt has been obtained from the reaction of the Keggin-type silicotungstate anion with ferrocene in a water/methanol mixture as a result of the partial oxidation of ferrocene molecules to ferrocenium cations. Single-crystal X-ray diffraction analysis reveals the presence of four ferrocenium (FeIII) cations and one ferrocene (FeII) molecule per plenary Keggin anion in the crystal structure of [FeIII (Cp)2]4[SiW12O40]·[FeII(Cp)2]·2CH3OH (1). Compound 1 thus constitutes the first example in the literature in which ferrocenium and ferrocene species coexist in the structure of a polyoxometalate-based salt. The two crystallographically independent ferrocenium species in the asymmetric unit of 1 exhibit different configurations: One displays an eclipsed conformation with ideal D5h symmetry, whereas the conformation in the other one is staggered D5d. The crystal packing of 1 can be best described as an organometallic sub-lattice of ferrocenium and ferrocene species linked by a network of π-π interactions that generates rectangular cavities of about 14 × 10 Å in which strings of Keggin anions and methanol molecules are hosted, further connected to each other via weak OPOM···CMeOH-OMeOH···OPOM type hydrogen bonds. The charge-transfer nature of the salt has been studied by solid-state diffuse reflectance UV-Vis spectroscopy and the presence of magnetically isolated FeIII/FeII centres has been confirmed by Mössbauer spectroscopy. A topological study carried out on all of the pristine ferrocenyl species deposited in the Cambridge Structural Database (CSD) has allowed two main conclusions to be drawn: (1) these species tend to adopt extreme conformations (either eclipsed or staggered) with less than a 15% of examples showing intermediate states and (2) the oxidation state of the iron centres can be unequivocally assigned on the basis of a close inspection of the Fe···Cp distances, which allows ferrocene neutral molecules and ferrocenium cations to be easily distinguished.

Single-crystal-to-single-crystal transformations triggered by dehydration in polyoxometalate-based compounds.

Single-crystal-to-single-crystal transformations are solid-state phase transitions between different crystalline states in which the crystal integrity and the long-range structural order are retained through the whole transformation process. Such a phenomenon constitutes the structural response that some compounds afford when being exposed to a given external stimulus (temperature, pressure, light, etc.) and, therefore, its study has become a relevant focus of interest within crystal engineering because it allows for monitoring how certain properties (colour, magnetism, luminescence, porosity) of the stimuli-responsive material are modified as the structure evolves into the activated form. A range of organic, inorganic and hybrid systems have been found to undergo such phase transitions, but these examples only include a small number of compounds that incorporate polyoxometalate anions, among which the removal of guest solvent molecules (dehydration) stands out as the most common external stimulus able to induce the occurrence of a single-crystal-to-single-crystal transformation. This feature article compiles the examples of dehydration-triggered single-crystal-to-single-crystal transformation studies that have been reported to date for polyoxometalate-based compounds and reviews some of their most relevant structural aspects.

Immobilization of Polyoxometalates on Tailored Polymeric Surfaces.

Herein we describe the preparation of hybrid polymer-inorganic interfaces by the immobilization of polyoxometalate nanoclusters on functionalized polymer surfaces. The polymeric surfaces were made of polystyrene-b-poly(acrylic acid)/polystyrene (PS-b-PAA/PS) blends by spin coating on a silicon wafer. The functionalization of the polymer film was obtained by interfacial migration of the amphiphilic block copolymer toward the interface upon water vapor annealing. The carboxylic acid functional groups contained in the PAA block were then employed to anchor the [LnIII(α-SiW11O39)]5- polyoxometalates (Ln: Ce, Er). This purpose was achieved by immersing the films in aqueous solutions of the in situ-formed inorganic nanoclusters. X-ray photoelectron and confocal Raman spectroscopies, together with atomic force microscopy, confirmed the immobilization of the inorganic species at the interface.

Thermally-Triggered Crystal Dynamics and Permanent Porosity in the First Heptatungstate-Metalorganic Three-Dimensional Hybrid Framework.

The hybrid compound [{Cu(cyclam)}3 (W7 O24 )]⋅15.5 H2 O (1) (cyclam=1,4,8,11-tetraaza-cyclotetradecane) was synthesized by reacting the {Cu(cyclam)}2+ complex with a tungstate source in water at pH 8. Compound 1 exhibits an unprecedented three-dimensional covalent structure built of heptatungstate clusters linked through metalorganic complexes in a POMOF-like framework that displays water-filled channels. This dynamic architecture undergoes two sequential single-crystal-to-single-crystal transformations upon thermal evacuation of water molecules to result in the partially dehydrated [{Cu(cyclam)}3 (W7 O24 )]⋅12 H2 O (2) and anhydrous [Cu(cyclam)]0.5 [{Cu(cyclam)}2.5 (W7 O24 )] (3) crystalline phases. These transitions are associated with cluster rotations and modifications in the CuII coordination geometries, which reduce the dimensionality of the original lattice to layered systems but preserving the porous nature. Phase 3 reverts to 2 upon exposure to ambient moisture, whereas the transition between 1 and 2 proved to be irreversible. The permanent microporosity of 3 was confirmed by gas sorption measurements (N2 , CO2 ), which reveal a system of parallel channels made of wide cavities connected through narrow necks that limit the adsorption process. This observation is in good agreement with Grand Canonical Monte Carlo simulations.