J.M. Gutierrez-ZorrillaUniversidad del País Vasco / Euskal Herriko Unibertsitatea | UPV/EHU · Inorganic Chemistry
J.M. Gutierrez-Zorrilla
PhD
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Publications (193)
Single crystals of Na40K6[Ni(H2O)6]3 [K@K7Ce24Ge12W120O456 (OH)12(H2O)64]· 178H2O are synthesized by addition of KCl to a NaOAc/AcOH buffer solution containing Ce(NO3)3, GeO2, Na2WO4, and NiCl2 followed by slow evaporation at room temperature (24% yield).
The autoassembly process of copper-oxalate dimers and Keggin type polyoxometalates leads to the first example of a new family of organic-inorganic hybrids, K(14)[(Cu(2)(bpy)(2)(mu-ox))(SiW(11)O(39)Cu(H(2)O))](2)[SiW(11)O(39)Cu(H(2)O)]. approximately 55H(2)O. This compound crystallizes in the monoclinic space group C2/m, a = 37.932(6) A, b = 21.303(...
Four hybrid inorganic-metalorganic compounds containing copper(II)-monosubstituted Keggin polyoxotungstates, K3[Cu(I)(4,4'-bpy)]3[SiW11Cu(II)O39].11H2O (1), (paraquat)3[SiW11Cu(II)O39].6H2O (2; paraquat = N,N'-dimethyl-4,4'-bipyridinium), K3[Cu(I)(4,4'-bpy)]3[GeW11Cu(II)O39].11H2O (3), and Na2[Cu(I)(4,4'-bpy)]3[PW11Cu(II)O39(H2O)].4H2O (4), have be...
Reaction of in situ generated copper(II)-monosubstituted Keggin polyoxometalates and copper(II)-phenanthroline-oxalato complexes in ammonium or rubidium acetate buffers led to the formation of the hybrid inorganic-metalorganic compounds E4[Cu(phen)(H2O)4]2[Cu4(phen)4(H2O)4(ox)3]0.6[Cu2(phen)2(H2O)4(ox)]0.4[Cu(phen)(ox)]0.8[{SiW11O39Cu(H2O)}2{Cu2(ph...
Background:
Increased cancer stem cell (CSC) content and SOX2 overexpression are common features in the development of resistance to therapy in hormone-dependent breast cancer, which remains an important clinical challenge. SOX2 has potential as biomarker of resistance to treatment and as therapeutic target, but targeting transcription factors is...
Compound [C(NH 2 ) 3 ] 10 [{PW 11 O 39 Cu(H 2 O)} 2 {Cu(pic) 2 }]·10H 2 O (1, pic = picolinate) undergoes a thermally-triggered single-crystal-to-single-crystal transformation that involves an unprecedented solid-state polymerisation of monosubstituted Keggin anions.
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) an...
The 3D hybrid framework [{Cu(cyclam)}3(κ‐Mo8O27)] ⋅ 14H2O (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‐M...
The 3D hybrid framework [{Cu(cyclam)} 3 (κ‐Mo 8 O 27 )] ⋅ 14H 2 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‐octamo...
The well-known compound tetrakis(tert-butylammonium)-cyclo-tetrametavanadate (V), [(CH3)3CNH3]4[V4O12] (1h_RT), which crystallizes in the tetragonal I4/m space group, undergoes an irreversible solid state transformation upon heating, constituting one of the few examples in which the initial and the final stages are structurally characterized by sc-...
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 sandwic...
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 co...
The unprecedented heptavanadate cluster has been isolated from reactions between trisalkoxide ligands and vanadate in water at pH = 2 as a series of alkylammonium [H
x
V7O18(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 multinucle...
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 photoc...
Hydrothermal reaction between the monolacunary polyoxometalate [SiW11O39]8–, a copper(II) salt and 1,4,8,11-tetraazacyclotetradecane (cyclam) affords the first example of a hybrid compound combining metal complexes of such N4-tetradentate macrocyclic ligand and Keggin-type clusters, namely [Cu(cyclam)(H2O)][{Cu(cyclam)}2SiW11O39Cu(H2O)]·5H2O (1). T...
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...
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-be...
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) th...
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 devel...
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...
Structures are reported for six closely related salts of tris(bipyridyl)iron(II) cations, namely tris(2,2′-bipyridine)iron(II) bis(1,1,3,3-tetracyano-2-methoxypropenide) 0.776-hydrate, [Fe(C10H8N2)3](C8H3N4O)2.0.776H2O, (I), tris(2,2′-bipyridine)iron(II) 1,1,3,3-tetracyano-2-(propylsulfanyl)propenide perchlorate, [Fe(C10H8N2)3](C10H...
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 giv...
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 ob...
A new organic-inorganic compound based on octamolybdate building blocks and copper(II) complexes of tetradentate N-donor ligands has been hydrothermally synthesized, namely [Cu(cyclam)]2[Mo8O26]·1.5H2O (1), (cyclam: 1,4,8,11–tetraazacyclotetradecane). Compound 1 has been chemically (elemental and thermal analyses), spectroscopically (infrared spect...
The hybrid compound [{Cu(cyclam)}3(W7O24)]·15.5H2O (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 P...
Polioxometalatoak (POM-ak) kimika ez-organikoaren munduan ezagunak diren metal eta oxigenoz osatutako kluster anionikoak dira. Azaldu ohi duten forma, konposizio eta propietate aniztasunaren ondorioz, POM-ek aplikazio ugari aurkezten dituzte teknologia, ekonomia edo ingurugiroari lotutako arlo ezberdinetan. Nahiz eta aspaldidanik aplikazio kataliti...
Among solid-state phase transitions, those in which crystalline order is retained along the process are at the forefront of the crystal engineering. Single-crystal-to-single-crystal transformations triggered by external stimuli have gathered great attention because they allow for correlating structural changes with how properties of the stimuli-res...
The two polyoxometalate salts K9LiNa[Fe16O2(OH)23(H2O)9(P8W49O189)Gd4(H2O)20] and Na22[(2,3-pyzdc)2{NaNi2(H2O)4Sb2W20O70}2] (2,3-pyzdc: 2,3-pyrazinedicarboxylate) demonstrate macroionic self-assembly phenomenon in dilute solution, but with the trends of assembly size vs. solvent polarity opposite to what has been reported to date. This reveals the...
The use of lacunary polyoxometalates (POMs) as polydentate O-donor ligands toward 3d (M) or 4f (Ln) metal ions has resulted in some of the most spectacular POM architectures in terms of size and structural complexity. However, little work has been dedicated to heterometallic 3d–4f POMs in spite of their potential magnetic or bifunctional optomagnet...
The reaction of [VO3]– anions and [Cu(cyclam)]2+ complex cations (cyclam = 1,4,8,11-tetraazacyclotetradecane) results in the [{Cu(cyclam)}(VO3)2]•5H2O (1•5H2O) and [Cu(cyclam)][{Cu(cyclam)}2(V10O28)]•10H2O (2•10H2O) open-framework materials at pH > 6 and pH 4–6, respectively. The dynamic structure of 1•5H2O undergoes up to three sequential and reve...
New organophosphonate derivatives of monovacant Keggin-type polyoxotungstates that contain naphthyl groups have been synthesized and characterized in both solid state and solution. Single-crystal structural analysis shows that two phosphonate groups occupy the vacant position of the lacunary cluster unit in the isostructural compounds [N(C4H9)4]3[H...
The first decavanadate-based microporous hybrid, namely, [Cu(cyclam)][{Cu(cyclam)}2(V10O28)]·10H2O (1, cyclam = 1,4,8,11-tetraazacyclotetradecane) was prepared by reaction of (VO3)(-) anions and {Cu(cyclam)}(2+) complexes in NaCl (aq) at pH 4.6-4.7 and characterized by elemental analyses, thermogravimetry, and X-ray diffraction (powder, single-crys...
Two new Melamine-Keggin hybrid nanorods, MELH-PMo12 and MELH-PW12, for the first time are successfully synthesized by two chemical methods, one-step solid-state chemical reaction method and experimental solvent diffusion method at room temperature. One-step solid-state reactions involve grounded nanorod materials along with grinding of row material...
A series of nine [Sb7 W36 O133 Ln3 M2 (OAc)(H2 O)8 ](17-) heterometallic anions (Ln3 M2 ; Ln=La-Gd, M=Co; Ln=Ce, M=Ni and Zn) have been obtained by reacting 3 d metal disubstituted Krebs-type tungstoantimonates(III) with early lanthanides. Their unique tetrameric structure contains a novel {MW9 O33 } capping unit formed by a planar {MW6 O24 } fragm...
In a new polymorph of the title salt, [Ni(H2O)6](C6H4NO3)2, the metal atom of the cationic complex lies on a symmetry centre and is coordinated by six water molecules to provide a quite regular octahedral coordination environment. These cations interact with 6-oxo-1,6-dihydropyridine-3-carboxylate anions through electrostatic interactions an...
In the title compound, [Cu(C4H3N2O2)2(H2O)2]·2H2O, the CuII ion is located on an inversion centre and exhibits an axially elongated octahedral coordination geometry. The equatorial plane is formed by two N,O-bidentate 1H-pyrazole-3-carboxylate ligands in a trans configuration. The axial positions are occupied by two water molecules. The mononucl...
In this work we demonstrate the efficiency of some dimeric [Ln4(H2O)6(β-GeW10O38)2]12− anions composed of lanthanide-stabilised dilacunary Keggin tungstogermanate fragments (ββ-Ln4, Ln = Dy, Ho, Er, Tm) as heterogeneous catalysts for the organic phase oxidation of aniline with hydrogen peroxide. The results obtained evidence total conversion of ani...
The porous hybrid metavanadate [{Cu(cyclam)}(VO3)2]•5H2O (1) (cyclam = 1,4,8,11–tetraazacyclotetradecane) undergoes thermally triggered sequential single–crystal–to–single–crystal (SCSC) transformations upon gradual dehydration to produce three new porous crystalline phases, namely [{Cu(cyclam)}(VO3)2]•3H2O (2), [{Cu(cyclam)}(VO3)2]•1.3H2O (3) and...
Organic derivatization of polyoxometalates (POMs) is a current hot topic for these anionic clusters composed of oxo-bridged early transition metals. The replacement of labile terminal molecules with organic ligands in 3d-metal substituted POMs is a suitable approach to obtain such type of hybrid derivatives, but still remains largely unexplored. We...
Three new hybrid inorganic-metalorganic compounds containing Keggin-type polyoxometalates, neutral copper(II)-picolinate complexes and guanidinium cations have been synthesized in bench conditions and characterized by elemental analysis, infrared spectroscopy and single-crystal X-ray diffraction: the isostructural [C(NH2)3]4[{XW12O40}{Cu2(pic)4}]·[...
Three new hybrid inorganic-metalorganic compounds containing Keggin-type polyoxometalates, neutral copper(II)-picolinate complexes and guanidinium cations have been synthesized in bench conditions and characterized by elemental analysis, infrared spectroscopy and single-crystal X-ray diffraction: the isostructural [C(NH2)3]4[{XW12O40}{Cu2(pic)4}]·[...
Three new hybrid inorganic-metalorganic compounds containing Keggin-type polyoxometalates, neutral copper(II)-picolinate complexes and guanidinium cations have been synthesized in bench conditions and characterized by elemental analysis, infrared spectroscopy and single-crystal X-ray diffraction: the isostructural [C(NH2)3]4[{XW12O40}{Cu2(pic)4}]·[...
Three new hybrid inorganic-metalorganic compounds containing Keggin-type polyoxometalates, neutral copper(II)-picolinate complexes and guanidinium cations have been synthesized in bench conditions and characterized by elemental analysis, infrared spectroscopy and single-crystal X-ray diffraction: the isostructural [C(NH2)3]4[{XW12O40}{Cu2(pic)4}]·[...