Stefania Tanase

Stefania Tanase
University of Amsterdam | UVA · Van 't Hoff Institute for Molecular Sciences

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111
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3,689
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Additional affiliations
January 2011 - present
University of Bucharest
January 2010 - December 2011
University of Amsterdam
January 2006 - present
Utrecht University

Publications

Publications (111)
Article
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NiO electrodes are widely applied in p-type dye-sensitized solar cells (DSSCs) and photoelectrochemical cells, but due to excessive charge recombination, the efficiencies of these devices are still too low for commercial applications. To understand which factors induce charge recombination, we studied electrodes with a varying number of NiO layers...
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UiO-66 is a benchmark metal-organic framework that holds great promise for the design of new functional materials. In this work, we perform two-dimensional infrared measurements on polycrystalline membranes of UiO-66 grown on c-sapphire substrates. We study the symmetric and antisymmetric stretch vibrations of the carboxylate groups of the terephth...
Article
Considering the discharge of radioactive and non-radioactive effluents during the mining process, we report on a study that proposes to use optical sensing for the detection and monitoring of pollutants.
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Chiral induction is a simple and inexpensive approach to synthesise chiral metal-organic frameworks, even when using achiral building-blocks. The challenge lies in selecting the proper chiral inductor. This can only be achieved upon understanding the mechanism behind the chirality transfer from the chiral guest to the achiral MOF. In this work, the...
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Correction for ‘Role of additives and solvents in the synthesis of chiral isoreticular MOF-74 topologies’ by Andreea Gheorghe et al. , Dalton Trans. , 2021, DOI: 10.1039/D1DT01945G.
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Monitoring CO2 levels in the atmosphere as well as in work place environments is strictly regulated. Curent commercial solid-state polymeric sensors have low operating temperature, yet exhibit low selectivity. Molecular...
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The synthesis of chiral metal–organic frameworks (MOFs) is highly relevant for asymmetric heterogenous catalysis, yet very challenging. Chiral MOFs with MOF‐74 topology were synthesised by using post‐synthetic modification with proline. Vibrational circular dichroism studies demonstrate that proline is the source of chirality. The solvents used in...
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Stefania Tanase and Anastasios J. Tasiopoulos introduce the Molecular Systems Design & Engineering themed collection on molecular systems for sensing.
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Determining accurately the CO2 levels is highly relevant when monitoring the indoor air quality. Nondispersive Infrared (NDIR) sensors are the most often used for measuring carbon dioxide concentration. However, the complexity of the device, the power consumption as well as scalability are the main drawbacks associated with the state-of-the-art dev...
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This review gives an overview of the synthetic strategies used for designing metal-organic frameworks (MOFs) and MOFs-based composites studied for water-alcohol separation applications. It shows that various organic linkers, including flexible, hydrophobic and zwitterionic ligands have been used for the synthesis of MOFs with flexible frameworks, h...
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This study presents a straightforward approach for the in situ polymerization of PNIPAM chains within the 1D pores of the five-coordinated zinc-based metal-organic framework DMOF in order to obtain new MOF-based composites. The loading amount of PNIPAM within DMOFPNIPAM composites can be tuned by changing the initial weight ratio between NIPAM, wh...
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A multiluminescent composite material, CDs@EuW–MOF, is synthesized by self‐assembling molecular building‐blocks in the presence of carbon dots (CDs). Using water soluble CDs within the growth media of a hydrophilic metal‐organic framework (MOF) enables the incorporation of the CDs within MOF pores through a one‐pot synthesis. The emission spectra o...
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This work reports a new approach for the synthesis of a zeolitic imidazolate framework (ZIF-8) composite. It employs the direct growth of the crystalline ZIF-8 on a mixed-metal oxide support TiO2-SiO2 (TSO), which mimics the porous structure of populous nigra. Using the natural leaf as a template, the TSO support was prepared using a sol-gel method...
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Supramolecular isomerism of metal-organic frameworks (MOFs) is known for several MOF structures, having direct implications on the properties of these materials. Although the synthesis of MOF isomers is mainly serendipitous in nature, achieving controlled formation of a target framework is highly relevant for practical applications. This work discu...
Article
A new series of alkaline-earth-metal based coordination polymers were synthesized by using a pyrazine-2,5-dicarboxylic acid (2,5-H2pzdc) ligand under hydrothermal conditions. These compounds show a variety of structural topologies, reflecting the variable coordination geometries of the alkaline-earth ions as well as the key role of the metal precur...
Article
A new series of cyanide-bridged assemblies, {KH[Ln2(2,3-pzdc)2(CH3OH)(H2O)7][M(CN)8]}·5H2O (Ln3+ = Nd, Gd, Tb, Dy; M4+ = Mo, W), was synthesised by self-assembling lanthanide ions and octacyanometallates ions in the presence of pyrazine-2,3- dicarboxylic acid (2,3-H2pzdc). These compounds have a 3D structure in which octagon-like Ln4M4(CN)8 rings a...
Article
Homochiral metal-organic frameworks (HMOFs) are attractive materials for asymmetric catalysis because they have high surface area and uniform active sites. The variety of catalytic applications reported so far indicate that HMOFs catalyse a range of transformations, including cyanosilylation, aldol condensation and hydrogenation reactions. Besides...
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Four novel metal-organic frameworks (MOFs) built from alkaline-earth metal ions and the flexible tetrahedral carboxylate ligand tetrakis[4-(carboxyphenyl)oxamethyl]methane acid (H4L) were synthesized using solvothermal methods. A variety of three-dimensional frameworks were obtained when employing different alkaline earth ions with the formula [Mg2...
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Petrochemical refineries must separate hydrocarbons mixtures on a large scale for the production of fuels and chemicals. Most often, these hydrocarbons are separated by distillation, which is extremely energy-intensive. This high energy cost can be mitigated by developing materials that can enable efficient adsorptive separation. In this critical r...
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Combined photoluminescence and impedance spectroscopy studies show that an europium-based metal-organic framework behaves as a highly effective and reliable humidity sensor, enabling dual-mode humidity detection.
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Light upconversion by triplet–triplet annihilation (TTA-UC) in nanoparticles has received considerable attention for bioimaging and light activation of prodrugs. However, the mechanism of TTA-UC is inherently sensitive for quenching by molecular oxygen. A potential oxygen protection strategy is the coating of TTA-UC nanoparticles with a layer of ox...
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This short critical review outlines the main synthetic strategies used in the designed synthesis of lanthanide-based metal organic frameworks (Ln-MOFs). It explains the impact of the choice of organic linker on the final network topology, and highlights the applications of Ln-MOFs in the catalysis of organic reactions.
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Controlled mixtures of novel Mg-based metal-organic frameworks (MOFs) were prepared, with H(+) or K(+) as counterions. A linear relation was found between synthesis pH and K/H ratio in the resultant mixture, establishing the tunability of the synthesis. Upon pyrolysis, these precursor mixtures yield nitrogen-doped, hierarchically porous carbons, wh...
Article
A ratiometric thermometer based on a mixed-metal Ln(III) metal-organic framework is reported that has good sensitivity in a wide temperature range from 4 to 290 K and a quantum yield of 22% at room temperature. The sensing mechanism in the europium-doped compound Tb0.95Eu0.05HL (H4L = 5-hydroxy-1,2,4-benzenetricarboxylic acid) is based not only on...
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We investigate and discuss the proton conductivity properties of the cyanide-bridged metal–organic framework (MOF) [Nd(mpca)2Nd(H2O)6Mo(CN)8]·nH2O (where mpca is 5-methyl-2-pyrazinecarboxylate). This MOF is one of an exciting class of cyanide-bridged materials that can combine porosity with magnetism, luminescence, and proton conductivity. Specific...
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We present a new coordination polymer, {[VO(pzdc)(H2O)2] H2O}n, built from vanadyl and pyrazine-2,5-dicarboxylate (pzdc) ions. It consists of a one-dimensional chain of vanadyl ions linked by pzdc ions. The carboxylate groups show monodentate coordination, while the pyrazine ring is present both in non-coordinated and coordinated modes. This novel...
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This short critical review outlines possible scenarios for using lignin as a feedstock in a biorefinery environment. We first explain the position of biomass with respect to fossil carbon sources and the possibilities of substituting these in tomorrow's transportation fuels, energy, and chemicals sectors. Of these, the conversion of biomass to chem...
Chapter
We present a selection of metal-organic frameworks based on d–f and f–f linkages, discussing their structural features and properties from experimental and theoretical viewpoints. We give an overview of our own synthetic and modeling methodologies, highlighting the complexity of the interdisciplinary approach developed. Significant experimental and...
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We present a simple method for solubilising lignin using liquid ammonia. Unlike water, which requires harsh conditions, ammonia can solubilise technical lignins, in particular kraft lignin. A commercial pine wood Kraft lignin (Indulin AT) was solubilized instantaneously at room temperature and 7–11 bars auto-geneous pressure, while a commercial mix...
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We present a new metal–organic framework (MOF) built from lanthanum and pyrazine-2,5-dicarboxylate (pyzdc) ions. This MOF, [La(pyzdc)1.5(H2O)2]⋅2 H2O, is microporous, with 1D channels that easily accommodate water molecules. Its framework is highly robust to dehydration/hydration cycles. Unusually for a MOF, it also features a high hydrothermal sta...
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Metal-organic frameworks (MOFs) form a new class of materials with well-defined yet tunable properties. These are crystalline, highly porous and exhibit strong metal-ligand interactions. Importantly, their physical and chemical properties, including pore size, pore structure, acidity, and magnetic and optical characteristics, can be tailored by cho...
Article
Metal-organic frameworks (MOFs) form a new class of materials with well-defined yet tunable properties. These are crystalline, highly porous and exhibit strong metal-ligand interactions. Importantly, their physical and chemical properties, including pore size, pore structure, acidity, and magnetic and optical characteristics, can be tailored by cho...
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Copper on γ-alumina and on mixed magnesia–alumina, Cu/MgO–Al2O3, catalyse the hydrodeoxygenation (HDO) of β-O-4 lignin-type dimers, giving valuable aromatics. The typical selectivity to phenol is as high as 20%. By changing the support's acidity we can modify the dispersion of copper. Interestingly, more HDO occurs with larger copper agglomerates t...
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We report the synthesis and characterization of new V(2)O(5)/Al(2)O(3)-MgO catalysts and their application in oxidative dehydrogenation and epoxidation reactions. The materials were prepared by wet impregnation under excess acid conditions. Anchoring of the desired species on the support occurs via an exchange reaction between the vanadium complex...
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The fabrication of nanoporous poly(vinylidene fluoride) (PVDF) and PVDF/nickel nanocomposites from semicrystalline block copolymer precursors is reported. Polystyrene-block-poly(vinylidene fluoride)-block-polystyrene (PS-b-PVDF-b-PS) is prepared through functional benzoyl peroxide initiated polymerization of VDF, followed by atom transfer radical p...
Article
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New manganese compounds [Mn(HphpzMe)(2)(H(2)phpzMe)(HCO(2))] (1), [Mn(2)(phpzMe)(2)(HphpzMe)(2)(OCH(3))]·2CH(3)OH (2), Na{[Mn(HphpzPh)(phpzPh)(MeOH)(2)](2)}(HCO(2)) (3), [Mn(HphpzPh)(2)(EtOH)(2)]ClO(4)·2EtOH (4) and [Mn(HphpzPh)(2)N(3)] (5) were synthesized and characterized with various techniques. 1, 4 and 5 are mononuclear manganese(III) compoun...
Article
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Sulfated zirconia catalysts obtained by employing chlorosulfuric acid show significantly higher activity in the esterification of fatty acids with different alcohols compared with catalysts made using sulfuric acid. The superior performance results from higher sulfur content, larger pores and stronger acid sites. These catalysts are robust and do n...
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We report the magnetic behavior of the one-dimensional (1D) cyanido-bridged chain complex [Tb(pzam)3(H2O)M(CN)8]·H2O, where M = W(V). The system shows qualitatively similar magnetic behavior with its already reported M = Mo(V): a broad anomaly in the specific heat ascribed to the magnetic interactions, a transition to three-dimensional magnetic ord...
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Reacting Mn(ClO4)2·6H2O and H2phpzEt (H2phpzEt = 5(3)-(2-hydroxyphenyl)-3(5)-ethylpyrazole) in methanol in the presence of sodium hydroxide yields the compound [Mn2(HphpzEt)4(H2O)2](ClO4)2 (1). The pentanuclear [Mn5(μ3-O)2(HphpzEt)3(phpzEt)3(OCH3)(HOCH3)2(O2CPh)] (2) is obtained when performing a similar reaction with Mn(O2CPh)2·2H2O. Compound 1 co...
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We present evidence of 1D S=1/2 anisotropic XY ferromagnetism in the paramagnetic phase of the cyanido-bridged chain complex [Tb(pzam)3(H2O)M(CN)8]H2O, with M=W(V), based upon the measurement of the specific heat, the uniform susceptibility and the magnetization curve on a powder sample. Both the specific heat and the susceptibility exhibit a trans...
Article
The synthesis and characterization of two Fe-Gd systems based on bpca(-) (Hbpca = bis(2-pyridilcarbonyl)amine) as bridging ligand is presented, taking the systems as a case study for structure-property correlations. Compound 1, [Fe(LS)(II)(μ-bpca)(2)Gd(NO(3))(2)(H(2)O)]NO(3)·2CH(3)NO(2), is a zigzag polymer, incorporating the diamagnetic low spin F...
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We report a building blocks approach providing a direct route to multifunctional MOFs, that display photoluminescent properties, robustness, porosity and in some cases unique magnetic properties. The self-assembly of [Mo(CN)8]4− with several in situ prepared lanthanide building blocks gives 3D robust porous networks with open channels. This approac...
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We present and develop alternative catalysts for biomass conversion and specifically lignin conversion into aromatics. Unlike the conventional CoMo and NiMo formulations, our catalysts can convert low-sulfur feedstocks. A set of five magnesia–alumina mixed oxides were screened in the hydrodealkylation of alkyl phenyl ethers as lignin model compound...
Article
Magnetic properties of new d-f cyanido-bridged 1D assemblies [RE(pzam)(3)(H(2)O)W(CN)(8)]·H(2)O (RE(III) = Gd, 1, Tb, 2, Dy, 3; pzam = pyrazine-2-carboxamide) were studied by temperature- and field-dependent magnetization measurements. No evidence for 3D interchain magnetic ordering is found above 2 K. Multiconfiguration ab initio calculations and...
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Two new d-f cyanido-bridged 1D assemblies [RE(pzam)(3)(H(2)O)Mo(CN)(8)]·H(2)O (RE = Sm(III), Er(III)) were synthesized and their magneto-structural properties have been studied by field-dependent magnetization and specific heat measurements at low temperatures (≥0.3 K). Below ≈ 10 K the ground state of both the Sm(III) and Er(III) ions is found to...
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We report the structural and functional features of two new catalysts: a mononuclear [Fe(N5mpy)(CH3CN)](BF4)2 (N5mpy=(N,N′E,N,N′E)-N,N′-(pyridine-2,6-diylbis(ethan-1-yl-1-ylidene))bis(1-(pyridin-2-yl)methanamine)) complex and a binuclear {[Fe(N5mpy)]2O}(BF4)4 complex. Both compounds catalyze the oxidation of alkanes by H2O2, in MeCN or acetone to y...
Article
The synthesis of transition-metal and rare-earth clusters has become a very active research field, mainly because these compounds can behave as molecule-based magnets. The formation of such compounds strongly depends on the choice of the bridging ligand. This review covers the progress made by pyrazole-based ligands in the formation of new transiti...
Article
Rare-earth(III) complexes of the general formula [RE{(Hsal)3tren}2](CF3SO3)3·nCH3CN, where RE is Eu (1), Gd (2), and Tb (3), and (Hsal)3tren is tris[2-(salicylideneimino)ethyl]amine, have been synthesized and structurally characterized. X-ray crystallographic studies show that the rare-earth(III) center is coordinated by six oxygen atoms that belon...
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Three high-nuclearity manganese(III) clusters have been synthesized and characterized: [Mn₈(μ₄-O)₄(phpzH)₈(thf)₄] (1), [Mn₈(μ₄-O)₄(phpzH)₄(EtOH)₄]·2EtOH (2), and [Mn₆(μ₃-O)₄(μ₃-Br)₂(HphpzEt)₆(phpzEt)] (3). Compounds 1 and 2 contain a [Mn₈(μ₄-O₄)(phpzH)₈] core in which antiferromagnetic interactions between the manganese(III) ions are found. Compoun...
Article
A new oxide-centered trinuclear manganese(III) compound with the formula [Mn3(μ3-O)(naphpz)3(O2CMe)(MeOH)2]n (1) {H2naphpz = 2-[1H-pyrazol-5(3)-yl]naphthalen-1-ol} has been synthesized and characterized. Three bulky doubly deprotonated phenol-pyrazole ligands are coordinated to the three manganese(III) ions with a μ3-oxide bridge in the same plane....
Article
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The reaction of H2phpzR (R = Me, Ph; H2phpzMe = 3(5)-(2-hydroxyphenyl)-5(3)-methylpyrazole and H2phpzPh = 3(5)-(2-hydroxyphenyl)-5(3)-phenylpyrazole) with Mn(O2CR').nH2O (R' = Me and Ph) and (nBu4N)MnO4 in ethanol (EtOH) affords three new manganese(III) compounds, [Mn3(mu3-O)(phpzMe)3(O2CMe)(EtOH)].EtOH (1), (nBu4N)[Mn3(mu3-O)(phpzMe)3(O2CPh)2] (2)...
Article
A combination of density functional theory (DFT) calculations and Mössbauer spectroscopy has been used to determine that the magnetic easy-axis is coincident with its crystallographic c-axis in [Fe(pca)(2)(py)(2)] x py, where pac is the 2-pyrazinecarboxylate ligand. This easy-axis bisects the approximately axial O-Fe-O coordination axes of molecule...
Article
A new fluorescent platinum(II) compound containing the N,N'-bis-(anthracen-9-ylmethyl)propane-1,3-diamine as a carrier ligand has been designed, synthesized and characterized. High cytotoxic activity of cis-[Pt(bapda)Cl2] is observed in A2780 and A2780R cells (human ovarian carcinoma sensitive and cisplatin-resistant, respectively). Nevertheless, c...
Article
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The synthesis, crystal structure, and magnetic properties of three new manganese(III) clusters are reported, [Mn 3 (µ 3-O)(phpzH) 3 (MeOH) 3 (OAc)] (1), [Mn 3 (µ 3-O)(phpzMe) 3 (MeOH) 3 (OAc)] · 1.5MeOH (2), and [Mn 3 (µ 3-O)(phpzH) 3 (MeOH) 4-(N 3)] · MeOH (3) (H 2 phpzH) 3(5)-(2-hydroxyphenyl)-pyrazole and H 2 phpzMe) 3(5)-(2-hydroxyphenyl)-5(3)-...
Article
New mononuclear compounds of the ligand 1-(2-hydroxyphenyl)-3-phenylpropane-1,3-dione (H2L) with Cu(II) and several lanthanoid(III) ions, where Ln(III)=Pr, Nd, Eu, Gd, have been synthesized and characterized by spectroscopic methods and X-ray crystal structure determinations. In all compounds, the ligand coordinates in a bidentate chelating manner,...
Article
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Reaction of H2phpzR (R = H, Me, Ph; H2phpzH = 3(5)-(2-hydroxyphenyl)pyrazole, H2phpzMe = 3(5)-(2-hydroxyphenyl)-5(3)-methylpyrazole, and H2phpzPh = 3(5)-(2-hydroxyphenyl)-5(3)-phenylpyrazole)) with MnCl2·2H2O or MnBr2·4H2O in an acetonitrile−methanol mixture and in the presence of a small quantity of triethylamine affords the compounds [Mn(HphpzR)2...
Article
A highly asymmetric Ni(II) cluster [Ni(4)(OH)(OMe)(3)(Hphpz)(4)(MeOH)(3)](MeOH) (1) (H(2)phpz=3-methyl-5-(2-hydroxyphenyl)pyrazole) has been prepared and its structure determined by means of single-crystal X-ray diffraction by using synchrotron radiation. Variable-temperature bulk-magnetization measurements show that the complex exhibits intramolec...
Article
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The new d–f cyanido-bridged 1D assembly [Nd(pzam)3(H2O)Mo(CN)8]·H2O was prepared by self-assembly of pyrazine-2-carboxamide (pzam), Nd(NO3)·nH2O and (Bu3NH)3[Mo(CN)8]·4H2O in acetonitrile. X-ray crystallographic studies indicate that the complex comprises chains of alternating, cyanido-bridged [Nd(pzam)3(H2O)]3+ and Mo(CN)8]3− fragments. The magnet...
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Antiferromagnetic superexchange: Two new 1D ferrimagnetic chains [Gd(pzam)3(H2O)M(CN)8]⋅H2O (MV=Mo 1, W 2) are synthesized and characterized; magnetic susceptibility data indicate antiferromagnetic superexchange between GdIII and MV via the cyanido bridge, and the occurrence of long-range magnetic ordering between chains at Tc≈0.7 K in 1 (see figur...
Article
The synthesis, crystal structure, and magnetic properties of three new manganese(III) clusters are reported, [Mn 3(mu 3-O)(phpzH) 3(MeOH) 3(OAc)] (1), [Mn 3(mu 3-O)(phpzMe) 3(MeOH) 3(OAc)].1.5MeOH (2), and [Mn 3(mu 3-O)(phpzH) 3(MeOH) 4(N 3)].MeOH (3) (H 2phpzH = 3(5)-(2-hydroxyphenyl)-pyrazole and H 2phpzMe = 3(5)-(2-hydroxyphenyl)-5(3)-methylpyra...
Article
The reaction of the ligand 1,4-bis(pyridine-2-carboxamido)butane (L) with RECl3 afforded complexes of general formula [RE(L)1.5Cl2(CH3OH)]Cl·nS (RE = Pr, Nd, Eu, Tb; n = 4, S = H2O; n = 5, S = CH3OH). The structural determination reveals that complexes [RE(L)1.5Cl2(CH3OH)]Cl·5CH3OH (RE = Nd 2b, Eu 3b) are isomorphous, crystallizing in the monoclini...
Article
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The reactivity towards H(2)O(2) of the complexes [Fe(pca)(2)(py)(2)].py (1) and Na(2){[Fe(pca(3))](2)O}.2H(2)O.CH(3)CN (2) (where pca(-) is pyrazine-2-carboxylate) and their catalytic activity in the oxidation of hydrocarbons is reported. Addition of H(2)O(2) to 1 results in the formation of a dinuclear Fe(III)-(mu-O)-Fe(III) species characterized...
Article
A novel linear bis(chlorido)-bridged Cu(II) compound with the ligand 7-azaindole (abbreviated as Haza) have been synthesized and fully characterized by spectroscopy, EPR and X-ray structure analysis. The geometry around the Cu(II) ion in the compound [Cu–μ-Cl2(Haza)2]n, is distorted octahedral with the basal plane formed by two chloride anions with...
Article
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In conclusion, we have prepared and structurally characterized the first TbIII–MoV quasi-1D cyanido-bridged complex, which consists of ferromagnetic TbIII–MoV chains that become 3D magnetically ordered below Tc=1.0 K. From magnetization and specific heat data, we find a ferromagnetic intrachain interaction J/kB=3.6 K between the MoV and TbIII magne...
Article
New complexes with 5(3)-(2-hydroxyphenyl)-3(5)-methylpyrazole (H2phpz), [Co2(H2phpz)(Hphpz)2(phpz)2]·3CH3CN (1), [Ni(Hphpz)2] (2) and [Cu(Hphpz)2] (3), were synthesized and structurally characterized. The ligand coordinates in the form of 3-(2-hydroxyphenyl)-5-methylpyrazole in all cases, except for one ligand in the CoIII complex, where it coordin...
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A linear trinuclear copper(II) complex containing phenoxido- and alkoxido-bridges between the metal centers has been isolated and structurally characterized. The complex cation consists of a linear array of three copper ions, assembled by means of two doubly deprotonated ligands. The octahedral coordination sphere of the two peripheral copper(II) i...
Article
Iron complexes of two ligands, HphoxCOOH and HphoxiPr, have been synthesized and characterized by crystal structure analyses. The complexes (HNEt3)2[Fe(phoxCOO)2](ClO4) and [Fe(phoxiPr)3] are reported. Reactions of the ligands rac-HphoxCOOH and rac- HphoxiPr with iron(II) or iron(III) perchlorate result in the formation of iron(III) complexes with...