Patrizia Rossi

University of Florence, Florens, Tuscany, Italy

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Publications (88)222.31 Total impact

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    ABSTRACT: The N,N′-bis[(3-hydroxy-4-pyron-2-yl)methyl]-N,N′-dimethylethylendiamine (Malten=L) forms the highly stable [CuH−2L] species in water, in which the converging maltol oxygen atoms form an electron-rich area able to host hard metal ions. When considering the alkaline earth series (AE), the [Cu(H−2L)] species binds all metal ions, with the exception of Mg2+, exhibiting the relevant property to discriminate Ca2+ versus Mg2+ at physiological pH 7.4; the binding of the AE metal is visible to the naked eye. The stability constant values of the trinuclear [AE{Cu(H−2L)}2]2+ species formed reach the maximum for Ca2+ (log K=7.7). Ca2+ also forms a tetranuclear [Ca{Cu(H−2L)}]24+ species at a high Ca2+ concentration. Tri- and tetranuclear calcium complexes show blue- and pink-colored crystals, respectively. [Cu(H−2L)] is the most active species in inducing DNA alterations. The DNA damages are compatible with its hydrolytic cleavages.
    Chemistry 07/2014; · 5.93 Impact Factor
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    ABSTRACT: Ligand L (2,6-bis{[7-(7-nitrobenzo[1,2,5]oxadiazole-4-yl)-3,10-dimethyl-1,4,7,10-tetraazacyclododeca-1-yl]methyl}phenol) is a fluorescent sensor that is useful for detecting Cu(II), Zn(II), and Cd(II). Some of the complexes formed are able to sense the presence of halides in solution. L passes through the cellular membrane, becoming fluorescent inside cells. The H-1L(-) species is able to form dinuclear complexes with [M2H-1L](3+) stoichiometry with Cu(II), Zn(II), and Cd(II) ions, experiencing a CHEF effect upon metal coordination in an acetonitrile/water 95:5 (v/v) solution. In all three of the complexes investigated, the metal cations are coordinatively unsaturated and can therefore bind secondary ligands as anionic species. The crystal structure of [Cd2(H-1L)Cl2](ClO4)·4H2O is discussed. The Zn(II) complex behaves as an OFF-ON sensor for fluoride and chloride anions.
    Inorganic Chemistry 04/2014; · 4.59 Impact Factor
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    ABSTRACT: A combined X-ray diffraction (XRD), solid state nuclear magnetic resonance (SSNMR), differential scanning calorimetry (DSC), and modeling approach has been applied to study the solid–solid transition of ibuprofen sodium salt between the hydrated racemic compound (RS-H) and the anhydrous conglomerate (RS-A). For comparison, the dihydrate → anhydrous transformation of the sodium salt of the pure S-enantiomer of ibuprofen was also investigated by means of SSNMR and DSC. All the solid state studies indicate that the RS-H → RS-A transition is fully reversible under different experimental conditions [temperature, pressure (ambient and vacuum), and type of atmosphere (N2, air, and static dry by P2O5)]. The static and dynamic disorder affecting the isobutyl fragment in RS-H, already observed by SSNMR, has been further investigated by single crystal XRD and computational techniques. On these grounds, a model for the dihydrate → anhydrous solid–solid transformations is proposed.
    Crystal Growth & Design 04/2014; 14(5):2441–2452. · 4.69 Impact Factor
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    ABSTRACT: The effect of the catalyst structure on the stereoselectivity of CO/vinyl arene copolymerization has been studied with the aim of developing catalytic systems able to improve the yields while maintaining the high degree of copolymer isotacticity previously obtained using achiral nitrogen ligands. Aryl α-diimine ligands having extended aromatic rings (Ar)2DABMe2, with Ar = 1-C10H7 (e), 1-C14H9 (f), 9-C14H9 (g), have been synthesized, and α-diimine coordination to cationic methylpalladium complexes has been investigated in solution, by means of NMR spectroscopy, and in the solid state for [Pd(Me)(NCMe)((9-C14H9)2DABMe2)][PF6] (2g). The performance of these catalysts in CO/vinyl arene copolymerization, under mild conditions, was analyzed in terms of productivity and degree of stereoregularity of the resulting polyketones. In comparison with previous results, a remarkable enhancement in the yield of isotactic copolymer was observed using the new achiral 9-anthryl α-diimine ligand g, confirming that the ortho disubstitution and the extended aromatic rings play key roles in obtaining good stereoselectivity and good productivity. To perform a structural analysis of the first steps of the CO/p-methylstyrene copolymerization, complex [Pd(Me)(CO)((9-C14H9)2DABMe2)][BAr′4] (3g) was used as a starting point: NMR investigation reveals the stereoselective formation of the olefin/CO/olefin insertion product (6g), which prevalently exists in solution in only one diastereoisomeric form, thus justifying the observed high polymer isotacticity.
    Organometallics 01/2014; 33:129-144. · 4.15 Impact Factor
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    ABSTRACT: In the title chiral sulfinic acid ester, C18H26O4S, the cyclo-hexane ring of the menthyl fragment adopts a chair conformation. The mol-ecular shape is defined by the dihedral angle of 47.87 (8)° between the mean planes of the cyclo-hexane and benzene rings. In the crystal, mol-ecules related by the screw axis are connected into chains along [010] by weak Car-H⋯O=S contacts.
    Acta Crystallographica Section E Structure Reports Online 05/2013; 69(Pt 5):o731. · 0.35 Impact Factor
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    ABSTRACT: The binding properties of the two ligands (L) N,N'-bis[(3-hydroxy-4-pyron-2-yl)methyl]-N,N'-dimethylethylendiamine (Malten) and 4,10-bis[(3-hydroxy-4-pyron-2-yl)methyl]-1,7-dimethyl-1,4,7,10-tetraazacyclododecane (Maltonis) towards M(ii) transition metal ions (M(ii) = Cu(ii) for Malten and Co(ii) for Maltonis, respectively), were investigated in aqueous solution. Each compound contains two 3-hydroxy-2-methyl-4-pyrone units (Maltol) symmetrically spaced by a different polyamine fragment. The formation of only mononuclear complexes was detected and the main species present in a wide range of pH is the neutral [M(ii)(H-2L)] complex. This is able to stabilize one hard M(iii) metal ion such as Gd(iii) and Y(iii), giving rise to the formation of new hetero-trinuclear complexes of M(ii)-M(iii)-M(ii) sequence. The trinuclear species having the formula {M(iii)[M(ii)(H-2L)]2}3+ (M(ii) = Cu(ii) and M(iii) = Y(iii) or Gd(iii) for Malten and M(ii) = Co(ii) and M(iii) = Gd(iii) for Maltonis) are also formed in a wide range of pH, including pH = 7 and can be isolated in high yield as a perchlorate salt. The crystal structures of all the studied hetero-trinuclear species highlight that such systems are formed thanks to the synergy between the different stereochemical requirement of the transition metal (Cu(ii) or Co(ii)) and the different donor atoms set of the ligands which preorganize the maltol units for the binding of the hard M(iii) metal, otherwise difficult to bind in water, through L/M(ii)/M(iii) self-assembling. The magnetic properties of the hetero-trinuclear spin systems were investigated; in the M(ii)-Gd(iii)-M(ii) species, Gd(iii) interacts with the two 3d ions of this class of compounds by similar coupling mechanism.
    Dalton Transactions 03/2013; · 3.81 Impact Factor
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    ABSTRACT: The complex, Mn(hfa)2•tmeda [(H-hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentandione, tmeda = N,N,N′,N′-tetramethylethylendiamine)], is synthesized in a single-step reaction and characterized by elemental analysis, thermal analysis, and infrared (IR) spectroscopy. The solid-state crystal structure of Mn(hfa)2•tmeda provides evidence of a mononuclear structure. The thermal analyses show that the complex is thermally stable and can be evaporated to leave less than 2% residue. The complex properties are compared with the first generation, commercially available MnII and MnIII precursors, Mn(acac)2 (Hacac = acetylacetone) and Mn(tmhd)3 (Htmhd = 2,2,6,6-tetramethyl-3,5-heptanedione), respectively. Mn(hfa)2•tmeda represents the first example of manganese(II) precursor that can be used in the liquid phase without decomposition, thus providing constant evaporation rates, even for long deposition times. It is successfully applied to the reduced-pressure, metal-organic (MO)CVD of the Mn3O4 phase.
    Chemical Vapor Deposition 03/2013; 19(1‐3). · 1.32 Impact Factor
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    ABSTRACT: The binding properties of 4,10-bis[(3-hydroxy-4-pyron-2-yl)methyl]-1,7-dimethyl-1,4,7,10-tetraazacyclododecane () and 4,10-bis[(2-hydroxy-5-nitrophenyl)methyl]-1,7-dimethyl-1,4,7,10-tetraazacyclododecane () towards Cu(ii) and Co(ii) transition metal ions in aqueous solution and in the solid state were studied and compared. Each system consists of a cyclen scaffold bearing two different side-arms; the role of the two transition metal ions to involve side-arms in coordination was investigated. Each metal ion is coordinated in a similar way by both ligands although a different side-arm arrangement occurs. The Me(2)Cyclen base is always involved in the coordination of the transition metal cation with the four amine functions; both side-arms bind Co(ii) while only one of them binds Cu(ii). As a consequence, Co(ii) forms only mononuclear species with both ligands; the main [Co(H(-2)L)] species exhibits both side-arms on the same part with respect to the macrocyclic plane. In the case of , this allows the formation of an electron rich area, formed by the four converging oxygen atoms of the two maltol functions, able to lodge one hard metal ion such as sodium. On the other hand, forms a dinuclear Cu(ii)-species using the remaining unbound maltolic function which affords a Cu(ii)-tetranuclear species in the solid state. This behavior is attributed to the different coordination requirements of the two metals, thus providing information for the choice of a suitable metal to preorganize side-arms on a polyamine macrocyclic scaffold. Potentiometric and UV-Vis solution studies as well as four crystal structures of metal-complexes support this conclusion.
    Dalton Transactions 12/2012; · 3.81 Impact Factor
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    ABSTRACT: In the title hydrated salt, CHNO·6ClO ·1.5HO, the asymmetric unit consists of a hexa-protonated [H ] cation, five perchlorate anions in general positions, two on twofold rotation axes (one of which is disordered), and two water mol-ecules of crystallization in general positions, one of them disordered around a twofold crystallographic axis. In the [H ] cation, two strong intra-molecular N-H⋯N hydrogen bonds occur, involving the N atoms of the oxadiazole ring as acceptors and the closest NH groups of each dipropyl-enetriamine unit. In the crystal, the [H ] cations form channels along the axis direction, in which the perchlorate counter-ions and the water mol-ecules are lodged. The crystal packing features a network of N-H⋯O and O-H⋯O hydrogen bonds involving the NH groups of the [H ] cation, the perchlorate anions and the water mol-ecules.
    Acta Crystallographica Section E Structure Reports Online 12/2012; 68(Pt 12):o3453-4. · 0.35 Impact Factor
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    ABSTRACT: In the title compound, CHBrClNOS, the sulfonamide group adopts a staggered conformation about the N-S bond [the C-S-N-H torsion angle is 97 (3)°] with the N-atom lone pair bis-ecting the O=S=O angle. For the C(Ar)-S bond, the -substituted C atom bis-ects one of O=S-N angles [the C-C-S-N torsion angle is -57.7 (3)°]. The mean planes of the aromatic rings form a dihedral angle of 75.1 (1)°. In the crystal, mol-ecules form inversion dimers through pairs of N-H⋯NH hydrogen bonds. The mol-ecules are further consolidated into layers along the plane by weaker N-H⋯O inter-actions.
    Acta Crystallographica Section E Structure Reports Online 12/2012; 68(Pt 12):o3308-9. · 0.35 Impact Factor
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    ABSTRACT: In the title hydrated salt, C36H66N8O6+·6ClO4−·1.5H2O, the asymmetric unit consists of a hexa­protonated [H6L]6+ cation, five perchlorate anions in general positions, two on twofold rotation axes (one of which is disordered), and two water mol­ecules of crystallization in general positions, one of them disordered around a twofold crystallographic axis. In the [H6L]6+ cation, two strong intra­molecular N—H⋯N hydrogen bonds occur, involving the N atoms of the oxadiazole ring as acceptors and the closest NH+ groups of each dipropyl­enetriamine unit. In the crystal, the [H6L]6+ cations form channels along the a-axis direction, in which the perchlorate counter-ions and the water mol­ecules are lodged. The crystal packing features a network of N—H⋯O and O—H⋯O hydrogen bonds involving the NH+ groups of the [H6L]6+ cation, the perchlorate anions and the water mol­ecules.
    Acta Crystallographica Section E Structure Reports Online 11/2012; 68(12). · 0.35 Impact Factor
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    ABSTRACT: The asymmetric unit of the title compound, C(18)H(22)N(2)O(3)S, contains two mol-ecules, exhibiting similar conformations [C-S-N-C torsion angles of -82.2 (2) and -70.4 (2)°, and dihedral angles between the mean planes of the aromatic rings of 56.6 (6) and 51.6 (6)° in mol-ecules I and II, respectively]. However, the two independent mol-ecules show distinctly different hydrogen-bonding patterns. In the crystal, molecules I form inversion dimers via pairs of N-H⋯O hydrogen bonds, whereas for molecules II the N-H⋯O hydrogen bond is intramolecular. The hydrogen-bonded dimers of I further propagate along the b-axis direction through π-π inter-actions [the distance between ring centroids is 3.8424 (8) Å].
    Acta Crystallographica Section E Structure Reports Online 11/2012; 68(Pt 11):o3144-5. · 0.35 Impact Factor
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    ABSTRACT: The title compound (C(16)H(22)N(2)O(6))[PtCl(4)]·2H(2)O, shows anti-proliferative activity in eight tumor cell lines. The asymmetric unit consists of one solvent water mol-ecule on a general position, and one half of each of the polyammonium cation and the tetrachloridoplatinate(II) anion, both of them located on centers of inversion. In the crystal, the cations are connected via hydrogen bonding between the carbonyl O atoms and the hydroxyl H atoms into zigzag chains that elongate in the c-axis direction. In addition, the carbonyl O atom is hydrogen-bonded to the water mol-ecule which, in turn, inter-acts with the [PtCl(4)](2-) anion. Finally, the chains are linked by N-H(+)⋯Cl inter-actions into a three-dimensional network.
    Acta Crystallographica Section E Structure Reports Online 11/2012; 68(Pt 11):m1323-4. · 0.35 Impact Factor
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    ABSTRACT: In the title compound, C(17)H(18)N(2)S, the thia-zepine ring adopts a boat conformation and the dihedral angle between the benzene rings is 75.92 (5)°, resulting in a butterfly-like conformation. In the crystal, mol-ecules are connected via weak C(aromatic)-H⋯N contacts involving the imine N atom as acceptor and through a quite short C-H⋯π inter-action. The resulting mol-ecular chains propagate along the c-axis direction.
    Acta Crystallographica Section E Structure Reports Online 11/2012; 68(Pt 11):o3133-4. · 0.35 Impact Factor
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    ABSTRACT: The iminodiphosphine 2-(PPh(2))C(6)H(4)-1-CH[double bond, length as m-dash]NC(6)H(4)-2-(PPh(2)) (P-N-P') is used for the preparation of the complexes [Pd(η(1)-CHR(1)-CH[double bond, length as m-dash]CR(2)R(3))(P-N-P')]BF(4) [R(1) = R(2) = R(3) = H: (); R(1) = R(2) = Ph, R(3) = H: (); R(1) = R(3) = H, R(2) = Ph: (); R(1) = H, R(2) = R(3) = Me: ()]. The P-N-P' tridentate coordination and the η(1)-allyl bonding mode in the solid are confirmed by the X-ray structural analysis of . In solution, the complexes and undergo an η(1)-η(3)-η(1) rearrangement at 298 K interconverting the bonding site of the allyl group. A five-coordinate structure with the phosphine ligands in the axial position is proposed for the η(3)-allyl intermediate. For the dynamic process, a ΔG(≠) value of 53.8 kJ mol(-1) is obtained from (1)H NMR data of . In and , the allyl ligand is rigidly bound to the metal through the less substituted terminus, in line with the higher free energy content of the corresponding isomers: [Pd(η(1)-CHPh-CH[double bond, length as m-dash]CH(2))(P-N-P')](+) +48.78 kJ mol(-1); [Pd(η(1)-CMe(2)-CH[double bond, length as m-dash]CH(2))(P-N-P')](+) +69.35 kJ mol(-1). The complexes react with secondary amines in the presence of fumaronitrile at different rates yielding allylamines and the palladium(0) derivative [Pd(η(2)-fn)(P-N-P')] (). On the basis of charge distribution on the allylic carbon atoms and of steric factors, the difference in rate and the regioselectivity in the amination of are better rationalized by a mechanism with nucleophilic attack at the η(3)-intermediate rather than by an S(N)2 mechanism with nucleophilic attack at the Pd-CHR(1) carbon atom. The high regioselectivity in the reaction of with piperidine implies an S(N)2' mechanism with nucleophilic attack at the CMe(2) allyl carbon. A dynamic process occurs also for the 18-electron complex consisting in a dissociation-association equilibrium of the olefin.
    Dalton Transactions 09/2012; 41(40):12490-500. · 3.81 Impact Factor
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    ABSTRACT: The N,N'-bis[(3-hydroxy-4-pyron-2-yl)methyl]-N,N'-dimethylethylendiamine (malten) and 4,10-bis[(3-hydroxy-4-pyron-2-yl)methyl]-1,7-dimethyl-1,4,7,10-tetraazacyclododecane (maltonis) were synthesized and characterized. The acid-base behavior, structural characterizations, and biochemical studies in aqueous solution were reported. Each compound contains two 3-hydroxy-2-methyl-4-pyrone units (maltol) symmetrically spaced by a polyamine fragment, the 1,4-dimethylethylendiamine (malten), or the 1,7-dimethyl-1,4,7,10-tetraazacyclododecane (maltonis). They are present at physiological pH 7.4 in the form of differently charged species: neutral but in a zwitterion form for malten and monopositive with an internal separation of charges for maltonis. Malten and maltonis are both able to alter the chromatin structure inducing the covalent binding of genomic DNA with proteins, a feature consistent with the known antiproliferative activity exerted by this class of molecules. Solid-state results and MD simulations in water show that malten, because of its molecular topology, should be more prone than maltonis to act as a donor of H-bonds in intermolecular contacts, thus it should give a better noncovalent approach with the negatively charged DNA. Crystal structures of [H(2)malten](2+) and [H(2)maltonis](2+) cations were also reported.
    The Journal of Organic Chemistry 03/2012; 77(5):2207-18. · 4.56 Impact Factor
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    ABSTRACT: MnF2 nanorod assemblies in a pompon-like fashion were synthesized by using a new complex, Mn(hfa)2·tmeda [(Hhfa = 1,1,1,5,5,5-hexafluoro-2,4-pentandione, tmeda = N,N,N′,N′-tetramethylethylenediamine)]. The complex was synthesized in a single-step reaction, and single-crystal X-ray diffraction studies provide evidence of a mononuclear structure. The thermal analyses have shown that the complex is thermally stable and can be evaporated to leave less than 2 % residue at atmospheric pressure. On the basis of its thermal properties, it has been successfully applied to the atmospheric pressure metalorganic chemical vapor deposition (AP-MOCVD) of MnF2 nanostructures
    European Journal of Inorganic Chemistry 03/2012; · 3.12 Impact Factor
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    ABSTRACT: Ligand L (4-(7-nitrobenzo[1,2,5]oxadiazole-4-yl)-1,7-dimethyl-1,4,7,10-tetra-azacyclododecane) is a versatile fluorescent sensor useful for Cu(II), Zn(II) and Cd(II) metal detection, as a building block of fluorescent metallo-receptor for halide detection, and as an organelle marker inside live cells. Ligand L undergoes a chelation-enhanced fluorescence (CHEF) effect upon metal coordination in acetonitrile solution. In all three complexes investigated the metal cation is coordinatively unsaturated; thus, it can bind secondary ligands as anionic species. The crystal structure of [ZnLCl](ClO(4)) is discussed. Cu(II) and Zn(II) complexes are quenched upon halide interaction, whereas the [CdL](2+) species behaves as an OFF-ON sensor for halide anions in acetonitrile solution. The mechanism of the fluorescence response in the presence of the anion depends on the nature of the metal ion employed and has been studied by spectroscopic methods, such as NMR spectroscopy, UV/Vis and fluorescence techniques and by computational methods. Subcellular localization experiments performed on HeLa cells show that L mainly localizes in spot-like structures in a polarized portion of the cytosol that is occupied by the Golgi apparatus to give a green fluorescence signal.
    Chemistry 02/2012; 18(14):4274-84. · 5.93 Impact Factor
  • Chemistry: a European Journal. 01/2012;
  • The Journal of Organic Chemistry 01/2012; · 4.56 Impact Factor

Publication Stats

202 Citations
222.31 Total Impact Points

Institutions

  • 1998–2014
    • University of Florence
      • • Dipartimento di Chimica "Ugo Schiff"
      • • Dipartimento di Ingegneria Industriale
      Florens, Tuscany, Italy
  • 2010–2012
    • University of Rome Tor Vergata
      • Dipartimento di Scinze e Tecnologie Chimiche
      Roma, Latium, Italy
  • 2000–2012
    • Università degli Studi di Urbino "Carlo Bo"
      • Department of Biomolecular Science
      Urbino, The Marches, Italy
  • 2002–2010
    • University of Catania
      • Department of Chemical Sciences
      Catania, Sicily, Italy