Francesco Demartin

University of Milan, Milano, Lombardy, Italy

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Publications (263)527.39 Total impact

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    Plinius. 09/2014; 40:170.
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    ABSTRACT: In the context of the development of new electron mediators for Dye-Sensitized Solar Cells that could efficiently substitute the more common I3-/I- redox couple, we have prepared a series of Cu(I)- phenanthroline complexes through an easy synthetic route. The novel [Cu(2-mesityl-4,7-dimethyl-1,10-phenanthroline)2]PF6 (3) is of particular interest because the presence of the bulky mesityl groups protects as a kiss lock the Cu center, leading to superior dye regeneration kinetics with respect to simpler phenanthroline based Cu(I) complexes and to a lower dark current with respect the I3-/I- . The exploitation of a dual-component electrolyte constituted by (3) and a Fe(II) co-mediator, in combination with the [Ru(4,4'-dicarboxy-2,2'-bipyridine)2(4,4'-dinonyl-2,2'-bipyridine)](PF6)2 sensitizer, allowed to increase the performance of the cell reaching Jsc values of 4.0 mA cm-2, comparable to that recorded with I3-/I- (3.8 mA cm-2).
    ACS Applied Materials & Interfaces 07/2014; · 5.01 Impact Factor
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    GMT2014, Tavagnasco, 6 and 7 Juin 2014, Tavagnasco, Piedmont, Italy; 06/2014
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    ABSTRACT: The new mineral parascandolaite, isotypic to cubic perovskites, space group Pm overline{3} m (no. 221) is the natural analog of the synthetic fluoride KMgF3 and is related to neighborite, NaMgF3. It was found as a volcanic sublimate at Vesuvius volcano on 1944 eruption lava scoria, associated with opal, cerussite, mimetite, phoenicochroite and coulsellite. It occurs as transparent colorless to white cubic crystals up to 0.5 mm in length with vitreous luster. The density measured by flotation in a diiodomethane-toluene mixture is 3.11(1) g/cm3; that calculated from the empirical formula and single-crystal X-ray data is 3.123 g/cm3. The mineral is isotropic with n = 1.395(5) (580 nm). The six strongest reflections in the X-ray powder diffraction pattern are: [d obs in Å(I)(h k l)] 2.001(100)(2 0 0), 2.831(83)(1 1 0), 2.311(78)(1 1 1), 1.415(56)(2 2 0), 1.633(35)(2 1 1) and 1.206(22)(3 1 1). The unit-cell parameter is a = 4.0032(9) Å. The structure was refined to a final R(F) = 0.0149 for 35 independent observed reflections [I > 2σ(I)]. The mineral is named after the Italian mineralogist Antonio Parascandola (1902-1977).
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    ABSTRACT: The new mineral therasiaite, ideally (NH4)3KNa2Fe2+Fe3+(SO4)3Cl5, was found in a medium-temperature (∼250°C) intracrater active fumarole at La Fossa crater, Vulcano, Aeolian Islands, Sicily, Italy. It occurs on a pyroclastic breccia as brown to dark brown equant to short prismatic crystals up to 0.1 mm in length, in association with salammoniac, kremersite and adranosite. The mineral is monoclinic, space group: Cc (no. 9) with a = 18.284(4), b = 12.073(2), c = 9.535(2) Å, b = 108.10(3)°, V = 2000.6(7) Å3 and Z = 4. The six strongest reflections in the X-ray powder diffraction pattern are: [d obs in Å (I)(h k l)] 2.812(100)(223), 2.664(77)(513), 3.297(28)(331), 3.208(14)(512), 3.008(12)(040), 2.942(11)(331). The empirical formula (based on 17 anions per formula unit (p.f.u.)) is (NH4)2.68K1.32Na2.04Fe1.76Al0.12Mn0.12S2.98O11.95Cl5.05. The measured density is 2.41(1) g cm–3, d calc = 2.395 g cm–3. The mineral is biaxial (–) with α = 1.585(3) β = 1.615(3) and γ = 1.630(3) (white light). Using single-crystal diffraction data, the structure was refined to a final R(F) = 0.0240 for 5574 independent observed reflections [I > 2σ(I)]. The structure of therasiaite displays a novel topology and contains two independent, distorted octahedral Fe sites, with the Fe atoms in oxidation state 3+ and 2+, respectively, each surrounded by three Cl atoms and three oxygens of the sulfate ions. The Fe octahedra and the three independent sulfate anions are connected to form chains running along [001]. Voids between the chains are occupied by three independent ammonium ions (partially replaced by K+), one K+ and two Na+ ions. The formula resulting from the structure refinement is [(NH4)2.25K0.75]KNa2Fe2(SO4)3Cl5.
    Mineralogical Magazine 01/2014; 78(1). · 2.21 Impact Factor
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    ABSTRACT: The reactions of 1,3,8,10-tetrakis(4'-fluorophenyl)-4,5,6,7-tetrathiocino[1,2-b:3,4-b']diimidazolyl-2,9-dithione (4) and molecular diiodine afforded spoke adducts with stoichiometries 4⋅I2 and 4⋅3I2 , isolated in the compound 4⋅3I2 ⋅xCH2 Cl2 ⋅(1-x)I2 (x=0.70), and characterized by single-crystal XRD and FT-Raman spectroscopy. The nature of the reaction products was investigated under the prism of theoretical calculations carried out at the DFT level. The structural data, FT-Raman spectroscopy, and quantum mechanical calculations agree in indicating that the introduction of fluorophenyl substituents results in a lowering of the Lewis basicity of this class of bis(thiocarbonyl) donors compared with alkyl-substituted tetrathiocino donors and fluorine allows for extended interactions that are responsible for solid-state crystal packing.
    Chemistry - An Asian Journal 09/2013; · 4.57 Impact Factor
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    ABSTRACT: The trinuclear [Ln(NO3)3(CuL)2] complexes (Ln = La, Ce, Sm, Eu and Er, L = N,N'-1,3-propylen-bis(salicylideniminato) have been investigated by a combination of HLS and EFISH techniques to evaluate both the dipolar and octupolar contributions to their significant quadratic hyperpolarizability and to confirm that f electrons may tune their second-order NLO response. In the complexes investigated, the major contribution to the total quadratic hyperpolarizability is largely controlled by the octupolar contribution, but the values of both βEFISH and ∥β(J=1)∥, that is the dipolar part, are significantly influenced by the number of f electrons, confirming that the unexpected polarizable character of f electrons may be the origin of such fascinating evidence.
    Inorganic Chemistry 06/2013; · 4.59 Impact Factor
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    ABSTRACT: A chemodosimeter Ph2P(S)NP(–S–CH2–anthracene)Ph2 (L1), featuring the methylanthracenyl moiety covalently linked to one of the two S atoms of an S,S′-tetraphenyldithioimidodiphosphinate (L) unit exhibited good selectivity and sensitivity for Hg2+ in an aqueous environment. The chemical reaction involved differs from those reported in the literature for other Hg2+ chemodosimeters: the binding of Hg2+ induces the cleavage of the PS–CH2 bond to form the stable neutral complex [HgL2] and an emissive anthracenyl derivative. The X-ray crystal structure of L1 is reported (CCDC number 919620).
    RSC Advances 06/2013; · 3.71 Impact Factor
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    ABSTRACT: The 1D coordination polymers [Cu2(syn,syn-g1:g1:l-RCOO)4(anti,anti-g1:g1:l-RCOO)(Et3NH)]n, R =Me (1) and H (2), and the dimer [Cu2(syn,syn-g1:g1:l-PhCOO)4(anti-g1-PhCOO)2(Et3NH)2] (3) are formed by reaction of copper carboxylates with the corresponding carboxylic acid and NEt3. Moreover, the compound [Cu2(syn,syn-g1:g1:l-MeCOO)4(anti-g1-MeCOO)2(Et2NH2)2] (4) can be obtained with the use of NHEt2. The crystal structures of 1�CH3CN and 2 comprise linear anionic 1D chains of paddle-wheel copper carboxylates [Cu2(RCOO)4], bridged together by anti,anti-g1:g1:l acetato or formato ions. The negative charges are balanced by hydrogen-bonded triethylammonium countercations, and in compound 1 acetonitrile molecules are hosted in the voids between the chains. In compounds 3 and 4, two anti-g1-benzoato or -acetato anions occupy the apical positions of the paddle-wheel dimers [Cu2(RCOO)4], with Et3NH+ or Et2NH2 + cations balancing the negative charges, without the formation of coordination polymer chains. In compound 4, the dimeric units are held together in a 1D network by hydrogen bonds between the apical carboxylates and the diethylammonium cations. In order to evaluate the effect of the simultaneous presence of syn,syn- and anti,anti-g1:g1:l acetato ions on the Cu–Cu magnetic communication, the magnetic susceptibility of 1 has been measured. Data were fitted to a model based on an alternating chain of copper dimers based on the Heisenberg–Zeeman Hamiltonian (�2J Sˆ 1�Sˆ 2 convention). The results show the presence of a strong antiferromagnetic coupling within the dimer 2J1 = �(310.8 ± 0.1) cm�1 and a weak antiferromagnetic coupling between dimers 2J2 = �(25 ± 1) cm�1. The latter coupling is significant since its introduction in the fit model leads to a well-behaved error surface and to a �35% decrease of the sum of squared residuals. The electron paramagnetic resonance (EPR) spectra of powder sample of 1 have been recorded between 5 and 295 K, and they are typical of the triplet state of an antiferromagnetic copper dimer (zero field splitting |D| = 0.34 cm�1).
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    Mineralogical Magazine 01/2013; 2013(77). · 2.21 Impact Factor
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    Campostrini I., Demartin F., Russo M.
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    ABSTRACT: As a part of the scientific agreement between the Dipartimento di Chimica - Università degli Studi di Milano and the Osservatorio Vesuviano (Napoli), the content of the bottles belonging to the historical collection of the Osservatorio, most of them collected before the 1944 eruption, was examined. The study allowed to identify several new phases, among which the recently described d’ansite-(Mn). In samples collected by A. Malladra in 1920, leonardsenite, MgAlF5(H2O)2, was identified. The mineral occurs as minute colorless prismatic crystals, wit maximum size of about 100 microns. The identification was obtained by single-crystal X-ray diffraction. The unit-cell data are: a 7.083(3); b 10.155(4); c 6.816(3) Å. This is the second discovery in the world.
    Micro. 01/2013; 3/2013(11):135-141.
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    ABSTRACT: Ekanite, Ca2ThSi8O20, was found for the first time at the Monte Somma in fragments of a sanidinic project in the early 90s at San Vito quarry (Ercolano, Naples, Italy) in three light green bipyramidal crystals (with a maximum size of about 0.3 mm) associated with sanidine, “amphibole”, anorthite and scarce “mica”. The identification was obtained with a preliminary SEM-EDS analysis and confirmed by determination of the parameters of the elementary cell (I422): a 7.462 (5), b 15.047 (11) Å.
    Micro. 01/2013; 3/2013(11):142-144.
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    ABSTRACT: The reactions of 4,5,6,7-tetrathiocino-[1,2-b:3,4-b']-1,3,8,10-tetrasubstituted-diimidazolyl-2,9-dithiones (R(2) ,R'(2) -todit; 1: R=R'=Et; 2: R=R'=Ph; 3: R=Et, R'=Ph) with Br(2) exclusively afforded 1:1 and 1:2 "T-shaped" adducts, as established by FT-Raman spectroscopy and single-crystal X-ray diffraction in the case of complex 1⋅2 Br(2) . On the other hand, the reactions of compounds 1-3 with molecular I(2) provided charge-transfer (CT) "spoke" adducts, among which the solvated species 3⋅2 I(2) ⋅(1-x)I(2) ⋅x CH(2) Cl(2) (x=0.94) and (3)(2) ⋅7 I(2) ⋅x CH(2) Cl(2,) (x=0.66) were structurally characterized. The nature of all of the reaction products was elucidated based on elemental analysis and FT-Raman spectroscopy and supported by theoretical calculations at the DFT level.
    Chemistry - An Asian Journal 12/2012; · 4.57 Impact Factor
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    ABSTRACT: Elemental gold powder is easily oxidised under mild reaction conditions with 1 : 1 I(2)-adducts of the thioamides 3-methyl-benzothiazole-2-thione (mbtt) and 1-methyl-1H-benzimidazole-2(3H)-thione (mbit) with separation of the ionic complexes [Au(I)(mbtt)(2)]I(3) () and [(mtbiH)(2)](AuI(4))I(3) () [mtbiH = the imido protonated form of 2-(methylthio)benzimidazole] (gold oxidation yield >78% and 45%, respectively). The X-ray crystal structure of shows the Au(i) centre linearly bound by two neutral ligands via the sulphur atom, whereas the X-ray crystal structure of shows the Au(iii) centre surrounded by four iodides in a square-planar arrangement. The oxidising/complexing properties of the mbtt·I(2) and mbit·I(2) adducts were interpreted considering the S-donor to I(2) interaction that leads to a charge separation between the I(b) and I(t) iodine atoms in the fragment S-I(b)-I(t). The oxidation of gold in a non-aqueous solvent by thioamide-I(2) adducts could be a promising alternative process to the numerous hydrometallurgical ones for the recovery of gold from secondary sources.
    Dalton Transactions 10/2012; · 3.81 Impact Factor
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    ABSTRACT: The X-ray structures of 4-amidiniumpyridine acetate, (1·H)AcO, and of cis-[Pt(1) 2 (PPh 3) 2 ](NO 3) 2 (2), as well as their IR spectra, reveal intramolecular hydrogen bonding, which held together the cations and the anions. The IR spectroscopic data suggest that this may be so also in cis-[PtCl(1)(PPh3)2](BF4) (3). In (1·H)AcO and in 2 extensive intermolecular hydrogen bonding networks span through the whole crystals.
    Zeitschrift für anorganische Chemie 10/2012; 638(14). · 1.16 Impact Factor
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    ABSTRACT: Cu(II) complexes with 1,10-orthophenanthroline (phen) show cytotoxic and antitumoral effects. To enhance and exploit these features, we studied complexes containing one or two phen units together with N,N'-substituted-imidazolidine-2-thione (L). We synthesized and structurally characterized the precursor molecule Cu(phen)(OH(2))(2)(OClO(3))(2), and determined the complex formation constants of [Cu(phen)(L)](2+). We studied the cytotoxic activity of [Cu(phen)(2)(L)](ClO(4))(2) versus human hematologic (CCRF-CEM and CCRF-SB) and solid tumor-derived cell lines (K-MES-1, DU-145). The cytotoxic activities, in the 1-3 μM range, show that our Cu(II)-complexes possess comparable inhibitory activities against both leukemia and carcinoma cells, unlike the majority of antineoplastic agents, usually more potent against hematologic cancer cells than against solid tumor cells. Because the free Cu(II) ion is reduced by glutathione (GSH), we studied the reactivity of our complexes with GSH, providing evidence that no redox reaction occurred under the chosen experimental conditions. Complex formation equilibria were present, studied by spectrophotometric titrations. The redox properties of the prepared compounds were also investigated by cyclic voltammetry, confirming that the mixed Cu(II) complexes were resistant to reduction.
    Journal of inorganic biochemistry 05/2012; 114:28-37. · 3.25 Impact Factor
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    ABSTRACT: [PtL(6)X] {X = Cl or NCS and L(6) = 5-mesityl-1,3-di(2-pyridyl)-benzene} display similar luminescence in solution but, in the solid state, the packing of the molecules is different, with short PtPt interactions for X = NCS, leading to a red-shifted emission band. The effect has been used to generate OLEDs that emit squarely in the NIR region (855 nm).
    Chemical Communications 02/2012; 48(26):3182-4. · 6.38 Impact Factor
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    ABSTRACT: The new mineral sarrabusite Pb(5)CuCl(4)(SeO(3))(4) has been discovered in the Sardinian mine of Baccu Locci, near Villaputzu. It occurs as small lemon-yellow spherical aggregates of tabular crystals (< 10 µm) of less than 100 µm in diameter. The crystal structure has been solved from and refined against electron diffraction of a microcrystal. Data sets have been measured by both a manual and an automated version of the new electron-diffraction tomography technique combined with the precession of the electron beam. The sarrabusite structure is monoclinic and consists of (010) layers of straight chains formed by alternating edge-sharing CuO(4)Cl(2) and PbO(8) polyhedra parallel to the c axis, which share corners laterally with two zigzag corner-sharing chains of PbO(6)Cl(2) and PbO(4)Cl(4) bicapped trigonal prisms. These blocks are linked together by SeO(3)(2-) flat-pyramidal groups.
    Acta crystallographica. Section B, Structural science 02/2012; 68(Pt 1):15-23. · 1.80 Impact Factor
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    ABSTRACT: The possibility of constructing extended networks based on NH+N charge-assisted hydrogen bonding and NI interactions was explored. The organic modules 3,5-di-(3-pyridyl)-1,2,4-thiadiazole (L1) and 3,5-di-(4-pyridyl)-1,2,4-thiadiazole (L2) possess two pyridyl groups, allowing them to act both as hydrogen-bond acceptors and hydrogen-bond donors with H+ acting as the main linker between the molecular units. The crystal structure of the ionic compounds (HL1)I3, (HL1)I5, (HL1)IBr2, (HL2)I3, and (HL2)IBr2 are described; the position of the nitrogen atoms in the outwards pyridyl rings in L1 and L2 leads to the formation of 1D helices of interacting cations (HL1)+ and zig-zag chains of interacting cations (HL2)+. In the case of (HL1)I5, cationic helices of (HL1)+ and helices of I5− take place in a highly shape-complementary arrangement. The crystal structure of the bis-adduct L1·2I2 features the presence of intermolecular iodine–iodine long contacts to form infinite I2 chains. A comparative structural analysis carried out using the XPac procedure identifies three common molecular arrangements and confirms the importance of directional interactions and molecular shape of the target molecules in directing the packing preferences of this family of structures.
    CrystEngComm 01/2012; 14(18):5809-5823. · 3.88 Impact Factor
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    ABSTRACT: The new minerals d’ansite-(Mn), Na21Mn2+(SO4)10Cl3, and d’ansite-(Fe), Na21Fe2+(SO4)10Cl3, occur as encrustations in fumaroles at Vesuvius, Naples, Italy and La Fossa crater, Vulcano, Aeolian Islands, Italy, respectively. Both minerals are cubic and crystallize in space group I4¯ 3d. D’ansite-(Mn) forms colourless translucent tristetrahedral crystals up to 0.2 mm on edge; d’ansite-(Fe) forms aggregates of colourless to white complex isometric crystals of about the same size. Chemical analyses obtained by energy-dispersive spectrometry on an electron microprobe gave the following mean compositions: d’ansite-(Mn), Na2O 39.37, MnO 3.46, MgO 0.13, SO3 49.99, Cl 6.36, O=Cl �1.44, total 97.87 wt.%, c o r r e s p o n d i n g t o a n e m p i r i c a l f o r m u l a , on t h e ba s i s o f 43 a n i o n s , of Na20.61(Mn2+ 0.79Mg0.05)S0.84S10.13O40.09Cl2.91; and d’ansite-(Fe), Na2O 39.12, FeO 4.18, MgO 0.12, SO3 49.91, Cl 6.81, O=Cl �1.54, total 98.60 wt.%, corresponding to an empirical formula of Na20.42(Fe2+ 0.94Mg0.05)S0.99S10.08O39.89Cl3.11. The six strongest reflections in the X-ray powder diffraction pattern of d’ansite-(Fe) [listed as dobs(A˚) (I) (hkl)] are as follows: 2.807(100)(044), 2.570(37)(235), 1.714(29)(129), 3.384(27)(233), 3.113(26)(134), 2.108(15)(237). The unit-cell parameters obtained from single-crystal data are 15.9291(9) and 15.882(3) A ˚ for d’ansite-(Mn) and d’ansite-(Fe), respectively. The structure of both minerals was refined, using single-crystal diffraction data, to final R parameters of 0.0309 and 0.0336 on reflections with I > 2s(I). The structure contains three independent Na sites, one of which is partially occupied by Mn2+ or Fe2+, two independent sulfate anions and one chlorine site.
    Mineralogical Magazine 01/2012; 76(7):2773-2783. · 2.21 Impact Factor

Publication Stats

524 Citations
527.39 Total Impact Points


  • 1984–2014
    • University of Milan
      • • Department of Chemistry, Biochemistry and Biotechnologies for Medical Sciences
      • • Department of Inorganic, Organometallic and Analytical Chemistry "Lamberto Malatesta" CIMA
      • • Department of Organic and Industrial Chemistry
      Milano, Lombardy, Italy
  • 1998–2010
    • Università degli studi di Cagliari
      • Department of Chemical and Geological Science
      Cagliari, Sardinia, Italy
  • 2008
    • Royal Ontario Museum
      Toronto, Ontario, Canada
  • 1997–2003
    • Università degli Studi del Sannio
      Benevento, Campania, Italy
  • 1988–2001
    • University of Bologna
      • • "Giacomo Ciamician" Department of Chemistry CHIM
      • • "Toso Montanari" Department of Industrial Chemistry CHIMIND
      Bologna, Emilia-Romagna, Italy
  • 2000
    • Università degli Studi di Sassari
      • Dipartimento di Chimica e Farmacia
      Sassari, Sardinia, Italy