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Vito Lippolis

Publications and source records attributed to Vito Lippolis.

At least 19 recordsLinked to original sources
PubMed2006

Synthesis, reactivity and structural studies of selenide bridged carboranyl compounds.

Reaction of the lithium salt Li[1-R-1,2-closo-C(2)B(10)H(10)] with selenium under mild conditions, followed by hydrolysis gave the diselenide compound (1-Se-2-R-1,2-closo-C(2)B(10)H(10))(2) in contrast to the well-reported mercapto compounds 1-SH-2-R-1,2-closo-C(2)B(10)H(10) obtained using a similar synthetic procedure. Details for the preparation and X-ray structural characterisation of the new compounds (2-Me-1,2-closo-C(2)B(10)H(10))(2)Se, (1-Se-2-R-1,2-closo-C(2)B(10)H(10))(2) (R = Me, Ph, ) are specified. To further explore the mechanism of the dimerization reaction, the complex [Au(1-Se-2-Me-1,2-closo-C(2)B(10)H(10))(PPh(3))] was synthesized, confirming the existence of the intermediate Li[1-Se-2-R-1,2-closo-C(2)B(10)H(10)] at the early stages of the reaction before selenium oxidation. Theoretical calculations and cyclic voltammetry (CV) studies were carried out to compare the bonding nature of the sulfur and the selenium analog compounds. It was determined that diselenides have a higher tendency to reduce with respect to the disulfides and all chalcogen atoms were found to be positively charged.

Journal Article↗
PubMed2005

[M(R-dmet)2] bis(1,2-dithiolenes): a promising new class intermediate between [M(dmit)2] and [M(R,R'-timdt)2] (M = Ni, Pd, Pt).

We report the first examples of metal dithiolenes belonging to the class [M(R-dmet)(2)] [R-dmet = formally monoreduced N-substituted thiazolidine-2,4,5-trithione; R = Et, M = Ni (1), Pd (2), Pt (3)]. A comparative spectroscopic, electrochemical, and density functional theory theoretical investigation indicates that [M(R-dmet)(2)] complexes show features intermediate between those of the dithiolenes belonging to the previously reported classes [M(R,R'-timdt)(2)] and [M(dmit)(2)] (R,R'-timdt = formally monoreduced N,N'-disubstituted imidazolidine-2,4,5-trithione; dmit = 2-thioxo-1,3-dithiole-4,5-dithiolato). UV-vis-near-IR spectroscopy and cyclic voltammetry/differential pulsed voltammetry measurements performed on 1 and 3 proved that the new dithiolenes are stable as neutral, monoanionic, and bianionic species and feature a near-IR electrochromic absorption falling at about 1000 and 1250 nm for neutral and monoanionic species, respectively.

Journal Article↗
PubMed2005

Encapsulation of metal cations and anions within the cavity of bis(1,4,7-triazacyclononane) receptors.

The synthesis and characterisation of a new bis([9]aneN3) ligand (L4) containing two [9]aneN3 macrocyclic moieties separated by a 2,6-dimethylenepyridine unit is reported. A potentiometric and 1H NMR study in aqueous solution reveals that ligand protonation occurs on the secondary amine groups and does not involve the pyridine nitrogen. The coordination properties toward Cu(II), Zn(II), Cd(II) and Pb(II) were studied by means of potentiometric and UV spectrophotometric measurements. The ligand can form mono- and binuclear complexes in aqueous solution. In the 1 : 1 complexes, the metal is sandwiched between the two [9]aneN3 moieties and the pyridine N-donor is coordinated to the metal, as actually shown by the crystal structure of the compound [ZnL4](NO3)2.CH3NO2. L4 shows a higher binding ability for Cd(II) with respect to Zn(II), probably due to a better fitting of Cd(II) ion inside the cavity generated by the two facing [9]aneN3 units. The formation of binuclear complexes is accompanied by the assembly of OH-bridged M2(OH)x (x = 1-3) clusters inside the cavity defined by the two facing [9]aneN3 units, and pyridine is not involved in metal coordination. A potentiometric and (1)H NMR study on the coordination of halogenide anions by L4 and its structural analogous L3 in which the two [9]aneN3 units are separated by a shorter quinoxaline linkage, shows that bromide is selectively recognised by L4, while chloride is selectively bound by L3. Such a behaviour is discussed in terms of dimensional matching between the spherical anions and the cavities generated by the two [9]aneN3 units of the receptors.

Journal Article↗
PubMed2005

Coordination chemistry of N-aminopropyl pendant arm derivatives of mixed N/S-, and N/S/O-donor macrocycles, and construction of selective fluorimetric chemosensors for heavy metal ions.

The coordination chemistry of the N-aminopropyl pendant arm derivatives (L1c-4c) of the mixed donor macrocyclic ligands [12]aneNS2O, [12]aneNS3, [12]aneN2SO, and [15]aneNS2O2(L1a-4a) towards Cu(II), Zn(II), Cd(II), Hg(II), and Pb(II) in aqueous solution has been investigated. The protonation and stability constants with the aforementioned metal ions were determined potentiometrically and compared, where possible, with those of the unfunctionalised macrocycles. The measured values show that Hg(II) and Cu(II) in water have the highest affinity for all ligands considered, with the N-aminopropyl pendant arm weakly coordinating the metal centres. Crystals suitable for X-ray diffraction analysis were grown for the perchlorate salt (H2L1c)(ClO4)2.dmf, and for the 1 : 1 complexes [Cd(L3a)(NO3)2](1), [Cu(L4a)dmf](ClO4)2(2), [Zn(L1c)(ClO4)]ClO4(3), [Cd(L1c)(NO3)]NO3(4), and [Hg(L2c)](ClO4)2(5). Their structures show the macrocyclic ligands adopting a folded conformation, which for the 12-membered systems can be either [2424] or [3333] depending on the nature of the metal ion. L1c-4c were also functionalised at the primary amino pendant group with different fluorogenic subunits. In particular the N-dansylamidopropyl (Lnd, n= 1-4), and the N-(9-anthracenylmethyl)aminopropyl (Lne, n= 1, 2, 4, ) pendant arm derivatives of L1a-4a were synthesised and their optical responses to the above mentioned metal ions were investigated in MeCN/H2O (4 : 1 v/v) solutions.

Crystallography, X-Ray↗
PubMed2005

DFT calculations, structural and spectroscopic studies on the products formed between IBr and N,N'-dimethylbenzoimidazole-2(3H)-thione and -2(3H)-selone.

The NBO charge distribution calculated at DFT level on the [LEX](+) species [LE=N,N'-dimethylbenzoimidazole-2(3H)-thione (3) and -2(3H)-selone (4)(Scheme 1); X=I, Br] suggests that the most likely products from the reaction 3 of 4 and with IBr are the 10-X-2 charge-transfer (CT) adduct and the 10-Se-3 "T-shaped" hypervalent adduct featuring a linear Br--Se--I system, respectively. This prediction is confirmed by the synthesis, and X-ray diffraction analysis of 3.IBr (I) and 4.I(0.72)Br(1.28)(II). In particular II, is a 10-Se-3 "T-shaped" hypervalent adduct containing an almost linear X--Se--X system [X--Se--X 179.07(3) degrees, X=I(0.36)/Br(0.64)], which is roughly perpendicular to the average plane of the benzoimidazole moiety. The FT-Raman spectra of I and II agree very well with their structural features. In particular, the complexity of the FT-Raman spectrum of II reflects the disorder in the X-ray crystal structure of this compound.

Algorithms↗
PubMed2005

PVC membrane potentiometric sensor based on 5-pyridino-2,8-dithia[9](2,9)-1,10-phenanthroline-phane for selective determination of neodymium(III).

Spectrofluorometric studies on the binding properties of 5-pyridino-2,8-dithia[9](2,9)-1,10-phenanthrolinephane (L) toward La3+, Sm3+, Gd3+, Yb3+, and Nd3+ in methanol solution revealed the occurrence of both 1:1 and 2:1 (ligand/metal) complexation with a stability order of Nd3+ > Yb3+ > Gd3+ > Sm3+ > La3+. Consequently, L was used as a suitable neutral ionophore for the preparation of a novel polymeric membrane-selective electrode for Nd3+ ion. The electrode exhibited a Nernstian response over a wide concentration range (1.0 x 10(-6)-1.0 x 10(-2) M) with a low limit of detection of 7.9 x 10(-7) M. The electrode possesses a fast response time of <5 s and can be used for at least 9 weeks without observing any considerable deviation. The proposed electrode revealed a very good selectivity for Nd3+ over a wide variety of alkali, alkaline earth, transition, and heavy metal ions, including members of the lanthanide family other than Nd3+. The potentiometric response of the electrode is independent of the pH of test solution in the pH range 4.0-6.5. The proposed electrode was successfully applied to the recovery of Nd3+ ion from tap water samples and, also, as an indicator electrode, in potentiometric titration of neodymium(III) ions.

Journal Article↗
PubMed2004

A new pyridine-based 12-membered macrocycle functionalised with different fluorescent subunits; coordination chemistry towards Cu(II), Zn(II), Cd(II), Hg(II), and Pb(II).

The coordination chemistry of the new pyridine-based, N2S2-donating 12-membered macrocycle 2,8-dithia-5-aza-2,6-pyridinophane (L1) towards Cu(II), Zn(II), Cd(II), Hg(II), and Pb(II) has been investigated both in aqueous solution and in the solid state. The protonation constants for L1 and stability constants with the aforementioned metal ions have been determined potentiometrically and compared with those of ligand L2, which contains a N-aminopropyl side arm. The measured values show that Hg(II) in water has the highest affinity for both ligands followed by Cu(II), Cd(II), Pb(II), and Zn(II). For each metal ion considered, 1:1 complexes with L1 have also been isolated in the solid state, those of Cu(II) and Zn(II) having also been characterised by X-ray crystallography. In both complexes L1 adopts a folded conformation and the coordination environments around the two metal centres are very similar: four positions of a distorted octahedral coordination sphere are occupied by the donor atoms of the macrocyclic ligand, and the two mutually cis-positions unoccupied by L1 accommodate monodentate NO3- ligands. The macrocycle L1 has then been functionalised with different fluorogenic subunits. In particular, the N-dansylamidopropyl (L3), N-(9-anthracenyl)methyl (L4), and N-(8-hydroxy-2-quinolinyl)methyl (L5) pendant arm derivatives of L1 have been synthesised and their optical response to the above mentioned metal ions investigated in MeCN/H2O (4:1 v/v) solutions.

Journal Article↗
PubMed2004

Monoreduced [M(R,R'timdt)2]- dithiolenes (M = Ni, Pd, Pt; R,R'timdt = disubstituted imidazolidine-2,4,5-trithione): solid state photoconducting properties in the third optical fiber window.

Electrochemically monoreduced [M(R,R'timdt)(2)](-) dithiolenes, showing unprecedented wavelength selective photoconducting properties in the third optical fiber window (1500-1800 nm), fine-tunable through modifications in the chemical structure, allowed for the fabrication of a test photodetector with a bit rate of about 85 kbit s(-1).

Journal Article↗
PubMed2004

Co-ordination chemistry of amino pendant arm derivatives of 1,4,7-triazacyclononane.

The binding properties of 1,4,7-triazacyclononane ([9]aneN3) to metal cations can be adapted through sequential functionalisation of the secondary amines with aminoethyl or aminopropyl pendant arms to generate ligands with increasing numbers of donor atoms. The new amino functionalised pendant arm derivative of 1,4,7-triazacyclononane ([9]aneN3), L1, has been synthesised and its salt [H2L1]Cl2 characterised by X-ray diffraction. The protonation constants of the ligands L1-L4 having one, two or three aminoethyl or three aminopropyl pendant arms, respectively, on the [9]aneN3 framework, and the thermodynamic stabilities of their mononuclear complexes with CuII and ZnII have been investigated by potentiometric measurements in aqueous solutions. In order to discern the protonation sites of ligands L1-L4, 1H NMR spectroscopic studies were performed in D2O as a function of pH. While the stability constants of the CuII complexes increase on going from L1 to L2 and then decrease on going from L2 to L3 and L4, those for ZnII complexes increase from L1 to L3 and then decrease for L4. The X-ray crystal structures of the complexes [Cu(L1)(Br)]Br, [Zn(L1)(NO3)]NO3, [Cu(L2)](ClO4)2, [Ni(L2)(MeCN)](BF4)2, [Zn(L4)](BF4)2.MeCN and [Mn(L4)](NO3)2.1/2H2O have been determined. In both [Cu(L1)(Br)]Br and [Zn(L1)(NO3)]NO3 the metal ion is five co-ordinate and bound by four N-donors of the macrocyclic ligand and by one of the two counter-anions. The crystal structures of [Cu(L2)](ClO4)2 and [Ni(L2)(MeCN)](BF4)2 show the metal centre in slightly distorted square-based pyramidal and octahedral geometry, respectively, with a MeCN molecule completing the co-ordination sphere around NiII in the latter. In both [Zn(L4)](BF4)2.MeCN and [Mn(L4)](NO3)2.1/2H2O the metal ion is bound by all six N-donors of the macrocyclic ligand in a distorted octahedral geometry. Interestingly, and in agreement with the solution studies and with the marked preference of CuII to assume a square-based pyramidal geometry with these types of ligands, the reaction of L4 with one equivalent of Cu(BF4)2.4H2O in MeOH at room temperature yields a square-based pyramidal five co-ordinate CuII complex [Cu(L6)](BF4)2 where one of the three propylamino pendant arms of the starting ligand has been cleaved to give L6.

Journal Article↗
PubMed2003

Coordination chemistry of a new cofacial binucleating macropolycycle derived from 1,4,7-triazacyclononane.

We have prepared and characterized a new phenol-based compartmental ligand (H(2)L) incorporating 1,4,7-triazacyclononane ([9]aneN(3)), and we have investigated its coordination behavior with Cu(II), Zn(II), Cd(II), and Pb(II). The protonation constants of the ligand and the thermodynamic stabilities of the 1:1 and 2:1 (metal/ligand) complexes with these metal ions have been investigated by means of potentiometric measurements in aqueous solutions. The mononuclear [M(L)] complexes show remarkably high stability suggesting that, along with the large number of nitrogen donors available for metal binding, deprotonated phenolic functions are also involved in binding the metal ion. The mononuclear complexes [M(L)] show a marked tendency to add a second metal ion to afford binuclear species. The formation of complexes [M(2)(H(2)L)](4+) occurs at neutral or slightly acidic pH and is generally followed by metal-assisted deprotonation of the phenolic groups to give [M(2)(HL)](3+) and [M(2)(L)](2+) in weakly basic solutions. The complexation properties of H(2)L have also been investigated in the solid state. Crystals suitable for X-ray structural analysis were obtained for the binuclear complexes [Cu(2)(L)](BF(4))(2).(1)/(2)MeCN (1), [Zn(2)(HL)](ClO(4))(3).(1)/(2)MeCN (2), and [Pb(2)(L)](ClO(4))(2).2MeCN (4). In 1 and 2, the phenolate O-donors do not bridge the two metal centers, which are, therefore, segregated each within an N(5)O-donor compartment. However, in the case of the binuclear complex [Pb(2)(L)](ClO(4))(2).2MeCN (4), the two Pb(II) centers are bridged by the phenolate oxygen atoms with each metal ion sited within an N(5)O(2)-donor compartment of L(2)(-), with a Pb.Pb distance of 3.9427(5) A.

Journal Article↗
PubMed2003

Intramolecular cyclization of 4,7-bis(2-bromoacetyl)-1-thia-4,7-diazacyclononane.

The reaction of 1-thia-4,7-diazacyclononane with bromoacetyl bromide in CHCl(3) affords the unexpected salt 4-(2-bromoacetyl)-8-oxo-1-thionia-4,7-diazabicyclo[5.2.2]undecane bromide, C(10)H(16)BrN(2)O(2)S(+).Br(-). Two units of the salt are linked by S.Br contacts about a crystallographic inversion centre, thus forming dimers that are linked by Br...Br contacts into extended ribbons. S...O contacts between these ribbons generate a two-dimensional sheet.

Journal Article↗
PubMed2003

PVC membrane and coated graphite potentiometric sensors based on Et4todit for selective determination of samarium(III).

Solution studies on the binding properties of 4,5,6,7-tetrathiocino[1,2-b:3,4-b']diimidazolyl-1,3,8,10-tetraethyl-2,9-dithione (Et(4)todit) toward a number of cationic species including some lanthanide ions revealed the occurrence of a selective 1:1 complexation of the ligand with Sm(3+) ion. Consequently, Et(4)todit was used as a suitable neutral ionophore for the preparation of novel polymeric membrane (PME) and coated graphite (CGE) Sm(3+)-selective electrodes. The electrodes exhibit a Nernstian behavior for Sm(3+) ions over wide concentration ranges (1.0 x 10(-5)-1.0 x 10(-1) M for PME and 1.0 x 10(-7)-1.0 x 10(-1) M for CGE) and very low limits of detection (8.0 x 10(-6) M for PME and 1.6 x 10(-8) M for CGE). The proposed potentiometric sensors manifest advantages of relatively fast response, and, most importantly, good selectivities relative to wide variety of other cations, including other lanthanide ions. The selectivity behavior of the proposed Sm(3+)-selective electrodes revealed a great improvement compared to the best previously reported electrode for samarium(III) ion. The potentiometric responses of the electrodes are independent of the pH of the test solution in the pH range 4.0-6.5. The electrodes were successfully applied to the recovery of Sm(3+) ion from tap water samples and also, as an indicator electrode, in potentiometric titration of samarium(III) ions.

Journal Article↗
PubMed2003

Coordination properties of new bis(1,4,7-triazacyclononane) ligands: a highly active dizinc complex in phosphate diester hydrolysis.

The synthesis and characterization of three new bis([9]aneN(3)) ligands, containing respectively 2,2'-bipyridine (L(1)), 1,10-phenanthroline (L(2)), and quinoxaline (L(3)) moieties linking the two macrocyclic units, are reported. Proton binding and Cu(II), Zn(II), Cd(II), and Pb(II) coordination with L(1)-L(3) have been studied by potentiometric titrations and, for L(1) and L(2), by spectrophotometric UV-vis measurements in aqueous solutions. All ligands can give stable mono- and dinuclear complexes. In the case of L(1), trinuclear Cu(II) complexes are also formed. The stability constants and structural features of the formed complexes are strongly affected by the different architecture and binding properties of the spacers bridging the two [9]aneN(3) units. In the case of the L(1) and L(2) mononuclear complexes, the metal is coordinated by the three donors of one [9]aneN(3) moiety; in the [ML(2)](2+) complexes, however, the phenanthroline nitrogens are also involved in metal binding. Finally, in the [ML(3)](2+) complexes both macrocyclic units, at a short distance from each other, can be involved in metal coordination, giving rise to sandwich complexes. In the binuclear complexes each metal ion is generally coordinated by one [9]aneN(3) unit. In L(1), however, the dipyridine nitrogens can also act as a potential binding site for metals. The dinuclear complexes show a marked tendency to form mono-, di-, and, in some cases, trihydroxo species in aqueous solutions. The resulting M-OH functions may behave as nucleophiles in hydrolytic reactions. The hydrolysis rate of bis(p-nitrophenyl)phosphate (BNPP) was measured in aqueous solution at 308.1 K in the presence of the L(2) and L(3) dinuclear Zn(II) complexes. Both the L(2) complexes [Zn(2)L(2)(OH)(2)](2+) and [Zn(2)L(2)(OH)(3)](+) and the L(3) complex [Zn(2)L(3)(OH)(3)](+) promote BNPP hydrolysis. The [Zn(2)L(3)(OH)(3)](+) complex is ca. 2 orders of magnitude more active than the L(2) complexes, due both to the short distance between the metal centers in [Zn(2)L(3)(OH)(3)](+), which could allow a bridging interaction of the phosphate ester, and to the simultaneous presence of single-metal bound nucleophilic Zn-OH functions. These structural features are substantially corroborated by semiempirical PM3 calculations carried out on the mono-, di-, and trihydroxo species of the L(3) dizinc complex.

Journal Article↗
PubMed2003

First example of an infinite polybromide 2D-network.

The reaction of the neutral dithiolene [Pd(Et2timdt)2] (Et2timdt = formally monoreduced diethylimidazolidine-2,4,5-trithione) with an excess of Br2 yielded few crystals of [1(Et) x 2Br](2+)(Br-)2(Br2)3 as a by-product (1(Et) = 4,5,9,10-tetrathiocino-[1,2-b:5,6-b']-1,3,6,8-tetraethyl-diimidazolyl-2,7-dithione); X-ray diffraction analysis showed that this compound represents the first example of a polybromide 2D-network templated by [1(Et) x 2Br](+2) dications, and featuring all the Br-Br distances shorter than those found in solid state bromine.

Journal Article↗
PubMed2003

Helical templating of polyiodide networks at a binuclear metallo complex.

A homobimetallic supramolecular helicate has been prepared from a new multimodal ligand, and used to template the formation of two polyiodide networks, one containing an unprecedented figure-of-eight polyiodide helix, the other dominated by peripheral C-H...I polyiodide chain interactions.

Journal Article↗
PubMed2002

Fluorometric chemosensors. Interaction of toxic heavy metal ions Pb(II), Cd(II), and Hg(II) with novel mixed-donor phenanthroline-containing macrocycles: spectrofluorometric, conductometric, and crystallographic studies.

The macrocycles L(1)-L(3) incorporating N(2)S(3)-, N(2)S(2)O-, and N(2)S(2)-donor sets, respectively, and containing the 1,10-phenanthroline unit interact in acetonitrile solution with heavy metal ions such as Pb(II), Cd(II), and Hg(II) to give 1:1 ML, 1:2 ML(2), and 2:1 M(2)L complex species, which specifically modulate the photochemical properties of the ligands. The stoichiometry of the complex species formed during spectrofluorometric titrations and their formation constants in MeCN at 25 degrees C were determined from fluorescence vs M(II)/L molar ratio data. The complexes [Pb(L(1))][ClO(4)](2).(1)/(2)H(2)O (1), [Pb(L(2))][ClO(4)](2).MeNO(2) (1a), [Pb(L(3))(2)][ClO(4)](2).2MeCN (1b), and [Cd(L(3))][NO(3)](2) (2b) were also characterized by X-ray diffraction studies. The conformation adopted by L(1)-L(3) in these species reveals the aliphatic portion of the rings folded over the plane containing the heteroaromatic moiety with the ligands trying to encapsulate the metal center within their cavity. In 1, 1a, and 2b the metal ion completes the coordination sphere by interacting with counteranion units and solvent molecules. On the contrary, the 1:2 complex 1b shows Pb(II) sandwiched between two symmetry-related molecules of L(3) reaching an overall [4N + 4S] eight-coordination.

Journal Article↗
PubMed2002

An unprecedented example of a cis-phosphonodithioato nickel(II) complex built by an extensive hydrogen bonding supramolecular network.

The P-N bond hydrolysis of the 4-methoxyphenyl-ammonium ethylamido-phosphonodithioato ligand during its complexation to NiII leads to the first example of phosphonodithioato nickel(II) complex having a cis configuration; this complex is stabilised in the solid state by an extensive and intricate network of hydrogen bondings involving the released ethylenediamine and a water molecule.

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