Mauro Maestri

University of Groningen, Groningen, Groningen, Netherlands

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Publications (113)280.31 Total impact

  • 08/2011: pages 181 - 226; , ISBN: 9783527634408
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    ABSTRACT: We have synthesized two cyclam-cored dendrimers appended with dendrons of two different types by proper protection/deprotection of the cyclam unit. The resulting dendrimers contain six naphthyl and two dansyl units (N6 D2) or two dansyl and six naphthyl units (N2 D6) at the periphery. Their photophysical properties have been compared to those of a dendrimer containing 8 dansyl units (D8) and a previously investigated dendrimer containing 8 naphthyl units (N8). The absorption spectra are those expected on the basis of the number of chromophores, demonstrating that no ground state interaction takes place. The emission spectra of N2 D6 and N6 D2 show naphthalene localized and naphthalene excimer emission similar to those observed in the case of N8, together with a much stronger dansyl emission with maximum at 525 nm. Addition of CF(3)SO(3)H to dendrimer solutions in CH(3)CN/CH(2)Cl(2) 1:1 (v/v) leads to protonation of the aliphatic amine units of the cyclam core at first and then of the aromatic amine of each dansyl chromophores. Cyclam can be diprotonated and this affects dansyl absorption and, most significantly, emission bands by a charge perturbation effect. Each dansyl unit is independently protonated in both dendrimers. The most interesting photophysical feature of these heterofunctionalized cyclam-cored dendrimers is the occurrence of an intradendrimer photoinduced energy transfer from naphthyl to dansyl chromophores of two different dendrons (interdendron mechanism). The efficiency of this process is 50 % for N6 D2 and it can be increased up to 75 % upon protonation of the cyclam core and formation of N6 D2(2H(+)). This arises from the fact that protonation of the amine units of the cyclam prevents formation of exciplexes upon naphthyl excitation, thus shutting down one of the deactivation processes of the fluorescent naphthyl excited state.
    Chemistry - An Asian Journal 08/2010; 5(8):1884-95. · 4.57 Impact Factor
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    ABSTRACT: The excited state proton transfer (ESPT) observed in the compounds 4-methyl-7-hydroxyflavylium and 4′,7-dihydroxyflavylium is described, and the results are quantitatively interpreted on the basis of the Weller approach. ESPT is especially efficient in the case of 4-methyl-7-hydroxyflavylium. For pH>2, proton recombination in the excited state does not occur and the yield of the adiabatic formation of excited base (A*) through the excited acid (AH+*) is 0.93. This result compares with 0.45 for 4′,7-dihydroxyflavylium under identical conditions. The use of adiabatic proton transfer to obtain the inversion of the population of the excited state is discussed.
    ChemInform 01/2010; 30(10).
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    ABSTRACT: Three dendrimers consisting of a dimethoxybenzil core and branches that contain two (G0), four (G1), and eight (G2) naphthalene units at the periphery and zero (G0), two (G1), and six (G2) dimethoxybenzene units in the branches have been synthesized and their photophysical, photochemical, and electrochemical properties have been investigated. For comparison purposes, the properties of dimethoxybenzil (MB) and of a dendron containing four naphthalene and three dimethoxybenzene units (D2) have also been studied. The properties of the dendrimers in the ground state (absorption spectra and electrochemical behavior) are those expected for their noninteracting component units. The excited state properties, however, are substantially controlled by electronic interactions between the dimethoxybenzil core and the naphthalene units contained in the branches. In dichloromethane-chloroform 1 : 1 (v/v) solution at 298 K, energy transfer from the lowest excited state (S-1) of the naphthalene units to the lower lying S-1 excited state of the dimethoxybenzil core takes place with high efficiency. In a rigid matrix at 77 K, selective excitation of the dimethoxybenzil chromophore yields an emission band that exhibits a spectral evolution: in the millisecond time scale it shows a spectral pro. le very similar to the dimethoxybenzil phosphorescence, whereas in the second time scale it is very similar to the naphthalene-type phosphorescence. Energy transfer from the T-1 excited state of the dimethoxybenzil core to the T-1 excited state of the naphthalene units takes place at 77 K, but not at 298 K, because the T-1 excited state of the dimethoxybenzil core moves to energy lower than that of the naphthalene chromophore. The photochemical results show that the dimethoxybenzil core maintains its intrinsic photoreactivity toward dioxygen, and that on increasing dendrimer generation a photoreaction between core and branches predominates.
    New Journal of Chemistry 07/2007; 31(7):1250-1258. · 2.97 Impact Factor
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    ABSTRACT: The complex network of chemical reactions of the compound 6-hydroxyflavylium perchlorate was studied by different techniques including UV-vis absorption spectrophotometry, stopped-flow, electrochemistry, and photochemistry. The network is characterized by the formation of a very reactive zwitterionic base as well as by p-quinoidal chalcones. The trans-chalcone is metastable in very acidic solutions and exhibits reversible redox reactions, allowing to introduce for the first time in the flavylium network an electrochemical input.
    Photochemical and Photobiological Sciences 04/2007; 6(4):372-80. · 2.92 Impact Factor
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    ABSTRACT: We report the photophysical properties (absorption and emission spectra, quantum yield, and lifetime) of five dendrimers of first generation based on a TREN (tris(2-aminoethyl)amine) skeleton functionalized at the periphery with naphthyl and/or 5-dimethylamino-1-naphthalenesulfonamide (hereafter called dansyl) chromophores. Each dendrimer comprises one tertiary amine unit in the core and three branches carrying a sulfonimido unit at the periphery, each one substituted by two identical or different moieties. In particular, TD6 and TN6 contain dansyl (D) or naphthyl (N) units, respectively, while TD3B3, TN3B3 and TN3D3 contain dansyl, naphthyl or benzyl (B) units at the periphery. The spectroscopic behaviour of these dendrimers has been investigated in acetonitrile solution and compared with that of reference compounds. For all dendrimers the absorption bands are red shifted compared to those of monomeric naphthyl and dansyl reference compounds. Moreover, the intense naphthyl and dansyl fluorescence is greatly quenched because of strong interactions between the two aromatic moieties linked by a sulfonimido unit. Protonation of the amine units of the dendrimers by addition of CF(3)SO(3)H (triflic) acid causes a decrease in intensity of the luminescence and a change in the shape of the emission bands. The shapes of the titration curves depend on the dendrimer, but in any case the effect of acid can be fully reversed by successive addition of base (tributylamine). The obtained results reveal that among the intradendrimer interactions the most important one is that taking place (via mesomeric interaction) between the various chromophores and a pair of sulfonimido groups.
    Photochemical and Photobiological Sciences 04/2007; 6(4):471-9. · 2.92 Impact Factor
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    ABSTRACT: We have investigated the photophysical properties of two dendrimers containing a cyclam core decorated with 4 naphthyl units (GO), 12 dimethoxybenzene and 16 naphthyl units (G2). These dendrimers show fluorescence bands that can be assigned to naphthyl localized excited states (lambda(max) = 337 nm), naphthyl-amine exciplexes (lambda(max) = 470 nm) and, for G2, naphthyl excimers (lambda(max) ca. 400 nm). Cyclam is a very good ligand for transition metal ions and we have investigated complex formation between these dendritic ligands and Ni(II), Co(II) and Cu(II), added as nitrate salts. This process can be monitored by the strong changes, both in shape and intensity, observed in the emission spectra of these dendrimers. Complexation with Cu(II) causes not only changes in the relative intensities of the fluorescence bands, but also the appearance of a new absorption band in the near UV spectral region. An analysis of the titration curves has allowed us to obtain clear evidence for the formation of not only 1:1 species, but also 1:2 metal to ligand species. G2 shows a clear preference, compared to GO, in forming complexes with a 1:2 metal-to-ligand stoichiometry, although it possesses very bulky dendrons appended to the cyclam central unit. (c) 2006 Elsevier B.V. All rights reserved.
    Inorganica Chimica Acta. 02/2007; 360(3):1043-1051.
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    ABSTRACT: We have investigated the photophysical properties of two metal complexes, [M(tpy-py)2][PF6]2, where tpy-py = 4′-(4-pyridyl)-2,2′:6′,2″-terpyridine and M = Ru(II) or Os(II), in acetonitrile and aqueous solutions at room temperature. Because the 4-pyridyl unit on the 4′-position of each tpy ligand contains a basic nitrogen atom, both of these compounds can exist in three different protonation states. We observed that the absorption and luminescence spectra of these compounds vary on changing the pH, because the protonation of the pendant pyridine unit makes it an electron acceptor by lowering the energy of its π∗ orbital. We employed the absorption and luminescence spectral changes to study the acid–base reactions for these complexes, and found that the two protonation stages exhibit different pKa values both in the electronic ground state and in the lowest (emitting) excited state. The absorption spectra and luminescence spectra and lifetimes of the deprotonated, mono-protonated and bis-protonated forms were also determined. While the absorption spectra of the variously protonated forms of both compounds can be intepreted in terms of a linear combination of two different and independent chromophores, namely M(tpy-py) and M(tpy-pyH+), the corresponding luminescence spectra exhibit a more complex behaviour, suggesting that the coupling between the two ligands in the lowest excited state is not negligible. Interestingly, at a low pH the luminescence of the Ru complex is switched on, whereas that of the Os complex is strongly quenched upon protonation of the pendant pyridine units. These compounds are of interest because they exhibit a luminescent signal in the red or far red spectral region that can be switched on or off by protons in solution. Hence, they could find applications as luminescent pH sensors and as molecular switches where a low-energy emission signal can be controlled by a chemical acid–base stimulation.
    Inorganica Chimica Acta. 02/2007; 360(3):1102–1110.
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    ABSTRACT: Phosphino-amino-thiazolines and -thiazoles can exist in solution in two tautomeric forms, in which the N-H proton involves the endo-cyclic or exo-cyclic nitrogen atom. The two tautomers show different reactivities toward alcoholysis; the imino form degrades more rapidly. Their bischelated platinum complexes were studied in the solid state by single crystal X-ray diffraction. Thus, the unique stereoelectronic features of the [Pt(PN(th))] (PN(th)=diphenylposphino-aminothiazoline) moiety were revealed. The complex cis-[Pt(PN(th))(2)] reacts with gold(I) salts to yield dimetallic compounds, the molecular structures of which have been determined by X-ray diffraction. Solid cis-[Pt(PN(th))(2)] shows vapoluminescent properties if exposed to alcohol vapors. A combined photophysical and crystallographic investigation has been carried out to clarify the unprecedented rigidochromic role of the alcohol in this phenomenon.
    Chemistry 02/2007; 13(36):10117-28. · 5.83 Impact Factor
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    ABSTRACT: Suitably designed molecular and supramolecular species are capable of combining light and chemical inputs to perform functions that mimic those of macroscopic devices. This paper describes the working principles of molecular-level photochemionic devices for i) chemical switching of photonic inputloutput signals, ii) chemical tuning of photonic inputloutput signals, and iii) the transformation of chemical and/or optical signals for logic operation.
    Advanced Functional Materials 01/2007; 17(5):740-750. · 9.77 Impact Factor
  • 01/2007: pages 1 - 68; , ISBN: 9780470133484
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    ABSTRACT: The network of chemical reactions of the compound 4′-methoxyflavylium was studied in the presence of SDS micelles, using stopped-flow, UV–vis absorption and flash photolysis techniques. The results were compared with analogous experiments carried out in water. The large stabilization of the flavylium cation onto the micelles was proven to be due to an increase in the rate of the dehydration reaction, rather than a decrease of the hydration reaction; the cis–trans isomerisation of the chalcone was not affected by the micelles. It is shown that SDS micelles can be considered as an external stimulus capable of changing the system from one state to another.
    Journal of Photochemistry and Photobiology A: Chemistry. 01/2007; 185:383-390.
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    ABSTRACT: We have synthesized a dendrimer (1) consisting of a 1,4,8,11-tetraazacyclotetradecane (cyclam) core, appended with four benzyl substituents that carry, in the 3- and 5-positions, a dansyl amide derivative (of type 2), in which the amide hydrogen is replaced by a benzyl unit that carries an oligoethylene glycol chain in the 3- and 5-positions. All together, the dendrimer contains 16 potentially luminescent moieties (eight dansyl- and eight dimethoxybenzene-type units) and three distinct types of multivalent sites that, in principle, can be protonated or coordinated to metal ions (the cyclam nitrogen atoms, the amine moieties of the eight dansyl units, and the 16 oligoethylene glycol chains). We have studied the absorption and luminescence properties of 1, 2, and 3 in acetonitrile and the changes taking place upon titration with acid and a variety of divalent (Co2+, Ni2+, Cu2+, Zn2+), and trivalent (Nd3+, Eu3+, Gd3+) metal ions as triflate and/or nitrate salts. The results obtained show that: 1) double protonation of the cyclam ring takes place before protonation of the dansyl units; 2) the oligoethylene glycol chains do not interfere with protonation of the cyclam core and the dansyl units in the ground state, but affect the luminescence of the protonated dansyl units; 3) the first equivalent of metal ion is coordinated by the cyclam core; 4) the interaction of the resulting cyclam complex with the appended dansyl units depends on the nature of the metal ion; 5) coordination of metal ions by the dansyl units follows at high metal-ion concentrations; 6) the effect of the metal ion depends on the nature of the counterion. This example demonstrates that dendrimers may exhibit complete functionality resulting from the integration of the specific properties of their component units.
    Chemistry 01/2007; 12(35):8926-34. · 5.83 Impact Factor
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    ABSTRACT: The network of chemical reactions of the compound 4�-methoxyflavylium was studied in the presence of SDS micelles, using stopped-flow, UV–vis absorption and flash photolysis techniques. The results were compared with analogous experiments carried out in water. The large stabilization of the flavylium cation onto the micelles was proven to be due to an increase in the rate of the dehydration reaction, rather than a decrease of the hydration reaction; the cis–trans isomerisation of the chalcone was not affected by the micelles. It is shown that SDS micelles can be considered as an external stimulus capable of changing the system from one state to another.
    Journal of Photochemistry and Photobiology A Chemistry 01/2007; 185:383-390. · 2.42 Impact Factor
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    ABSTRACT: Without Abstract
    04/2006: pages 1-64;
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    ABSTRACT: By a mild modified Eglinton coupling a series of diynebridged macrobicyclic hosts capable of endocavital complexation were synthesized and their structures and complexation properties investigated by X-ray analysis. The inclusion of DMSO in 7 suggests a direct correlation between steric fit and orientation of the guest. On the basis of this hypothesis, the orientation of acetone in an endocavital inclusion of 2 was predicted and verified by X-ray analysis. Comparison of the single-crystal X-ray structures of the vacant macrobicycle 3 and of a family of macrobicycles showing endocavital or “pocket” complexation of neutral organic guests suggests that torsion of the cavities upon complexation results from induced fit. Hydrogenation of the triple bonds leads to the more flexible macrobicycles 10–12 with collapsable cavities. The absorption and emission spectra of the diynebridged macrobicyclic hosts 1 and 3, of their hydrogenated analogues 11 and 12, and of a hemicage parent compound of 2 (14) were investigated. The macrobicyclic compounds 3, 11, 12 and 14 exhibit a strong fluorescence in CH2Cl2 solution at room temperature. The lack of fluorescence of 2 under such conditions is attributed to the presence of low-energy charge-transfer excited states, as indicated by the charge-transfer bands in the absorption spectrum. In a rigid CH2Cl2 matrix at 77 K all the examined compounds are fluorescent.
    Annalen der Chemie und Pharmacie 01/2006; 1996(11):1697 - 1704. · 3.10 Impact Factor
  • Chemistry-a European Journal - CHEM-EUR J. 01/2006; 12(35):8879-8879.
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    ABSTRACT: 1,4,8,11-tetraazacyclotetradecane (cyclam), which is one of the most extensively investigated ligands in coordination chemistry, in its protonated forms, can play the role of host toward cyanide metal complexes. We have investigated the acid-driven adducts formed in acetonitrile-dichloromethane (1:1 v/v) solution by [Ru(bpy)(CN)4](2-) with 1,4,8,11-tetrakis(naphthylmethyl)cyclam (1) and a dendrimer consisting of a cyclam core appended with 12 dimethoxybenzene and 16 naphthyl units (2). [Ru(bpy)(CN)4](2-), 1, and 2 exhibit characteristic absorption and emission bands, in distinct spectral regions, that are strongly affected by addition of acid. When a solution containing equimolar amounts of [Ru(bpy)(CN)4](2-) and 1 or 2 is titrated by trifluoroacetic acid, or when [Ru(bpy)(CN)4](2-) is titrated with (1.2H)2+ or (2.2H)2+, [[Ru(bpy)(CN)4](2-).(2H+).1] or [[Ru(bpy)(CN)4](2-).(2H+).2] adducts are formed in which the fluorescence of the naphthyl units is strongly quenched by very efficient energy transfer to the metal complex, as shown by the sensitized luminescence of the latter. The [[Ru(bpy)(CN)4]2-.(2H+).1] and [[Ru(bpy)(CN)4](2-).(2H+).2] adducts can be disrupted (i) by addition of a base (1,4-diazabicyclo[2.2.2]octane), yielding the starting species [Ru(bpy)(CN)4](2-) and 1 or 2, or (ii) by further addition of triflic acid, with formation of (1.2H)2+ or (2.2H)2+ and protonated forms of [Ru(bpy)(CN)4](2-). It is shown that upon stimulation with two chemical inputs (acid and base) both [[Ru(bpy)(CN)4](2-).(2H+).1] and [[Ru(bpy)(CN)4](2-).(2H+).2] exhibit two distinct optical outputs (a naphthalene-based and a Ru(bpy)-based emission) that behave according to an XOR and an XNOR logic, respectively.
    Journal of the American Chemical Society 01/2005; 126(50):16466-71. · 10.68 Impact Factor
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    ABSTRACT: Suitably designed luminescent dendrimers can play a role of ligands for luminescent and non-luminescent metal ions. This combination leads to species capable of exhibiting interesting and unusual properties, including (i) shielding excited states from quenching processes, (ii) light harvesting, (iii) conversion of incident UV light into visible or infrared emission, and (iv) metal ions sensing with signal amplification. (C) 2004 Elsevier B.V. All rights reserved.
    JOURNAL OF ORGANOMETALLIC CHEMISTRY. 11/2004; 689(24, SI):4375-4383.
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    ABSTRACT: The absorption spectra, luminescence spectra, and luminescence lifetimes of the isomeric [M(bph)(bpy)] and [M(phpy)2] complexes M = Pt(II) or Pd(II), bph2− = 1,1′-biphenyl-2,2′-diyl dianion, phpy− = 2-phenylpyridine-2′-yl anion, and bpy = 2,2′-bipyridine have been investigated and compared with those of [M(bpy)2]2+ complexes and of the free protonated ligands H2bph, Hbpy+, and Hphpy. In the absorption spectra, the region below 320 mm is dominated by ligand-centered (LC) transitions, whereas metal-to-ligand charge transfer (MLCT) transitions are responsible for the bands present in the near UV/VIS region. The MLCT bands move to higher energies on replacing Pt with Pd and in going from [M(bph)(bpy)] to the [M(phpy)2] isomer. For the mixed-ligand complexes, evidence for both M → bph2− (at higher energies) and M → bpy bands is found. The structured luminescence observed at 77 K shows lifetimes of 4.0 and 1.1 μs for [Pt(phpy)2] and [Pt(bph)(bpy)], respectively, and 480 and 250 μs for the analogous Pd complexes. On the basis of the energy and lifetime data, the luminescence of the Pt(II) complexes is assigned to the lowest triplet MLCT excited state, whereas for the Pd complexes the luminescent state is thought to result from a mixture of MLCT and LC triplet levels.
    Helvetica Chimica Acta 10/2004; 71(5):1053 - 1059. · 1.38 Impact Factor

Publication Stats

729 Citations
258 Downloads
280.31 Total Impact Points

Institutions

  • 2011
    • University of Groningen
      Groningen, Groningen, Netherlands
  • 1983–2011
    • University of Bologna
      • "Giacomo Ciamician" Department of Chemistry CHIM
      Bologna, Emilia-Romagna, Italy
  • 2003–2010
    • New University of Lisbon
      • Faculty of Sciences and Technology
      Lisboa, Lisbon, Portugal
  • 2007
    • Bowling Green State University
      Bowling Green, Ohio, United States
    • Universidad de Jaén
      • Department of Organic and Inorganic Chemistry
      Jaén, Andalusia, Spain
  • 2004
    • Cooperativa de Ensino Superior, Politécnico e Universitário
      Гандра, Porto, Portugal
    • University of Oxford
      • Department of Chemistry
      Oxford, ENG, United Kingdom
  • 2001–2002
    • University of Bonn
      • Kekulé Institute of Organic Chemistry and Biochemistry
      Bonn, North Rhine-Westphalia, Germany
  • 1984–1992
    • Université de Fribourg
      Freiburg, Fribourg, Switzerland