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Five cationic iridium(III) complexes (1-5) were synthesized exploiting two triazole-based cyclometalating ligands, namely, 1-methyl-4-phenyl-1H-1,2,3-triazole (A) and the corresponding mesoionic carbene 1,3-dimethyl-4-phenyl-1H-1,2,3-triazol-5-yliclene (B). From the combination of these two ligands and the ancillary one, i.e., 4,4'-di-tert-butyl-2,2'-bipyridine (for 1-3) or tert-butyl isocyanide (for 4 and 5), not only the typical bis-heteroleptic complexes but also the much less explored tris-heteroleptic analogues (2 and 5) could be synthesized. The redox and emission properties of all of the complexes are effectively fine-tuned by the different ligands: (i) cyclometalating ligand A induces a stronger highest occupied molecular orbital (HOMO) stabilization compared to B and leads to complexes with progressively narrower HOMO-lowest unoccupied molecular orbital (LUMO) and redox gaps, and lower emission energy; (ii) complexes 1-3, equipped with the bipyridine ancillary ligand, display fully reversible redox processes and emit from predominantly metal-to-ligand charge transfer (MLCT) states with high emission quantum yields, up to 60% in polymeric matrix; (iii) complexes 4 and 5, equipped with high-field isocyanide ligands, display irreversible redox processes and high-energy emission from strongly ligand-centered triplets with long emission lifetimes but relatively low quantum yields (below 6%, both in room-temperature solution and in solid state). This work demonstrates the versatility of phenyl-triazole derivatives as cyclometalating ligands with different chelation modes (i.e., CN and CC:) for the synthesis of photoactive iridium(III) complexes with highly tunable properties.

Iridium(III) complexes have assumed a prominent role in the areas of photochemistry and photophysics due to the peculiar properties of both the metal itself and the ligand environment that can be assembled around it. Ir(III) is larger, heavier, and bears a higher ionic charge than its analogue and widely used d6 ions such as Fe(II) and Ru(II). Accordingly, its complexes exhibit wider ligand-field d-d orbital splitting with electronic levels centered on the metal, typically nonemissive and photodissociative, not playing a relevant role in excited-state deactivations. In other words, iridium complexes are typically more stable and/or more emissive than Fe(II) and Ru(II) systems. Additionally, the particularly strong heavy-atom effect of iridium promotes singlet-triplet transitions, with characteristic absorption features in the UV-vis and relatively short excited-state lifetimes of emissive triplet levels. Ir(III) is also a platform for anchoring ligands of rather different sorts. Its versatile chemistry includes not only coordination with classic N∧N neutral ligands but also the binding of negatively charged chelators, typically having a cyclometalating C∧N anchor. The carbon-metal bond in these systems has some degree of covalent character, but this does not preclude a localized description of the excited states of the related complexes, which can be designated as metal-centered (MC), ligand-centered (LC), or charge transfer (CT), allowing a simplified description of electronic and photophysical properties. The possibility of binding different types of ligands and making heteroleptic complexes is a formidable tool for finely tuning the nature and energy of the lowest electronic excited state of cationic Ir(III) complexes by ligand design. Herein we give an account of our work on several families of iridium complexes typically equipped with two cyclometalating bidentate ligands (C∧N), in combination with mono or bidentate "ancillary"ligands with N∧N, C∧N, and C∧C motifs. We have explored new synthesis routes for both cyclometalating and ancillary ligands, obtaining primarily cationic complexes but also some neutral or even negatively charged systems. In the domain of the ancillary ligands, we have explored isocyanides, carbenes, mesoionic triazolylidenes, and bis-tetrazolic ligands. For the cyclometalating moiety, we have investigated carbene, mesoionic triazolylidene, and tetrazolic systems. Key results of our work include new strategies to modify both cyclometalating and ancillary ligands by relocating ionic charges, the determination of new factors affecting the stability of complexes, a demonstration of subtle structural effects that strongly modify the photophysical properties, new options to get blue-greenish emitters for optoelectronic devices, and a set of ligand modifications allowing the optimization of electrochemical and excited-state properties to obtain new promising Ir(III) complexes for photoredox catalysis. These results constitute a step forward in the preparation of custom iridium-based materials crafted by excited-state engineering, which is achieved through the concerted effort of computational and synthetic chemistry along with electrochemistry and photochemistry

Energy issue in Italian

Three new heteroleptic Cu(I) complexes containing one phenanthroline and one diphosphine type ligand ([Cu(N-N)(P-P)]+) have been prepared. In particular, one ligand is constituted by 1,10-phenanthroline (1), 2,9-dimethyl-1,10-phenanthroline (2) and 2,9-diphenethyl-1,10-phenanthroline (3) and the other ligand is in all cases 1,12-bis(diphenylphosphino)ferrocene (dppf). Therefore, copper and iron metal centres are quite close one another, as evidenced by X-ray crystal diffraction. The structure together with the electrochemical and photophysical properties of these complexes have been compared to that of the corresponding complexes where dppf has been replaced by bis[2-(diphenylphosphino)-phenyl]ether (POP). Cyclic voltammetric experiments evidenced that the first oxidation process is located on the ferrocene moiety and that oxidation of Cu(I) is moved to more positive potential values and a chemical reaction is coupled to the electron transfer process. The absorption spectra show a metal-to-ligand charge transfer (MLCT) band, typical of Cu(I) phenanthroline complexes, at a higher energy compared to the homoleptic [Cu(N-N)2]+ species. No emission at either room temperature or 77 K has been observed for compounds 2 and 3, contrary to the high luminescence observed for the corresponding POP complexes. This result is consistent with a photoinduced energy transfer from the Cu(I) complex to the ferrocene moiety.

Cu(I) complexes and clusters are the largest class of compounds of relevant photochemical and photophysical interest based on a relatively abundant metal element. Interestingly, Nature has given an essential role to copper compounds in some biological systems, relying on their kinetic lability and versatile coordination environment. Some basic properties of Cu(I) and Cu(II) such as their coordination geometries and electronic levels are compared, pointing out the limited significance of Cu(II) compounds (d 9 configuration) in terms of photophysical properties. Well-established synthetic protocols are available to build up a variety of molecular and supramolecular architectures (e.g. catenanes, rotaxanes, knots, helices, dendrimers, cages, grids, racks, etc.) containing Cu(I)-based centers and exhibiting photo- and electroluminescence as well as light-induced intercomponent processes. By far the largest class of copper complexes investigated to date is that of Cu(I)-bisphenanthrolines ([Cu(NN)2]+) and recent progress in the rationalization of their metal-to-ligand charge-transfer (MLCT) absorption and luminescence properties are critically reviewed, pointing out the criteria by which it is now possible to successfully design highly emissive [Cu(NN)2]+ compounds, a rather elusive goal for a long time. To this end the development of spectroscopic techniques such as light-initiated time-resolved X-ray absorption spectroscopy (LITR-XAS) and femtosecond transient absorption have been rather fruitful since they have allowed us to firmly ground the indirect proofs of the molecular rearrangements following light absorption that had accumulated in the past 20 years. A substantial breakthrough towards highly emissive Cu(I) coordination compounds is constituted by heteroleptic Cu(I) complexes containing both N- and P-coordinating ligands ([Cu(NN)(PP)]+) which may exhibit luminescence quantum yields close to 30% in deaerated CH2Cl2 solution and have been successfully employed as active materials in OLED and LEC optoelectronic devices. Also copper clusters may exhibit luminescence bands of halide-to-metal charge transfer (XMCT) and/or cluster centered (CC) character and they are briefly reviewed along with miscellaneous Cu(I) compounds that recently appeared in the literature, which show luminescence bands ranging from the blue to the red spectral region.

A Eu-III complex, tris-dibenzoylmethane mono-1,10-phenanthroline-europium(III) [Eu(DBM)(3)(Phen)], can be easily adsorbed If in situ via hydrophobic interactions to single-walled carbon nanotube (SWNT) surfaces from a methanol solution. The Eu-III containing material has been comprehensively characterized via thermogravimetric analysis (TGA), UV-vis-NIR absorption and luminescence spectroscopy, Raman spectroscopy, atomic force microscopy (AFM), high-resolution transmission electron microscopy (HR-TEM)), Z-contrast scanning transmission electron microscopy (STEM) imaging, and energy dispersive X-ray spectroscopy (EDS). The photophysical investigations revealed that the presence of a SWNT framework does not affect the lanthanide-centered luminescence stemming from the characteristic electronic transitions within the 4f shell of the Eu-III, ions. Such straightforward synthetic route leads to the preparation of luminescent SWNTs without significantly affecting the electronic and structural properties of the carbon framework, opening new possibilities of designing new classes of CNTs for biomedical applications.

Da un punto di vista ambientale la tecnologia a ciclo combinato a gas naturale è una valida scelta per la riconversione di vecchie centrali ad olio combustibile o a carbone. Le emissioni di gas serra ed inquinanti sono comunque tutt'altro che trascurabili, e includono rilevanti quantità di polveri fini. Nel caso di nuovi impianti di grandi dimensioni, l'autorizzazione andrebbe concessa con cautela ed in presenza di adeguate misure compensative sulla qualità dell'aria, seguendo l'esempio della legislazione statunitense.

A two-component ligand system (1) containing 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid (DO3A)as the hosting unit for the lanthanide cations and an appended asymmetrically functionalized 1,10-phenanthroline (phen) as the chromophore was synthesized. The 1:1 complexes with Eu3 +,Gd3+,Tb3+, and Yb3+ have been prepared and studied in aqueous solution. For Gd‚1, a relaxivity value of 2.4 mM-1 s-1 has been measured at 20 MHz and 25 °C, which indicates that there are no water molecules in the first coordination sphere of the metal ion. The analysis of high resolution 1H NMR spectra of Yb‚1 supports this view and suggests the direct involvement of the phen moiety in the coordination of the metal ion. For Eu‚1 and Tb‚1, the absorption and luminescence spectra, the overall luminescence efficiencies, and the metal-centered (MC) lifetimes were obtained; coordination features were also determined by comparing luminescence properties in water and deuterated water. For Eu‚1 and Tb‚1, the overall emission sensitization (se) process in air-equilibrated water was found to be notably effective with ?se= 0.21 and 0.11, respectively. A detailed study of the steps originating from light absorption at the phen unit and leading to MC sensitized emission was performed.

New oligophenylenevinylene-terminated phenylenevinylene dendrons have been prepared and attached to C-60 by a 1,3-dipolar cycloaddition of the azomethine ylides generated in situ from the dendritic aldehydes and N-methylglycine. Preliminary photophysical investigations of the resulting fullerodendrimers have revealed interesting light-harvesting properties.

Fullerene derivatives A-3PV and B-3PV in which an oligophenylenevinylene trimeric subunit (3PV) is attached to C60 through, respectively, a pyrrolidine or a pyrazoline ring have been prepared. The electrochemical and excited-state properties Of the multicomponent arrays A-3PV and B-3PV have been investigated in Solution using the related oligophenylenevinylene derivative 3PV, fullerenopyrrolidine A and fullerenopyrazoline B as reference Compounds. In A-3PV quantitative OPV --> C60 photoinduced singlet-singlet energy transfer has been observed. Population of the lowest fullerene singlet excited state is followed by nearly quantitative intersystem crossing to the lowest fullerene triplet excited state in CH2Cl2 and toluene. whereas OPV --> C60 electron transfer is able to compete significantly in the more polar solvent benzonitrile. In the case of B-3PV, the excited-state properties are more complex due to the electron donating ability of the pyrazoline ring. As observed for A-3PV, quantitative OPV --> C-60 photoinduced singlet-singlet energy transfer Occurs in B-3PV. However, in this case, the population of the lowest fullerene singlet excited state is followed by an efficient electron transfer from the pyrazoline ring in CH2Cl2 and benzonitrile. In B-3PV. studies of the dependence of photoinduced processes on solvent polarity. addition of acid. and temperature also reveal that this Compound can be considered as a fullerene-based molecular switch, the switchable parameters being the photoinduced processes. Finally, A-3PV and B-3PV have been tested as active materials in photovoltaic devices and the differences of light to energy conversion efficiencies found for the two compounds have been rationalised on the basis of their photophysical properties.

Poly(aryl ether) dendritic branches terminated with peripheral triethyleneglycol chains have been attached to C60. The resulting fullerodendrimers have been characterised by electrospray mass spectrometry (ESMS), which appears to be a particularly interesting analytical tool for the unambiguous structural assignment of such high molecular weight fullerene derivatives. Their photophysical properties have been systematically investigated in three solvents, namely toluene, dichloromethane, and acetonitrile. The changes observed in the photophysical properties along the series suggest an increasing interaction between the poly(aryl ether) dendritic wedges and the fullerene core, which brings about an increasing isolation of the central chromophore from the exterior. Finally, thanks to their high solubility, fullerodendrimers 1-4 have been easily incorporated in mesoporous silica glasses and preliminary measurements on the resulting doped samples have revealed efficient optical limiting properties.

The rhenium(I) and ruthemum(II) complexes of a fullerene-substituted bipyridine ligand have been prepared. Electrochemical studies indicate that so..,ne ground state electronic interaction between the fullerene subunit and the metal-complexed moiety are present in the Re(I) but not the Ru(II) complex. The photophysical properties have been investigated by steady-state and time-resolved UV/Vis-NIR luminescence spectroscopy and nanosecond laser flash photolysis in CH2Cl2 solution, and compared to those of the corresponding model compounds. Excitation of the methanofullerene moiety in the dyads does not lead to excited state intercomponent interactions. Instead, excitation of the metal-complexed unit shows that the lowest triplet metal-to-ligand-charge-transfer excited state (3MLCT) centered on the Re(I) or Ru(II)-type unit is quenched with a rate constant of about 2.5 x 10(8) s(-1). The quenching, is attributed to an electron-transfer (EIT) process leading to the reduction of the carbon sphere, as determined by luminescence spectroscopy for the Ru(II) dyad. Experimental detection of electron transfer in the Re(II) dyad is prevented clue to the unfavorable absorption of the metal-complexed moiety relative to the fullerene unit. However. it can tic postulated on the basis of energetic/ kinetic arguments and by comparison with the Ru(II)-type array. The primary EIT process is followed by charge-recombination to give [fie lowest-lying fullerene triplet excited state (3C60) with quantitative yield, as determined by sensitized singlet oxygen luminescence experiments. Direct 1MLCT --> 3C60 triplet-triplet energy-transfer (EnT) does not successfully compete with EIT since it is highly exoergonic and located in the Marcus inverted region. The quantum yield of singlet oxygen sensitization (1O2) of the Re(I)-based dyad is found to be lower (0.80) than for the cot-responding Ru(II) derivative (1.0). This is likely to be the consequence of different conformational structures for the two dyads, rather than a different yield of 3C60 formation.

Two novel cone calix[4]arene ligands 11a and 11b bearing two iminodiacetic chelating units and two C-6 or C substituted 2,2'-bipyridine chromophores in diametral position at the lower rim were synthesized. These ligands form complexes with lanthanide ions in methanol solution whose stability (4.5 < log K-ass < 6.2) depends on the substitution pattern (C-6 or C-5) of the 2,2'-bipyridine units. Contrary to that observed with other neutral calixarene ligands, the luminescence properties of the Eu3+ and Tb3+ complexes are not very much affected by the type of the 2,2'-bipyridine chromophore. Luminescence lifetimes (0.31 ms < tau < 1.1 ms) and quantum yields (0.017 < phi < 0.130) are higher for Terbium compared with the corresponding Europium complexes.

A two-component ligand system (1) containing 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid (DO3A) as the hosting unit for the lanthanide cations and an appended asymmetrically functionalized 1,10-phenanthroline (phen) as the chromophore was synthesized, The 1:1 complexes with Eu3+, Gd3+, Tb3+, and Yb3+ have been prepared and studied in aqueous solution. For Gd.1, a relaxivity value of 2.4 mM(-1) s(-1) has been measured at 20 MHz and 25degreesC, which indicates that there are no water molecules in the first coordination sphere of the metal ion. The analysis of high resolution H-1 NMR spectra of Yb.1 supports this view and suggests the direct involvement of the phen moiety in the coordination of the metal ion. For Eu.1 and Tb.1, the absorption and luminescence spectra, the overall luminescence efficiencies, and the metal-centered (MC) lifetimes were obtained; coordination features were also determined by comparing luminescence properties in water and deuterated water. For Eu.1 and Tb.1, the overall emission sensitization (se) process in air-equilibrated water was found to be notably effective with phi(se) = 0.21 and 0.11, respectively. A detailed study of the steps originating from light absorption at the phen unit and leading to MC sensitized emission was performed.