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Five cationic iridium(III) complexes with fluorinated cyclometalating tetrazole ligands [Ir(dfptrz)2L]+, where Hdfptrz = 5-(2,4-difluorophenyl)-2-methyl-2H-tetrazole and L = 2,2′-bypiridine (1F), 4,4′-ditert-butyl-2,2′-bipyridine (2F), 1,10-phenantroline (3F), 4,4′-bis(dimethylamino)-2,2′-bipyridine (4F), and tert-butyl isocyanide (5F), were prepared following a one-pot synthetic strategy based on a bis-cyclometalated solvato complex obtained via silver(I)-assisted cyclometalation, which was then reacted with the proper ancillary ligand to get the targeted complexes. The X-ray crystal structures of 2F and 4F were determined, showing that the tetrazole ligands are in a trans arrangement with respect to the iridium center. Electrochemical and photophysical properties, along with density functional theory calculations, allowed a full rationalization of the electronic properties of 1F-5F. In acetonitrile solution at 298 K, complexes 1F-3F, equipped with bipyridine and phenanthroline ligands, exhibit strong vibronically structured luminescence bands in the blue region with photoluminescence quantum yields (PLQYs) in the range 56-76%. This behavior is radically different from the nonfluorinated analogues reported previously, which emits in the green region from 3MLCT excited states. 4F shows relatively strong emission (PLQY = 40%) of charge transfer character centered on the amino-bipyridine ancillary ligand, whereas the emission of 5F is very weak (PLQY = 0.6%), further blue-shifted and attributed to the lowest ligand-centered (3LC) triplet state of the tetrazolyl cyclometalated moiety. A similar photophysical behavior is observed in PMMA at 298 K, whereas in a 77 K matrix, all of the compounds are strong emitters. This novel fluorinated phenyl-tetrazole cyclometalating ligand provides the corresponding iridium(III) complexes with a combination of excited-state energy and redox potentials that make them very promising as photoredox catalysts.

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.

The synthesis and photophysical properties of two multichromophoric systems, Pt(II)/B(III) and Pt(II)/Ir(III), based on novel N^O-julolidine ligands are reported. The functionalization of the julolidine core enables the introduction of two different anchoring sites, a terminal acetylene and an N^O chelating moiety, which allow the assembling of two different chromophoric centers. The complex photophysical behavior of these multicomponent arrays is rationalized by investigating a series of model compounds, which are prepared through specific synthetic pathways. The photophysical properties of the final multicomponent arrays are investigated in parallel with the models. The multichromophoric system, composed by a platinum(II) and an iridium(III) chromophore connected through a modified julolidine ditopic ligand, displays a peculiar excitation wavelength dependent luminescence behavior. It exhibits tuning of the emission color from blue to orange, passing through pure and warm white.

We report new bis-cyclometalated cationic indium(III) complexes [((CN)-N-boolean AND)(2)Ir(CN-tert-Bu)(2)](CF3SO3) that have tert-butyl isocyanides as neutral auxiliary ligands and 2-phenylpyridine or 2-(4'-fluoropheny1)-R-pyridines (where R is 4-methoxy, 4-tert-butyl, or 5-trifluoromethyl) as (CN)-N-boolean AND ligands. The complexes are white or pale yellow solids that show irreversible reduction and oxidation processes and have a large electrochemical gap of 3.58-3.83 V. They emit blue or bluegreen phosphorescence in liquid/solid solutions from a cyclometalating-ligand-centered excited state. Their emission spectra show vibronic structure with the highest-energy luminescence peak at 440-459 nm. The corresponding quantum yields and observed excited-state lifetimes are up to 76% and 46 mu s, respectively, and the calculated radiative lifetimes are in the range of 46-82 mu s. In solution, the photophysical properties of the complexes are solvent-independent, and their emission color is tuned by variation of the substituents in the cyclometalating ligand. For most of the complexes, an emission color red shift occurs in going from solution to neat solids. However, the shift is minimal for the complexes with bulky tert-butyl or trifluoromethyl groups on the cyclometalating ligands that prevent aggregation. We report the first example of an iridium(III) isocyanide complex that emits blue phosphorescence not only in solution but also as a neat solid.

The photophysical properties of a series of charged biscyclometalated [Ir(ppy)(2)(N boolean AND N)](1+) complexes, where ppyH is 2-phenylpyridine and N boolean AND N is 2,2'-bipyridine (bpy), 6-phenyl-2,2'-bipyridine (pbpy), and 6,6'-dipheny1-2,2'-bipyridine (dpbpy) for complexes 1, 2, and 3, respectively, have been investigated in detail. The photoluminescence performance in solution decreases from 1 to 3 upon attachment of phenyl groups to the ancillary ligand. The absorption spectra recorded over time suggest that complex 3 is less stable compared to complexes 1 and 2 likely due to a nucleophilic-assisted ancillary ligand-exchange reaction. To clarify this behavior, the temperature dependence of the experimental intrinsic deactivation rate constant, k(in) = 1/tau, has been investigated from 77 K to room temperature. Temperature-dependent studies show that nonemitting metal-centered (MC) states are accessible at room temperature for complex 3. The experimental results are interpreted with the help of theoretical calculations performed within the density functional theory (DFT) approach. Calculations suggest that attachment of a phenyl group to the ancillary ligand (2) promotes the temperature-independent deactivation pathways, whereas attachment of a second phenyl group (3) also makes the temperature-dependent ones accessible through population of nonradiative (3)MC excited states.

A series of cationic iridium(III) complexes with two carbene-based cyclometalating ligands and five different NN bipyridine and 1,10-phenanthroline ancillary ligands is presented. For the first time in the frame of a rarely studied class of bis(heteroleptic) iridium complexes with two carbene-based cyclometalating ligands a pair of cis and trans isomers has been isolated. All complexes (trans-1-5 and cis-3) were characterized by H-1 NMR, C-13 NMR, P-31 NMR, and HRMS (ESI-TOF); in addition, crystal structures of cis-3 and trans-4 are reported and discussed. Cyclic voltammetric studies show that the whole series exhibits highly reversible oxidation and reduction processes, suggesting promising potential for optoelectronic applications. Ground-state DFT and TD-DFT calculations nicely predict the blue shift experimentally observed in the room-temperature absorption and emission spectra of cis-3, compared to the trans complexes. In CH3CN, cis-3 displays a 4-fold increase in photoluminescence quantum yield (PLQY) with respect to trans-3, as a consequence of drastically slower nonradiative rate constant. By contrast, at 77 K, the emission properties of all the compounds, including the cis isomer, are much more similar, with a pronounced hypsochromic shift for the trans complexes. A similar behavior is found in solid state (1% w/w poly(methyl methacrylate) matrix), with all complexes displaying PLQY of similar to 70-80%, comparable emission lifetimes (tau approximate to 1.3 mu s), and a remarkable rigidochromic shift. To rationalize the more pronounced nonradiative deactivation (and smaller PLQY) observed for photoexcited trans complexes, comparative temperature-dependent emission studies in the range of 77-450 K for cis-3 and trans-3 were made in propylene glycol, showing that solvation effects are primarily responsible for the observed behavior.

Lanthanide(III) complexes have been prepared with [L1]- [the tetradentate chelating ligand bis{3-(2-pyridyl)pyrazolyl}dihydroborate], [L2]- [the tetradentate chelating ligand bis{3-(2-pyrazinyl)pyrazolyl}dihydroborate], [L3]- [the hexadentate chelating ligand bis[3-{6‘-(2,2‘-bipyridyl)}pyrazol-1-yl]dihydroborate], and [L4]2- [the 12-dentate compartmental ligand hexakis{3-(2-pyridyl)pyrazol-1-yl}diboran(IV)ate, which has two hexadentate tris(pyrazolyl)borate-based cavities linked “back-to-back” by a B−B bond]. [Ln(L1)2(NO)3] are 10-coordinate with two tetradentate N-donor ligands and one bidentate nitrate. [Ln(L2)2(NO)3] have 10-coordinate structures similar to those of the [L1]- complexes except that the coordinated N1 of the pyrazine rings is not such a good donor as the pyridine rings in the [L1]- complexes, leading to marked lengthening of these Ln−N bonds. [Ln(L3)(NO3)2] are also 10-coordinate from one hexadentate chelating ligand which has a pseudoequatorial coordination mode and two pseudoaxial bide...

The photophysical properties of a multicomponent array consisting of a free-base aryl-porphyrin and a gold(III) aryl-porphyrin, assembled via a central bis(terpyridine) ruthenium(II) complex, PH2−Ru−PAu, have been studied in low-temperature glassy media by steady state and time-resolved methods. Comparison of the photophysical properties of this triad with those of the reference molecular models and of the related dyads (Ru−PH2, Ru−PAu) allows the photoinduced processes occurring in PH2−Ru−PAu to be elucidated. The photoinduced processes in glassy media in the dyads Ru−PH2 and Ru−PAu are basically similar to those occurring at room temperature where the absorbed energy is transferred with 100% efficiency to the pertinent porphyrin lowest triplet state. For Ru-3PAu the decay to the ground state is similar to the model 3PAu and displays double-exponential behavior, while in the case of Ru−3PH2 some perturbing effect of the ruthenium center in accelerating the inter-system crossing to the ground state by the...

We have prepared the mononuclear complexes [Ru(bpy)2(AB)][PF6]2, [Ru(bpy)(AB)2][PF6]2, and [Ru(AB)3][PF6]2 (designated Ru−AB, Ru−AB2, and Ru−AB3, respectively) [where bpy is 2,2‘-bipyridine and AB is the asymmetric bis(bipyridyl) bridging ligand 2,2‘:3‘,2‘‘:6‘‘,2‘‘‘-quaterpyridine] in which there are one, two, or three (respectively) bpy-type fragments pendant from the {Ru(bpy)3}2+ core. In every case the less hindered site A of the ligand AB is coordinated to Ru(II) and the more hindered site B is pendant. Reaction with Re(CO)5Cl affords the heteronuclear complexes [Ru(bpy)2{ABRe(CO)3Cl}][PF6]2, [Ru(bpy){ABRe(CO)3Cl}2][PF6]2, and [Ru{ABRe(CO)3Cl}3][PF6]2 (designated Ru−ABRe, Ru−ABRe2, and Ru−ABRe3, respectively) in which each pendant site B is now coordinated to a {Re(CO)3Cl} fragment. Because of the conformational properties of the AB ligand, in the tetranuclear Ru−ABRe3 complex the Ru-based chromophore occupies an internal position in a sort of molecular ball, the three Re-based groups being located ou...

A new fullerene-substituted phenanthroline ligand has been obtained by reaction of a phenanthroline derivative bearing a 1,3-phenylenebis(methylene)-tethered bis-malonate with C(60) in a double Bingel cyclopropanation. The relative position of the two cyclopropane rings in the resulting bis-methanofullerene derivatives has been determined on the basis of the molecular symmetry (C(s)()) deduced from the (1)H and (13)C NMR spectra. The corresponding Cu(I) complex F-Cu-F has been prepared in good yields by treatment of the ligand with Cu(CH(3)CN)(4)BF(4). In the resulting multicomponent system, both C(60) moieties are in a tangential orientation relative to their bridging phenyl ring, and the central bis(phenanthroline)Cu(I) core is sandwiched between the two carbon spheres. The electrochemical properties of F-Cu-F suggest the existence of ground-state electronic interactions in this multicomponent array based on the mutual effects exerted by the fullerene units to the bis(2,9-diphenyl-1,10-phenanthroline)Cu(I) complex and vice versa. Close vicinity and electronic interactions between the inorganic core and the peripheral fullerene units are also suggested by increased electronic absorption around 430 nm. The distance between the two moieties is estimated to be 4.3 A by molecular modeling studies. The excited-state properties of F-Cu-F have also been investigated. Photoinduced electron transfer from the central chromophore to the external fullerene units occurs but, surprisingly, only following population of the excited states of the central inorganic unit and not of the external carbon spheres. This is mainly attributed to kinetic factors related to the different nature of the two types of excited states involved, namely charge transfer (excitation on the metal-complexed moiety) vs a localized state (excitation on the fullerene units).

Steady-state and time-resolved spectroscopic properties of bichromophoric species containing [Ru(bpy)(3)](2+) and pyrene (pyr) units linked together by flexible poly(ethylene glycol) chains of variable length, [Ru(bpy)(2)(bpy-pyr)](PF(6))(2) (1) and [Ru(bpy)(2)(bpy-O6-pyr)](PF(6))(2) (2), have been investigated in acetonitrile solvent. The complexes were designed with the aim of examining the intercomponent energy-transfer processes taking place after light absorption at the two chromophores and the influence of the distance separation between them; in the case of complex 2, the linking chain in the extended conformation is as long as 21 A. Direct excitation of the pyrene unit (lambda(exc) = 410 nm) results in singlet-to-singlet energy transfer (an antenna effect) to the Ru-based component, (1)pyr --(1)MLCT, which we analyze in terms of the Förster mechanism taking place with unit efficiency. Analysis of the time-resolved pyrene fluorescence reveals that the actual center-to-center distance separation (d(cc)) between the photoactive centers changes according to a Gaussian distribution, with an average d(cc) = 13.6 A (distribution width, a = 2.8 A) and 12 A (a = 10.2 A), for 1 and 2, respectively; this is ascribed to folding of the poly(ethylene glycol) linking chain. In O(2)-free solvent at room temperature, after population of the (1)MLCT level (which takes place either because of direct excitation by using lambda(exc)355 nm or via the "antenna" effect) and subsequent intersystem crossing localized at the Ru center, (1)MLCT --(3)MLCT, a triplet-triplet thermal equilibration is established which involves the physically separated centers, (3)MLCT--(3)pyr, with K(eq) = 11 (the energy gap between the two levels is 480 cm(-1), as determined from luminescence data obtained at 77 K). As a consequence of this equilibrium, the (3)MLCT luminescence lifetime becomes tau(Ru) approximately 9 micros both in 1 and 2, i.e., 1 order of magnitude longer than for the unsubstituted [Ru(bpy)(3)](2+) luminophore. In air-equilibrated solvent, diffusional quenching by O(2) effectively depletes the (3)pyr level and only the forward (3)MLCT --(3)pyr energy transfer step is observed with k(en) = 4 x 10(8) and 2 x 10(8) s(-1) for 1 and 2, respectively. As briefly discussed, reasons for the high rate constants observed for the various triplet-triplet steps may be traced back to the folding properties of the linking chains.

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 Eu(3+), Gd(3+), Tb(3+), and Yb(3+) 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 degrees C, which indicates that there are no water molecules in the first coordination sphere of the metal ion. The analysis of high resolution (1)H 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.