Highly luminescent bis-cyclometalated iridium(III) ethylenediamine complex: synthesis and correlation between the solid state polymorphism and the photophysical properties.

The solvent induced polymorphism observed in a cyclometalated iridium(iii) ethylenediamine ionic complex is a new tool to modulate and enhance emission in the solid crystalline state.

Non-classical anticancer agents: synthesis and biological evaluation of zinc(II) heteroleptic complexes.

New heteroleptic complexes (1-8) containing Zn(II) ion coordinated to an N,N-chelating ligand (the 4,4'-dinonyl-2,2'-bipyridine, bpy-9) and to diketonates L such as tropoloids (Tropolone and Hinokitiol) or 1-phenyl-3-methyl-4-R-5-pyrazolones have been synthesized by using different stoichiometric ratio with respect to the L ancillary ligand. The molecular structure of the bis-tropolonate derivative [(bpy-9)Zn(L)(2)] 5 has been determined by single-crystal X-ray diffraction. The antitumour activity of all Zn(II) complexes was tested in vitro against three different human prostate cancer cells: DU145, LNCaP and PC-3. Moreover, their effect on cell survival signalling and/or inhibitors of the PC-3 cell cycle have been analyzed. The results indicate that 1-8 exhibit strong cytotoxic activity against all cell lines affecting key molecules such as p-AKT and p21 waf, involved in the cell proliferation and/or arrest. Zinc(II) is thus a promising alternative to Pt(II) ion in the design of new, better performing antitumour agents.

Anion dependent mesomorphism in coordination networks based on 2,2'-bipyridine silver(I) complexes.

The reaction of the promesogenic dihexadecyl-2,2'-bipyridine-4,4'-dicarboxylate (L16) with a number of AgX salts produces a series of silver(I) complexes [(L16)Ag(sac)], 1, [(L16)Ag(NO3)], 2, [(L16)Ag(OTf)], 3, and [(L16)3Ag2](ClO4)2, 4, whose stoichiometries, molecular architectures, supramolecular networks and mesomorphic behaviour are "anion dependent". In spite of the large differences in the single molecular structure, the one-dimensional coordination networks involving the triflate and perchlorate in complexes 3 and 4, are the key element for inducing significant argentophilic intermolecular interactions responsible for the induction of lamello-columnar mesomorphism in both Ag(I) derivatives. Moreover, a series of Ag(I) triflate model complexes have been synthesized and in order to get more insights about their solid state architectures, systematic structural studies have been performed.

UV/Vis to NIR photoconduction in cyclopalladated complexes.

The incorporation of a rigid core, formed by a cyclopalladated azobenzene fragment bonded to an ancillary Schiff base ligand, into molecules with 12 or 11 peripheral alkyl chains has been successfully achieved. These new complexes, 1 and 2, respectively, are columnar liquid crystals between room temperature and about 50 degrees C. Both cyclometallated and ancillary ligands have been polyalkylated through either aryl ester (electron-withdrawing group) or aryl ether (electron-releasing group) linkages, in order to tune the HOMO/LUMO energy levels. The photoconductive properties of 1 and 2 have been studied as a function of their absorption properties before and after annealing, from the UV/Vis to NIR region. Compared with the reference compounds, tris-alkynyl benzene discotics, these new materials gave similar performances (sigma/I approximately 8x10(-13) S cm W(-1) with E = 10 V microm(-1) at lambda = 370 nm). Moreover, complex 2 shows a normalized photoconductivity sigma/I = 8.5x10(-13) S cm W(-1) at lambda = 760 nm. Organic photoconductors in such a high wavelength spectral range are not common and are usually assembled by mixing dyes with organic semiconductors.

Unsuspected mesomorphism in "tail-free" cyclopalladated 3,5-disubstituted-2-(2'-pyridyl)pyrroles.

The first cyclopalladation of 3,5-disubstituted-2-(2'-pyridyl)pyrroles leads to columnar metallomesogens of non-conventional molecular shape.

Bioactive fragments synergically involved in the design of new generation Pt(ii) and Pd(ii)-based anticancer compounds.

New Pt(ii) and Pd(ii) complexes with the metal center coordinated to two different chelating ligands, tropolone (trop) and dihexadecyl-2,2'-bipyridine-4,4'-dicarboxylate bipyridine (bipy), [(bipy)M(trop)][CF(3)SO(3)], have been synthesized and their biological evaluation has been performed demonstrating a remarkable cytotoxic activity in vitro against the human prostate DU145 and hormone-sensitive LNCaP cells lines. Moreover, for the Pt(ii) derivative, the molecular structure has been determined by single-crystal X-ray diffraction and computational analysis on the hydrolysis reaction mechanisms have been performed by density functional theory (DFT) calculations, in order to correlate molecular structure, biological activity and mechanism of action of this new class of complexes based on two different bioactive fragments.

A "jellyfish" shaped green emitting gallium(III)-containing metallomesogen.

The synthesis of the first gallium(III)-based liquid crystal has been achieved grafting around the metal centre two chelating 2-methylquinolin-8-olate anions and one monodentate 3,4,5-tris(hexadecyloxy)benzoyloxy ligand, allowing the resulting complex to be a soft luminescent material with the typical high quantum yield of pentacordinated gallium species.

Synthesis and solid state characterization of hexacoordinated 1:1 ionic gallium(III) complexes.

The coordination of the N,N ligands 2,2-bipyridine (bipy) and 1,10-phenanthroline (phen) to Ga(III) has been investigated via the formation of new ionic hexacoordinated complexes of general formula [Q'(2)Ga(N,N)][X], where HQ' stands for 2-methyl-8-hydroxyquinoline and the counter anion X(-) is nitrate (NO(3)(-)) or hexafluorophosphate (PF(6)(-)). All synthesized complexes were characterized by single-crystal X-ray diffraction analysis. The geometry of the Ga(III) cations is octahedral and a single geometric isomer (all N, N trans conformation) has been obtained in all cases. The role of both the N,N ligand and the counter anion has been investigated in the formation of the crystal supramolecular motifs occurring in the 3D-crystal networks of these new class of ionic Ga(III) derivatives. A full investigation of the photophysical properties of the new synthesized ionic species is reported and discussed in relation to their crystalline packing and the degree of crystallinity of thin solid films as well as the nature of the N,N ligand and the counter anion.

Curcumin and cyclopalladated complexes: a recipe for bifunctional biomaterials.

The first examples of binuclear and mononuclear ortho-palladated complexes based on a functionalized 2-phenylquinoline ligand have been synthesized and fully characterized. Conjugating cyclopalladated fragments to curcumin family biologically active beta-diketones gives in one single molecule two different functionalities. The structural variations based on the curcuminoid structure have been tested for their in vitro cytotoxic activity. The activity of complexes comprised of a cyclopalladated fragment conjugated to functionalized bioactive ligands, represents the potential of organometallic systems in generating new bifunctional biomaterials.

A new synthesis of 2,3-dihydrobenzo[1,4]dioxine and 3,4-dihydro-2H-benzo[1,4]oxazine derivatives by tandem palladium-catalyzed oxidative aminocarbonylation-cyclization of 2-prop-2-ynyloxyphenols and 2-prop-2-ynyloxyanilines.

2-[(Dialkylcarbamoyl)methylene]-2,3-dihydrobenzo[1,4]dioxine and 3-[(dialkylcarbamoyl)methylene]-3,4-dihydro-2H-benzo[1,4]oxazine derivatives (3 and 5, respectively) were synthesized for the first time starting from readily available 2-prop-2-ynyloxyphenols 1 and 2-prop-2-ynyloxyanilines 4, respectively, through tandem oxidative aminocarbonylation of the triple bond-intramolecular conjugate addition. Reactions were carried out in the presence of catalytic amounts of PdI2 in conjunction with an excess of KI in N,N-dimethylacetamide (DMA) as the solvent at 80-100 degrees C and under 20 atm (at 25 degrees C) of a 4:1 mixture of CO-air. The reaction showed a significant degree of stereoselectivity, the Z isomers being formed preferentially or exclusively. The configuration around the double bond of the major stereoisomers was unequivocally established by X-ray diffraction analysis.

Silver coordination complexes as room-temperature multifunctional materials.

A series of bischelate ionic silver complexes [Ag(L*)(2)][X] was prepared by complexation of a newly synthesized 2,2'-bipyridine containing chiral alkoxy chains in the 4,4' positions. The appropriate choice of the construction motifs allows the preparation of new materials in which several functionalities can be introduced. Indeed, when the anion X(-) is a triflate or a dodecylsulfate group, the right combination of intermolecular interactions promotes the production of liquid crystalline mesophases. Therefore, the presence of coordinating anions, which drives the supramolecular assembly, is essential to generate, at the same time, room-temperature columnar hexagonal mesomorphism, the columnar helical supramolecular structure, and excimeric emission.

Synthesis and anticancer activity of cyclopalladated complexes containing 4-hydroxy-acridine.

The synthesis and the characterization (elemental analysis, (1)H NMR and X-ray) of the first cyclopalladated complexes containing 4-hydroxyacridinate as complementary ligand are described. 4-Hydroxyacridine acts as a bidentate [N,O] chelating ligand, giving rise to square planar Pd(II) complexes in the coordination of a cyclopalladated fragment of phenylpyridine or phenylpyrimidine, characterized by the presence of two almost coplanar metalated rings. The biological activity studies conducted on these new Pd(II) complexes proved that the phenylpyridine Pd(II) derivative is more efficient than cis-platinum. The intrinsically substitutional inertness of the cyclopalladated ring and the presence of the [N,O] chelated acridine ligand make these systems of particular interest in their promising biological activity.

Synthesis and luminescent properties of novel lanthanide(III) beta-diketone complexes with nitrogen p,p'-disubstituted aromatic ligands.

Tris-beta-diketonate lanthanide(III) complexes (Ln = Eu, Er, Yb, Tb), of general formula [Ln(acac)3 L(m)], with chelating ligands such as 4,7-disubstituted-1,10-phenanthrolines and 4,4'-disubstituted-2,2'-bipyridines, have been synthesized and fully characterized. The inductive effects of the para-substituents on the aromatic N-donor ligands have been investigated both in the solid and in the solution states. Single-crystal X-ray structures have been determined for the diethyl 1,10-phenanthroline-4,7-dicarboxylate europium and 4,4'-dimethoxy-2,2'-bipyridine erbium derivatives, revealing a distorted square antiprismatic geometry around the lanthanide atom in both cases. The influence exerted by the p,p'-substituents with respect to the nitrogen coordinating atoms on the Ln-N bond distances is discussed comparing the geometrical parameters with those found for the crystal structures containing the fragments [Ln(III)(phen)] and [Ln(III)(bipy)] obtained from the Cambridge Structural Database. The influence exerted by the electron-attracting groups on the coordination ability of the ligands, that in some cases becomes lack of coordination of the lanthanide ions, has been also detected in solution where the loss of the ligand has been followed by UV-vis spectroscopy. Moreover, the use of relatively long alkoxy chains as substituents on the 1,10-phenanthroline ligand led to the formation of a promesogenic lanthanide complex, whose thermal behavior is encouraging for the synthesis of new lanthanide liquid-crystalline species.

Pain-reduction strategies in hypnotic context and hypnosis: ERPs and SCRs during a secondary auditory task.

Pain-rating scores were obtained from 10 high, 10 medium, and 10 low hypnotizable subjects who were holding a painful cold bottle in their left hands and were exposed to pain reduction treatments while they were performing a secondary oddball task. All subjects received suggestions of dissociative imagery and focused analgesia as cognitive strategies for pain reduction. The following measures were obtained for tone targets of the auditory oddball task: (a) reaction time; (b) P300 peak amplitude of the event-related potentials; (c) skin conductance levels and skin conductance responses. Focused analgesia produced the most pain reduction in high, but not medium or low, hypnotizable subjects who showed shorter reaction times, higher central and parietal P300 peaks, and higher skin conductance responses. These findings were discussed vis-a-vis the dissociated-control model assuming that capacity demands of hypnotic suggestion are low.

Pain perception, somatosensory event-related potentials and skin conductance responses to painful stimuli in high, mid, and low hypnotizable subjects: effects of differential pain reduction strategies.

In this study, pain perception, somatosensory event-related potential (SERP) and skin conductance response (SCR) changes during hypnotic suggestions of Deep Relaxation, Dissociated Imagery, Focused Analgesia, and Placebo, compared with a Waking baseline condition, were investigated. SERPs were recorded from frontal, temporal, central, and parietal scalp sites. Ten high, 9 mid, and 10 low hypnotizable right-handed women participated in the experiment. The following measures were obtained: (1) pain and distress tolerance ratings; (2) sensory and pain thresholds to biphasic electrical stimulation delivered to the right wrist; (3) reaction time and number of omitted responses; (4) N2 (280+/-11 ms) and P3 (405+/-19 ms) peak amplitudes of SERPs to target stimuli delivered using an odd-ball paradigm; (5) number of evoked SCRs and SCR amplitudes as a function of stimulus repetition. Results showed, high, mid and low hypnotizables exhibited significant reductions of reported pain and distress ratings during conditions of Deep Relaxation/Suggestion of Analgesia, Dissociated Imagery and Focused Analgesia. High hypnotizable subjects displayed significant reductions in pain and distress levels compared to mid and low hypnotizables during Dissociated Imagery, Focused Analgesia and, to a lesser degree, during Deep Relaxation. Placebo condition did not display significant differences among hypnotizability groups. High hypnotizables, compared to mid and low hypnotizables, also showed significant increases in sensory and pain thresholds during Dissociated Imagery and Focused Analgesia. High, mid, and low groups showed significant reductions in P3 peak amplitudes across all hypnosis conditions and, to a lesser degree, during Placebo. The temporal cortical region was the most sensitive in differentiating SERP responses among hypnotizability groups. On this recording area the subjects highly susceptible to hypnosis displayed significantly smaller P3 and greater N2 peaks during Focused Analgesia than did the other hypnotizable groups. In this condition highly susceptible subjects also reported the highest number of omitted responses and the shortest Reaction Times. These subjects also showed faster habituation of SCRs when compared with mid and low hypnotizables. During Dissociated Imagery and Focused Analgesia, highly hypnotizable subjects also disclosed a smaller total number of evoked SCRs than did mid and low hypnotizable subjects. The results are discussed considering possible common and different mechanisms to account for the effects of different hypnotic suggestions.