Chiara Pasquini

“Inherent chirality” and curvature

“Inherent chirality” in molecules like calix[4]arenes, fullerenes, and uranyl-salophen complexes can be related to the presence of curvature. This observation serves as a basis for the introduction of a new chirality descriptor.

Specific Supramolecular Interactions between Zn2+-Salophen Complexes and Biologically Relevant Anions

Recognition of inorganic phosphates PO(4)(3-), P(2)O(7)(4-), and P(3)O(10)(5-) and nucleotides AMP(2-), ADP(3-), and ATP(4-) by Zn(2+)-salophen complexes 1 and 2 in ethanol was investigated by different spectroscopic techniques. (31)P NMR and mass spectrometry showed that anions of both series are bound by 1 and 2, while absorption and emission studies revealed that only nucleotides produce relevant changes in the spectral properties of the two hosts. (1)H NMR studies proved that the adenine aromatic group is involved in the complexation, thus pointing out the role of supramolecular ditopic receptors played by salophen derivatives toward this class of biologically relevant substrates. The lifetime of the photogenerated triplet state of the Zn(2+)-salophen compounds was measured by nanosecond laser flash photolysis, and the observed changes upon increasing the concentration of nucleotides allowed the identification of the formation of a 1:0.5 host/guest intermediate complex additionally to the formation of a 1:1 complex.

Zinc–salophen complexes as selective receptors for tertiary amines

Zinc–salophen compounds 1–3 incorporating in the given order 1,2-diaminobenzene, 2,3-diaminonaphthalene, and 9,10-diaminophenantrene moieties were synthesised. Their binding properties toward a series of tertiary amines were assessed by UV-Vis and fluorescence spectroscopy in chloroform solution. Unprecedented selectivities of quinuclidine vs. triethylamine higher than 105 were recorded, thereby revealing the dramatic influence of steric effects on axial coordination of tertiary amines. X-Ray diffraction analyses showed that in the solid state compound 2 is dimeric, but its 1 : 1 quinuclidine complex is monomeric. Strong indications were obtained that both free receptors and their amine adducts are monomeric in dilute chloroform solution.

Network assembly of gold nanoparticles linked through fluorenyl dithiol bridges

Gold nanoparticles stabilized by two novel bifunctional fluorenyl thiols, generated in situ from 9,9-didodecyl-2,7-bis(acetylthio)fluorene (1) and 9,9-didodecyl-2,7-bis(acetylthiophenylethynyl)fluorene (2), exhibit bridged structures which self-assemble in parallel lines. The size, shape and structure of the AuNPs have been determined by means of dynamic light scattering (DLS), scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). AuNPs modified with fluorenyl thiol derivatives show diameters in the range of 3–7 nm. The linkage between the nanoparticles can be envisaged with the formation of dyads supported by TEM analysis and XPS measurements. Remarkably, investigation by scanning electron microscopy of the AuNP films revealed an ordered distribution of well-separated individual nanoparticles to form a 2D network. The formation of interconnected networks between AuNPs with different distances, depending on the nature of the thiol linkers (1) or (2), and the photoluminescence properties open perspectives for applications in optical devices and electronics.

Nonsymmetrically Substituted Uranyl-Salophen Receptors: New Opportunities for Molecular Recognition and Catalysis

This short review highlights recent results in the chemistry of nonsymmetrically substituted uranyl-salophen complexes with specific reference to their synthesis and properties. Their use as receptors and catalysts is also emphasized. The possibility of modulating their structure within wide limits by choosing the proper substituted aldehydes and/or ketones as starting materials, coupled with their inherent chirality offers new appealing opportunities for their applications.

Chiral anion-mediated asymmetric induction onto chiral diquats

Diquats—which are important electron transfer agents in biological and photocatalytic systems, as well as structural templates for efficient supramolecular synthesis—are noteworthy for their axial chirality and have been so far reported only in racemic form due to the rapid interconversion between the atropoisomers. We now report the first example of configurational ordering of chiral diquats through their asymmetric ion pairing with novel hexacoordinated phosphate anions TRISPHAT, HYPHAT and BINPHAT.

Unprecedented detection of inherent chirality in uranyl–salophen complexes

In complexes with the uranyl dication salophen ligands are highly puckered. This implies that non-symmetrically substituted uranyl-salophen derivatives exist in principle as a pair of enantiomers. However, due to easy disrotations about the bonds connecting the phenoxide units to the imine carbons, the rate of interconversion between enantiomeric forms of simple, sterically unhindered compounds is extremely fast. Bulky substituents in appropriate positions decrease the interconversion rate and make this novel type of inherent chirality detectable by 1H and 13C NMR.

One-step synthesis of low molecular weight poly(p- phenyleneethynylenevinylene)s via polyaddition of aromatic diynes by catalysis of the [Ru(p-cymene)Cl2]2/AcOH system

pi-Conjugated low molecular weight polymers characterized by regio- and stereoregular alternation of phenylene and ( E)-1-en-3-yne moieties have been synthesized by polyaddition of 1,4-diethynylbenzene or of 2,5-diethynyl-1,4-alkoxybenzene monomers, employing the commercially available di-micro-chlorobis[( p-cymene)chlororuthenium(II)] complex as the metal catalyst source, under homogeneous, atom-economical, amine- and phosphine-free conditions. Bulk materials of poly( p-phenyleneethynylenevinylene) derivatives are obtained with yields larger than 80%, from which polymers readily soluble in chlorinated solvents and in tetrahydrofuran are extracted in 60-75% yields. The polymers with average degrees of polymerization in the range n AV = 4-8 display optical properties in solution similar to those of the higher molecular weights analogues.

Aromatic Bridged Bis-phenol A Derived Cyclophanes. Synthesis, Molecular Structure and Binding Properties Toward Quats

Three novel polyoxyethylene bridged bis phenol A derived cyclophanes, with additional aromatic units in the bridge to increase the number of cation–π interactions with guest cations, were synthesized and characterized by means of X-ray crystal structure determinations. The binding properties of these receptors toward tetramethylammonium (TMA), N-methylpyridinium (NMP), acetylcholine (ACh) and N-methylquinolinium (NMQ) salts were evaluated by means of 1H NMR spectroscopy and compared with those of the previously reported receptor 1.