Luca Schiaffino

Allosteric, chelate, and interannular cooperativity: a mise au point.

The distinction between different types of cooperativity is essential for understanding the fundamentals involved. The three title cooperative effects arise from the interplay of intermolecular binding interactions, the presence of one or more intramolecular binding interactions, and, in the latter case, their possible interplay. A master equation for the stability of an assembly is outlined that takes into account all of the three possible types of cooperativity

“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.

Putting the mechanism of the Soai reaction to the test: DFT study of the role of aldehyde and dialkylzinc structure.

Previous DFT calculations provided support to the proposal that the Soai reaction involves a mechanism in which dimer catalysts serve as templates for the reaction of two molecules of dialkylzinc with two molecules of aldehyde so as to reproduce themselves (ref 11). Here it is shown that, from the point of view of formal kinetics, this mechanism can be reduced to a general model, dubbed the extended dimer model, that has the Blackmond-Brown dimer model as a particular case. Depending on the interplay of kinetic constants, the extended dimer model can give rise to either chiral amplification or depletion. Calculations of the kinetic constants at the M05-2X/6-31G(d) level of theory were carried out in order to theoretically evaluate the effect of the second aza group in the six-membered aromatic ring of the aldehydic substrate and the effect of dialkylzinc structure. Predictions of chiral amplification or depletion are in striking agreement with experimental data thus lending support to the proposed mechanism.

Anion recognition in water with use of a neutral uranyl-salophen receptor.

A new water-soluble uranyl-salophen complex incorporating two glucose units has been synthesized. This neutral derivative shows noteworthy binding affinity for fluoride in water thanks to the Lewis acid-base interaction occurring between the metal and the anion. Such interaction is strong enough to overcome the high hydration enthalpy of fluoride. Moreover this complex effectively binds hydrogen phosphate and exhibits remarkably strong association for nucleotide polyanions ADP(3-) and ATP(4-).

Mechanism of the Asymmetric Autocatalytic Soai Reaction Studied by Density Functional Theory

The mechanism of the Soai reaction has been thoroughly investigated at the M05-2X/6-31G(d) level of theory, by considering ten energetically distinct paths. The study indicates the fully enantioselective catalytic cycle of the homochiral dimers to be the dominant mechanism. Two other catalytic cycles are shown to both be important for correct understanding of the Soai reaction. These are the catalytic cycle of the heterochiral dimer and the non-enantioselective catalytic cycle of the homochiral dimers. The former has been proved to be not really competitive with the principal cycle, as required for the Soai reaction to manifest chiral amplification, whereas the latter, which is only slightly competitive with the principal one, nicely explains the experimental enantioselectivity observed in the reaction of 2-methylpyrimidine-5-carbaldehyde. The study has also evidenced the inadequacy of the B3LYP functional for mechanistic investigations of the Soai reaction.

A new water soluble Zn-salophen derivative as a receptor for α-aminoacids: Unexpected chiral discrimination†

A new water soluble zinc-salophen complex with appended D-glucose moieties was synthesized and characterized. Its binding properties toward six aminoacids were investigated by UV-vis spectrophotometric titrations. Association constants showed to be unfavorably affected by increasing steric hindrance of the side chain. Quite surprisingly, different association constants were measured for the L and D enantiomers. These data suggest that aminoacids are bound via two interactions, zinc-carboxylate coordination and two hydrogen bonds between the ammonium group of the aminoacid and two oxygen atoms of one D-glucose moiety. Such conclusion is supported by the result of semiempirical (PM3) calculations. Notably, the K(L)/K(D) value of 9.6 observed for the association of phenylalanine rivals with the highest values found for the chiral recognition of aminoacids in water.

Molecular Recognition of Carbonyl Compounds by Uranyl-salophen Based Neutral Receptors Driven by Van Der Waals Forces

The complexation of the salophen-uranyl metallocleft 2 and of its half-cleft analogue 3 with enones and other carbonyl compounds was assessed in chloroform by UV-Vis titration and, occasionally, by FT-IR measurements. Complexes with receptors 2 and 3 are in all cases more stable than those with the control unsubstituted uranyl-salophen 1 , showing that in addition to the primary binding force provided by coordination of the carbonyl oxygen to the uranium, a significant driving force for complexation, typically in the range of 2-3 kcal/mol, results from van der Waals interactions of the guest with the aromatic walls. Replacement of the phenyl group in 3 with larger aromatic residues to give 4 and 5 , led to enhanced complex stabilities, due to more extended contact surfaces between host and guest.

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.