Mononuclear and Dinuclear Copper Complexes of Tridentate Redox-active Ligands with Tunable H-bonding Donors: Structure,Spectroscopy and H+/e− Reactivity

In this research article, we describe the synthesis and characterization of mononuclear and dinuclear Cu complexes bound by a family of tridentate redox-active ligands with tunable H-bonding donors. The mononuclear Cu-anion complexes were oxidized to the corresponding “high-valent” intermediates by oxidation of the redox-active ligand. These species were capable of oxidizing phenols with weak O−H bonds via H-atom abstraction. Thermodynamic analysis of the H-atom abstractions, which included reduction potential measurements, pK_a determination and kinetic studies, revealed that modification of the anion coordinated to the Cu and changes in the H-bonding donor did not lead to major differences in the reactivity of the “high-valent” CuY complexes (Y: hydroxide, phenolate and acetate), which indicated that the tridentate ligand scaffold acts as the H⁺ and e⁻ acceptor.     

Chiral manganese complexes with pinene appended tetradentate ligands as stereoselective epoxidation catalysts

A novel family of chiral manganese complexes Lambda-1(CF(3)SO(3)) and Delta-2(CF(3)SO(3)), have been stereoselectively prepared, characterized and studied as epoxidation catalysts. The complexes are structurally related to [Mn(II)(CF(3)SO(3))(2)(alpha-MCP)] (MCP=N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)cyclohexane-trans-1,2-diamine), recently reported as a very efficient epoxidation catalyst in combination with peracetic acid. Pinene rings have been fused to the 4 and 5 positions of the two pyridine groups of the ligand, giving rise to complexes where the two labile binding sites of the manganese ion are confined in a better-defined chiral pocket than in the parent [Mn(II)(CF(3)SO(3))(2)(alpha-MCP)]. Chirality in these complexes arises from the stereochemistry of the trans-diaminocyclohexane ring, from the pinene ring and also from the topological chirality adopted by the ligand upon binding to the manganese ion. While previous studies have demonstrated that small modifications in the structure of the MCP ligand result in a dramatic loss of efficiency, Lambda-1(CF(3)SO(3)) and Delta-2(CF(3)SO(3)) exhibit comparable catalytic activity to [Mn(II)(CF(3)SO(3))(2)(alpha-MCP)]. In addition, the complexes exhibit a remarkable stereoselectivity (up to 46% ee) in the epoxidation of selected substrates. The results reported in this work point towards modification of the 4 and 5 positions of the pyridine groups as a new strategy towards the design of stereoselective versions of this family of highly active and environmentally benign epoxidation catalysts.     

Self‐Assembled Tetragonal Prismatic Molecular Cage Highly Selective for Anionic π Guests

The metal‐directed supramolecular synthetic approach has paved the way for the development of functional nanosized molecules. In this work, we report the preparation of the new nanocapsule 3? (CF₃SO₃)₈ with a A₄B₂ tetragonal prismatic geometry, where A corresponds to the dipalladium hexaazamacrocyclic complex Pd‐1 , and B corresponds to the tetraanionic form of palladium 5,10,15,20‐tetrakis(4‐carboxyphenyl)porphyrin ( 2 ). The large void space of the inner cavity and the supramolecular affinity for guest molecules towards porphyrin‐based hosts converts this nanoscale molecular 3D structure into a good candidate for host–guest chemistry. The interaction between this nanocage and different guest molecules has been studied by means of NMR, UV/Vis, ESI‐MS, and DOSY experiments, from which highly selective molecular recognition has been found for anionic, planar‐shaped π guests with association constants (K_a) higher than 10⁹ M ^?1, in front of non‐interacting aromatic neutral or cationic substrates. DFT theoretical calculations provided insights to further understand this strong interaction. Nanocage 3? (CF₃SO₃)₈ can not only strongly host one single molecule of M(dithiolene)₂ complexes (M=Au, Pt, Pd, and Ni), but also can finely tune their optical and redox properties. The very simple synthesis of both the supramolecular cage and the building blocks represents a step forward for the development of polyfunctional supramolecular nanovessels, which offer multiple applications as sensors or nanoreactors.     

The effects of Au aggregate morphology on surface-enhanced Raman scattering enhancement

We have identified empirically a relationship between the surface morphology of small individual aggregates (<100 Au nanoparticles) and surface-enhanced Raman scattering (SERS) enhancement. We have found that multilayer aggregates generated greater SERS enhancement than aggregates limited to two-dimensional (2D) or one-dimensional structures, independent of the number of particles. SERS intensity was measured using the 730 cm(-1) vibrational mode of the adsorbed adenine molecule on 75 nm Au particles, at an excitation wavelength of 632.8 nm. To gain insight into these relationships and its mechanism, we developed a qualitative model that considers the collections of interacting Au nanoparticles of an individual aggregate as a continuous single entity that retains its salient features. We found the dimensions of the modeled surface features to be comparable with those found in rough metal surfaces, known to sustain surface plasmon resonance and generate strong SERS enhancement. Among the aggregates that we have characterized, a three 75 nm nanoparticle system was the smallest to generate strong SERS enhancement. However, we also identified single individual Au nanoparticles as SERS active at the same wavelength, but with a diameter twice in size. For example, we observed a symmetric SERS-active particle of 180 nm in diameter. Such individual nanoparticles generated SERS enhancement on the same order of magnitude as the small monolayer Au aggregates, an intensity value significantly stronger than predicted in recent theoretical studies. We also found that an aspect of our model that relates the dimensions of its features to SERS enhancement is also applicable to single individual Au particles. We conclude that the size of the nanoparticle itself, or the size of a protrusion of an irregularly shaped single Au particle, will contribute to SERS enhancement provided that its dimensions satisfy the conditions for plasmon resonance. In addition, by considering the ratio of the generated intensities of typical 2D Au aggregates to the enhancement of individual SERS-active particles, a value of approximately 2 is determined. Its moderate value suggests that it is not the aggregation effect that is responsible for much of the observed SERS enhancement but the surface region associated with the SERS-active site.     

Template-guided organization of chromonic liquid crystals into micropatterned anisotropic organic solids

We have developed an approach to generate micropatterns of anisotropic organic materials which exploits the self-organization, driven by pi-stacking and hydrophobic interactions, of an ionic perylenebis(dicarboximide) in aqueous solutions.     

Ordering in asymmetric block copolymer films by a compressible fluid

We examine the morphological structures of asymmetric poly(ethylene oxide)-b-poly(1,1'-dihydroperflurooctyl methacrylate) (PEO-b-PFOMA) thin films upon annealing in a compressible fluid, supercritical CO2 (Sc-CO2). The strong affinity between PFOMA and CO2 is found to induce phase segregation when annealing PEO-b-PFOMA films at the same temperature as compared with vacuum. In vacuum, PEO-b-PFOMA films remain disordered from 80 to 180 degrees C, whereas, in Sc-CO2 at 13.9 MPa, an upper order-disorder transition (UODT) between 116 and 145 degrees C is found. In Sc-CO2, the observed ordered structure is layers of PEO spheres embedded in the matrix of PFOMA, followed by a brush layer, in which PEO wets the substrate. The swelling isotherms of PFOMA and PEO in CO2 are correlated with the Sanchez-Lacombe equation of state (SLEOS) to estimate the interaction parameters, XPFOMA-CO2 and XPEO-CO2. The phase segregation (order) induced by CO2 relative to vacuum at a given temperature is explained in terms of two factors: (1) copolymer volume fraction upon dilution with CO2, phi, and (2) the relative interaction parameter, DeltaX= XPEO-CO2 - XPFOMA-CO2. The latter factor favors order and is dominant at low temperatures over the phi factor, which always favors disorder. At high temperatures (above the T(ODT)), the preferential swelling of PFOMA by CO2 is less pronounced ( DeltaX decreases), and the copolymer is disordered.     

Umbilic point screening in random optical fields

Umbilic points--singular points of curvature characterized by a fractional topological charge q=+/-1/2--are the most numerous of all special points in the landscape of random optical fields (speckle patterns), outnumbering maxima, minima, saddle points, and optical vortices. To the best of our knowledge, we present the first experimental evidence that positive and negative umbilic points screen one another. Theory predicts that in the absence of screening the charge variance in a bounded region is proportional to the area of the region, whereas in the presence of screening the variance is drastically reduced and is proportional to the perimeter. Our data confirm this latter prediction and provide the first estimates of the screening lengths for umbilic points of the intensity and of the amplitude (field modulus).