Microwave-assisted synthesis of bipyrazolyls and pyrazolyl-substituted pyrimidines

We describe the preparation of 1,4′-bipyrazolyls and 4-pyrazolylpyrimidines by the reaction of 2-pyrazolyl-3-dimethylamino acrylate and acrylonitrile with double nucleophilic reagents such as hydrazines, urea and guanidine. Reactions were performed under microwave irradiation in 5-60 min. This is a useful procedure for the preparation of valuable compounds with applications in medicinal and coordination chemistry.     

Interactions of diethylenetriaminepentaacetic acid (dtpa) and triethylenetetraaminehexaacetic acid (ttha) with major components of natural waters

The binding ability of diethylene triamine pentaacetate (dtpa(5-)) and triethylene tetraamine hexaacetate (ttha(6-)) ligands towards major components, H(+), Na(+), Mg(2+) and Ca(2+), of natural waters was studied in both single and mixed ionic media at different ionic strengths and at T=25 degrees C. Some measurements, performed in Mg(2+)-Ca(2+) mixtures, allowed us to find the formation of new mixed species MgCa(dtpa), MgCa(ttha) and MgCaH(ttha), here reported for the first time. All the complexes formed in the various systems were characterized in terms of both stoichiometry and stability, and an attempt was made to find general rules for the stability of mixed metal complexes in comparison with that of simple species. To obtain quantitative information on the complexing ability of dtpa and ttha in seawater, measurements have been carried out in artificial seawater ionic medium (Na(+), K(+), Ca(2+), Mg(2+), Cl(-) and SO(4)(2-)). Calculations, performed by considering the salt mixture as single salt BA, allowed us to find some quite stable B(i)H(j)L species. Under the natural seawater conditions [S(salinity)=35], we found for the most important species logbeta( B(dtpa))=9.64 and. Literature data comparison is also reported.     

Poly(4‐vinylpyridine) as the host ligand of metal‐containing chromophores for second‐order nonlinear optical active materials

Two formulas of grafted polymers with metal‐containing chromophores, potentially suitable for second‐order nonlinear optics applications, are described. Two chromophores were obtained from a tridentate ligand coordinated to Cu(II) or Pd(II) ions. The organometallic chromophore fragments were grafted to poly(4‐vinylpyridine) by the pyridinic nitrogen of the host polymer. Some qualities displayed by the new metallated polymers are remarkable: (1) a high value of the first hyperpolarizability coefficient of the chromophores, (2) a high content of the grafted chromophore in the polymers (up to 60 wt %), (3) a considerable increase in the glass‐transition temperatures (up to 240 °C), (4) good thermal stability in air (ca. 280 °C), and (5) good optical transparency of the films. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2987–2993, 2002     

Optimizing Cs-exchange in titanosilicate with the mineral pharmacosiderite topology: framework substitution of Nb and Ge

Titanosilicates with complete or partial substitution of Ge or Nb in the framework and having the mineral pharmacosiderite topology were hydrothermally prepared and their ion-exchange properties towards Cs were studied for Ti/Ge/Si, Ti/Si, Nb/Ti/Si and pure Ge phases. The basis for the differences in the ion exchange properties measured as distribution coefficients (K_d) for these materials are detailed via structural characterization using the Rietveld refinement technique on the X-ray powder diffraction data. The differences in affinity towards Cs⁺ result either from the degree of hydration of the exchanger resulting in different coordination environments or the position of cesium ion in the eight-ring channel.     

New synthetic pathways into dithiazolyl radicals: Preparation and characterisation of 3′-methyl-benzo-1,3,2-dithiazolyl, M’BDTA

A general three-step synthesis to a range of benzo-fused-1,3,2-dithiazolylium salts bearing both electron-withdrawing (CN) and electron-donating (Me) groups is described. This methodology has also been extended to pyridyl derivatives and offers a potential route to a diversity of 1,3,2-dithiazolylium rings and their corresponding 1,3,2-dithiazolyl free radicals. The key steps in the reaction are treatment of a substituted 1,2,-dichlorobenzene with two equivalents of [^tBuS]Na, followed by chlorination to yield the corresponding bis(sulfenyl chloride). Subsequent ring closure with Me₃SiN₃ yields the target 1,3,2-dithiazolylium ring system in good yield. The preparation and crystal structures of 3′-methyl-benzo-1,3,2-dithiazolylium chloride and 3′-methyl-benzo-1,3,2-dithiazolyl are described and the electronic properties of the radical examined through EPR spectroscopy, DFT calculations and variable temperature magnetic susceptibility measurements.     

Identification of Earth Pigments by Applying Hierarchical Cluster Analysis to Solid State Voltammetry. Application to Severely Damaged Frescoes

Multivariate chemometric methods are applied for identifying earth pigments from square‐wave voltammetric measurements performed at pigment‐modified paraffin‐impregnated graphite electrodes allowing for a separation between hematite‐based earths, French ochres, Spanish ochres, siennas, umbers and green earths. This methodology is applied to the identification of the pigments in samples from the ceiling frescoes of Antonio Palomino (dated 1707) in the vaulted nave of the Sant Joan del Mercat church in Valencia (Spain). These frescoes suffered considerable damage by fire during the Spanish Civil War in 1936, resulting in severe chemical and chromatic alterations. Electrochemical data, supported by scanning electron microscopy/energy dispersive X‐ray microanalysis and Raman spectroscopy, indicate that thermal stress induced the transformation of goethite‐based yellow ochres into hematite and magnetite.     

Progress,highlights and perspectives on NiO in perovskite photovoltaics

The power conversion efficiency (PCE) of NiO based perovskite solar cells has recently hit a record 22.1% with a hybrid organic–inorganic perovskite composition and a PCE above 15% in a fully inorganic configuration was achieved. Moreover, NiO processing is a mature technology, with different industrially attractive processes demonstrated in the last few years. These considerations, along with the excellent stabilities reported, clearly point towards NiO as the most efficient inorganic hole selective layer for lead halide perovskite photovoltaics, which is the topic of this review. NiO optoelectronics is discussed by analysing the different doping mechanisms, with a focus on the case of alkaline and transition metal cation dopants. Doping allows tuning the conductivity and the energy levels of NiO, improving the overall performance and adapting the material to a variety of perovskite compositions. Furthermore, we summarise the main investigations on the NiO/perovskite interface stability. In fact, the surface of NiO is commonly oxidised and reactive with perovskite, also under the effect of light, thermal and electrical stress. Interface engineering strategies should be considered aiming at long term stability and the highest efficiency. Finally, we present the main achievements in flexible, fully printed and lead-free perovskite photovoltaics which employ NiO as a layer and provide our perspective to accelerate the improvement of these technologies. Overall, we show that adequately doped and passivated NiO might be an ideal hole selective layer in every possible application of perovskite solar cells.

The power conversion efficiency of NiO based perovskite solar cells has recently hit a record 22.1%. Here, the main advances are reviewed and the role of NiO in the next breakthroughs is discussed.     

Rheology of a lyotropic mesophase through a stress-relaxation experiment

We report on the first rheological study of the structural relaxations in a nematic liquid crystalline phase. Linear dynamic and transient shear experiments were applied to a polydomain nematic phase of the CTAB/water system: a liquid crystalline mixture composed of 28 wt% CTAB at 35 degrees C. The decay of the shear modulus, G(t), was analyzed using the CONTIN inverse Laplace transform to obtain a distribution of relaxation times which were compared with ones from the usual fitting procedure based on a generalized Maxwell model. The behavior of the nematic lyotropic structure of the CTAB/water system is characterized by the presence of both slow and fast relaxation times. These were interpreted as being due to a progressive loss of the lyotropic domain orientation and to the breaking/reforming process of the cylindrical aggregates, respectively.     

From achiral porphyrins to template-imprinted chiral aggregates and further. Self-replication of chiral memory from scratch

The presence of 10-13 M of chiral clusters of aromatic amino acids addresses aggregation of opposite-charged achiral porphyrin towards the formation of smart chiral assemblies. The latter supramolecular complexes are able to self-propagate and transfer their chiral information with a 100% yield. The chiral bias occurs through a correlated sequence of induction, memory, and amplification of chirality that strongly recalls possible prebiotic scenarios.     

DABCO-directed self-assembly of bisporphyrins (DABCO=1,4-diazabicyclo[2.2.2]octane)

Three isomeric zinc bisporphyrins have been prepared by covalently linking together two aminoporphyrins with an isophthalic acid derivative. The porphyrins differ in the substitution pattern on the meso phenyl groups, that is, ortho, meta, or para. Titrations carried out by UV-visible and 1H NMR spectroscopy have been used to map out the stabilities and the stoichiometries of the complexes formed with 1,4-diazabicyclo[2.2.2]octane (DABCO) in chloroform. The ortho- and meta-substituted bisporphyrins form 1:1 intramolecular sandwich complexes. The para-substituted bisporphyrin cannot adopt the cofacial conformation required for this type of complex and forms a higher order 2:2 intermolecular assembly, which is stable over a wide range of DABCO concentrations.