Synthesis,spectroelectrochemical characterization and solvatochromic studies of arylazoimidazolepalladium(II) catecholates

The ternary complexes, [Pd(RaaiCH₂Ph)(OO)](4–6), where RaaiCH₂Ph = N(1)-benzyl-2-(arylazo)imidazole [p-RC₆H₄N=NC₃H₂N₂CH₂Ph (2), R = H (4), Me (5) and Cl (6)] and (OO) = catechol [catH₂,(a)], 4-t-butylcatechol [tbcatH₂, (b)], 3,5-di-t-butylcatechol [dtbcatH₂, (c)] and tetrachlorocatechol [tccatH₂, (d)], have been prepared and characterized by elemental analyses, i.r., u.v.-vis. and ¹H-n.m.r. data. Cyclic voltammograms suggest four successive redox responses that are highly sensitive to the nature of the substituents. The complexes exhibit a ligand-to-ligand charge transfer (LLCT) band and a negative solvatochromic effect. The position of the band is largely dependent on the substituent type on the catechol frame and is qualitatively assigned as the 3b ₁(cat) → π*(aai) transition. This revised version was published online in June 2006 with corrections to the Cover Date.     

Dynamic solvation in imidazolium-based ionic liquids on short time scales

Steady-state and time-resolved Stokes shift data for the probe coumarin 153 in two imidazoles, six imidazolium-based ionic liquids, and several other solvents are presented. These results are consistent with our original suggestion (J. Phys. Chem. B 2004, 108, 10245-10255) that initial solvation is dominated by the organic moiety of the ionic liquid, and they show that for the imidazole-based liquids initial solvation is in all cases very rapid. Solvation by methylimidazole and butylimidazole is complete in 100 ps, and all of the imidazolium ionic liquids demonstrate similarly rapid initial solvation. Owing to the importance of determining the amount of initial solvation that is missed in a given experiment with finite time resolution, we discuss a method of estimating the intramolecular contribution to the reorganization energy. This method yields 2068 cm(-1) and is compared with an alternative method.     

Photophysical Investigations on Determination of Ionicity and Electronic Structures for the Non-covalent Complexes of Calix[4]resorcinarene with Fullerenes C<Subscript>60</Subscript> and C<Subscript>70</Subscript> in the Solution State

Ground state non-covalent interactions between a macrocyclic receptor, C-methylcalix[4]resorcinarene (1) and fullerenes (C₆₀ and C₇₀) have been studied in benzonitrile by an absorption spectrophotometric method. Absorption bands are located in the visible region due to the charge transfer (CT) transition between 1 and various electron acceptors (including fullerenes), namely, 2,3-dichloro-5,6-dicyano-p-benzoquinone, tetracyanoquinodimethane and p-chloranil. Utilizing the CT absorption bands, various important physicochemical parameters, including oscillator strength, resonance energy, transition dipole strength of all the acceptor-1 complexes and vertical ionization potential of 1 are determined. Job’s method of continuous variation reveals 1:1 stoichiometry between fullerenes and 1. The most fascinating feature of the present study is that 1 binds selectively to C₇₀ compared to C₆₀ as obtained from binding constant (K) data of C₆₀-1 (K_C60-1K_{\mathrm{C}60\mbox{-}\mathbf{1}}) and C₇₀-1 (K_C70-1K_{\mathrm{C}70\mbox{-}\mathbf{1}}) complexes, i.e., K_C60-1=190K_{\mathrm{C}60\mbox{-}\mathbf{1}}=190 dm³⋅mol⁻¹ and K_C70-1=5,800K_{\mathrm{C}70\mbox{-}\mathbf{1}}=5{,}800 dm³⋅mol⁻¹ and selectivity (K_C70-1 /K_C60-1 ) ∼30. Quantum chemical calculations based on hybrid density functional theory estimate the enthalpies of formation of the fullerene-1 complexes in vacuo and provide very good support for selectivity in the K values of the C₇₀ and C₆₀ complexes of 1. The exchange and correlation energies have been calculated using a hybrid DFT functional method. We have opted to use the hybrid DFT functional over the Hartree-Fock method, as it can account for correlation effects also. Molecular electrostatic potential map calculations give a clear picture on the electronic structures of the fullerene-1 complexes.     

Conformational supramolecular isomerism in one-dimensional silver(I) coordination polymer of a flexible bis(bidentate) N,N-donor ligand with p-xylyl spacer

The isolation and structural characterisation of three isomeric silver(I) complexes, 1a, 1b and 2 with the general formula {[AgL(1)]ClO(4)}(n) (where L(1) is a bis(bidentate) N,N-donor ligand derived from the Schiff-base condensation of α,α'-diamino-p-xylene and pyridine-2-carboxaldehyde) are discussed. Single-crystal X-ray structures reveal the polymeric nature for the complexes where all the silver ions are in pseudotetrahedral geometry with the AgN(4) coordination environment. Isomers 1a (Pc space group) and 1b (Cc space group) were crystallised from acetonitrile whereas 2 (C2/c space group) was crystallised during the synthesis from a solvent mixture of dicholormethane and methanol. The flexible ligand (L(1)) adopts only an anti conformation in 1b and the presence of two different anti conformations in the repeating unit results in the formation of a trapezoidal wave polymeric chain. However, both gauche and anti conformations of the ligand are found to be present in the polymeric chains of 1a. In the polymeric chain of 2, only one anti isomer of the ligand is present in the repeating unit resulting in a triangular wave chain. The structure of isomer 1a is solvent induced and solvent plays a major role in the crystal packing of this isomer. One-dimensional coordination polymers 1a, 1b and 2 are related to each other as conformational supramolecular isomers. Additionally, two independent polymeric chains parallel to each other: one triangular wave consisting of only an anti conformation and a trapezoidal wave chain consisting of alternate gauche and anti conformations of the ligand are observed in 1a. This is a rare example of two supramolecular isomers present in the same crystal. Six different conformers of the flexible ligand are observed in the crystals of coordination polymers.     

A simple HPLC method for quantitation of quercetin in herbal extracts

A reversed-phase HPLC method with UV detection was developed for the determination of quercetin. The method produced linear response over a wide concentration range, with an average accuracy of 95% and average intra- and interday variation of 0.75 and 0.3, respectively. The exactness of the method was proven by determining the recovery rates from 50 to 150% of standard concentration, which were found within the acceptable range of 95 to 105%. The method was used for quantitation of quercetin in the extracts of Psidium guajava, Vitis vinifera, and extracts rich in quercetin and other flavonols in the flavonoid family.     

Mechanochemical Synthesis of Functionalized Quinolines by Iodine Mediated Oxidative Annulation

An iodine‐mediated environmentally benign synthesis of multi‐substituted quinoline derivatives is developed using a solvent‐free mechanochemical process. Appropriately designed and easily accessible protecting group‐free aniline derivatives were used for the oxidative annulation reaction, and a series of quinoline derivatives with variable functionalities were synthesized up to 89 % isolated yield. Importantly, the activator iodine remains in the quinoline molecule and promotes further functionalizations. The present methodology is beneficial with regard to operational simplicity and mild reaction conditions.     

Triazine‐based Organic Polymer‐catalysed Conversion of Epoxide to Cyclic Carbonate under Ambient CO2 Pressure

In this work we have achieved epoxide to cyclic carbonate conversion using a metal‐free polymeric catalyst under ambient CO₂ pressure (1.02 atm) using a balloon setup. The triazine containing polymer (CYA‐ANIS) was prepared from cyanuric chloride (CYA?Cl) and o‐dianisidine (ANIS) in anhydrous DMF as solvent by refluxing under the N₂ gas environment. The presence of triazine and amine functional groups in the polymer results in the adsorption of CO₂ up to 7 cc/g at 273 K. This inspired us to utilize the polymer for the conversion of a series of functionalised epoxides into their corresponding cyclic carbonates in the presence of tetrabutyl ammonium iodide (TBAI) as co‐catalyst. The product has wide range of applications like solvent in lithium ion battery, precursor for polycarbonate, etc. The catalyst was efficient for the conversion of different mono and di‐epoxides into their corresponding cyclic carbonates under atmospheric pressure in the presence of TBAI as co‐catalyst. The study indicates that epoxide attached with electron withdrawing groups (like, CH₂Cl, glycidyl ether, etc.) displayed better conversion compared to simple alkane chain attached epoxides. This is mainly due to the stabilization of electron rich intermediates produced during the reaction (e. g. epoxide ring opening or CO₂ incorporation into the halo‐alkoxide anion). This catalyst mixture was capable to maintain its reactivity up to five cycles without losing its activity. Post catalytic characterization clearly supports the heterogeneous and recyclable nature of the catalyst.     

A Synergistic Approach towards Optimization of Coupled Cluster Amplitudes by Exploiting Dynamical Hierarchy

The coupled cluster iteration scheme for determining the cluster amplitudes involves a set of nonlinearly coupled difference equations. In the space spanned by the amplitudes, the set of equations are analyzed as a multivariate time-discrete map where the concept of time appears in an implicit manner. With the observation that the cluster amplitudes have difference in their relaxation timescales with respect to the distributions of their magnitudes, the coupled cluster iteration dynamics are considered as a synergistic motion of coexisting slow and fast relaxing modes, manifesting a dynamical hierarchical structure. With the identification of the highly damped auxiliary amplitudes, their time variation can be neglected compared to the principal amplitudes which take much longer time to reach the fixed points. We analytically establish the adiabatic approximation where each of these auxiliary amplitudes are expressed as unique parametric functions of the collective principal amplitudes, allowing us to study the optimization with the latter taken as the independent degrees of freedom. Such decoupling of the amplitudes significantly reduces the computational scaling without sacrificing the accuracy in the ground state energy as demonstrated by a number of challenging molecular applications. A road-map to treat higher order post-adiabatic effects is also discussed.     

Predicting the Surface Tension of Deep Eutectic Solvents: A Step Forward in the Use of Greener Solvents

Deep eutectic solvents (DES) are an important class of green solvents that have been developed as an alternative to toxic solvents. However, the large-scale industrial application of DESs requires fine-tuning their physicochemical properties. Among others, surface tension is one of such properties that have to be considered while designing novel DESs. In this work, we present the results of a detailed evaluation of Quantitative Structure-Property Relationships (QSPR) modeling efforts designed to predict the surface tension of DESs, following the Organization for Economic Co-operation and Development (OECD) guidelines. The data set used comprises a large number of structurally diverse binary DESs and the models were built systematically through rigorous validation methods, including ‘mixtures-out’- and ‘compounds-out’-based data splitting. The most predictive individual QSPR model found is shown to be statistically robust, besides providing valuable information about the structural and physicochemical features responsible for the surface tension of DESs. Furthermore, the intelligent consensus prediction strategy applied to multiple predictive models led to consensus models with similar statistical robustness to the individual QSPR model. The benefits of the present work stand out also from its reproducibility since it relies on fully specified computational procedures and on publicly available tools. Finally, our results not only guide the future design and screening of novel DESs with a desirable surface tension but also lays out strategies for efficiently setting up silico-based models for binary mixtures.