Model for triplet state engineering in organic light emitting diodes

Engineering the position of the lowest triplet state (T-1) relative to the first excited singlet state (S-1) is of great importance in improving the efficiencies of organic light emitting diodes and organic photovoltaic cells. We have carried out model exact calculations of substituted polyene chains to understand the factors that affect the energy gap between S-1 and T-1. The factors studied are backbone dimerisation, different donor-acceptor substitutions, and twisted geometry. The largest system studied is an 18 carbon polyene which spans a Hilbert space of about 991 x 10(6). We show that for reverse intersystem crossing process, the best system involves substituting all carbon sites on one half of the polyene with donors and the other half with acceptors. (C) 2014 AIP Publishing LLC.

Adsorption isotherms for neutral organic compounds-A hierarchy in modelling: Part II

A two-state model allowing for size disparity between the solvent and the adsorbate is analysed to derive the adsorption isotherm for electrosorption of organic compounds. Explicity, the organic adsorbate is assumed to occupy "n" lattice sites at the interface as compared to "one" by the solvent. The model parameters are the respective permanent and induced dipole moments apart from the nearest neighbour distance. The coulombic interactions due to permanent and induced dipole moments, discreteness of charge effects, and short-range and specific substrate interactions have all been incorporated. The adsorption isotherm is then derived using mean field approximation (MFA) and is found to be more general than the earlier multi-site versions of Bockris and Swinkels, Mohilner et al., and Bennes, as far as the entropy contributions are concerned. The role of electrostatic forces is explicity reflected in the adsorption isotherm via the Gibbs energy of adsorption term which itself is a quadratic function of the electrode charge-density. The approximation implicit in the adsorption isotherm of Mohilner et al. or Bennes is indicated briefly.

Adsorption isotherms for neutral organic compounds-A hierarchy in modelling: Part III

A simple three-state model permitting two different configurational states for the solvent, together with one for the organic adsorbate, is analysed to derive the adsorption isotherm. The implications of this model regarding pseudo-two-state and pseudo-Frumkin adsorption isotherms are indicated. A critique of the earlier theory of Bockris, Devanathan and Müller is presented in brief.

Adsorption isitherms for neutral organic compounds-A hierarchy in modelling: Part IV. Charge of maximum adsorption-Statistical mechanical basis

The charge at which adsorption of orgamc compounds attains a maximum ( \sigma MAX M) at an electrochenucal interface is analysed using several multi-state models in a hierarchical manner The analysis is based on statistical mechamcal results for the following models (A) two-state site parity, (B) two-state muhl-slte, and (C) three-state site parity The coulombic interactions due to permanent and reduced dipole effects (using mean field approximation), electrostatic field effects and specific substrate interactions have been taken into account. The simplest model in the hierarchy (two-state site parity) yields the exphcit dependence of ( \sigma MAX M) on the permanent dipole moment, polarizability of the solvent and the adsorbate, lattice spacing, effective coordination number, etc Other models in the baerarchy bring to hght the influence of the solvent structure and the role of substrate interactions, etc As a result of this approach, the "composition" of oM.x m terms of the fundamental molecular constants becomes clear. With a view to use these molecular results to maxamum advantage, the derived results for ( \sigma MAX M) have been converted into those involving experimentally observable parameters lake Co, C 1, E N, etc Wherever possible, some of the earlier phenomenologlcal relations reported for ( \sigma MAX M), notably by Parsons, Damaskm and Frumkln, and Trasattl, are shown to have a certain molecular basis, vlz a simple two-state sate panty model.As a corollary to the hxerarcbacal modelling, \sigma MAX M and the potential corresponding to at (Emax) are shown to be constants independent of 0max or Corg for all models The lmphcatlon of our analysis f o r OmMa x with respect to that predicted by the generalized surface layer equation (which postulates Om~ and Ema x varlaUon with 0) is discussed in detail Finally we discuss an passing o M. and the electrosorptlon valency an this context.

Adsorption isotherms for neutral organic compounds - A hierarchy in modelling: Part V. Models for the inner layer potential difference in the presence of dipolar adsorption

The relations for the inner layer potential &fference (E) in the presence of adsorbed orgamc molecules are derived for three hterarchlcal models, m terms of molecular constants like permanent &pole moments, polarlzablhtles, etc It is shown how the experimentally observed patterns of the E vs 0 plots (hnear m all ranges of $\sigma^M$, non-linear in one or both regions of o M, etc ) can be understood in a serm-quantltatlve manner from the simplest model in our hierarchy, viz the two-state site panty version Two-state multi-site and three-state (sxte panty) models are also analysed and the slope (3E/80),,M tabulated for these also The results for the Esm-Markov effect are denved for all the models and compared with the earlier result of Parsons. A comparison with the GSL phenomenologlcal equation is presented and its molecular basis, as well as the hmltatlons, is analysed. In partxcular, two-state multa-slte and three-state (site panty) models yield E-o M relations that are more general than the "umfied" GSL equation The posslblhty of vaewlng the compact layer as a "composite medium" with an "effective dlelectnc constant" and obtaimng novel phenomenological descnptions IS also indicated.

Quasi-2D XY Magnetic Properties and Slow Relaxation in a Body Centered Metal Organic Network of [Co-4] Clusters

Octahedral Co2+ centers have been connected by mu(3)-OH and mu(2)-OH2 units forming [Co-4] clusters which are linked by pyrazine forming a two-dimensional network. The two-dimensional layers are bridged by oxybisbenzoate (OBA) ligands giving rise to a three-dimensional structure. The [Co-4] clusters bond with the pyrazine and the OBA results in a body-centered arrangement of the clusters, which has been observed for the first time. Magnetic studies reveal a noncollinear frustrated spin structure of the bitriangular cluster, resulting in a net magnetic moment of 1.4 mu B per cluster. For T > 32 K, the correlation length of the cluster moments shows a stretched-exponential temperature dependence typical of a Berezinskii-Kosterlitz-Thouless model, which points to a quasi-2D XY behavior. At lower temperature and down to 14 K, the compound behaves as a soft ferromagnet and a slow relaxation is observed, with an energy barrier of ca. 500 K. Then, on further cooling, a hysteretic behavior takes place with a coercive field that reaches 5 Tat 4 K. The slow relaxation is assigned to the creation/annihilation of vortex-antivortex pairs, which are the elementary excitations of a 2D XY spin system.

Adsorption-desorption and photocatalytic properties of inorganic-organic hybrid cadmium thiosulfate compounds

Three inorganic-organic hybrid framework cadmium thiosulfate phases have been investigated for adsorption and photodegradation of organic dye molecules. Different classes of organic dyes, viz., triaryl methane, azo, xanthene, anthraquinone, have been studied. The anionic dyes with sulfonate groups appear to readily adsorb on the cadmium thiosulfate compounds in an aqueous medium. The adsorption of the dye molecules, however, does not create any structural changes on the cadmium thiosulfate compounds, though weak electronic interactions have been observed. The adsorbed dyes have been desorbed partially in an alcoholic medium, suggesting possible applications in scavenging specific anionic dyes from the aqueous solutions. Langmuir adsorption/desorption isotherms have been used to model this behavior. UV-assisted (lambda(max) = 365 nm) photocatalytic decomposition studies on the cationic dyes indicate reasonable activity comparable with that of Degussa P-25 (TiO2) catalyst. Sunlight assisted photocatalyti studies have been carried out in detail employing hybrid framework compounds. The Langmuir-Hinshelwood kinetics model, employed to follow the degradation profile of the organic dyes, indicates that the photocatalytic degradation follows the order: triaryl methane > azo > xanthene.

Sound Velocity Anomaly at the Mott Transition: Application to Organic Conductors and V2O3

Close to the Mott transition, lattice degrees of freedom react to the softening of electron degrees of freedom. This results in a change of lattice spacing, a diverging compressibility, and a critical anomaly of the sound velocity. These effects are investigated within a simple model, in the framework of dynamical mean-field theory. The results compare favorably to recent experiments on the layered organic-conductor kappa-(BEDT-TTF)(2)Cu[N(CN)(2)]Cl. We predict that effects of a similar magnitude are expected for V2O3, despite the much larger value of the elastic modulus of this material.

Structural studies of model peptides containing beta-, gamma- and delta-amino acids

The crystal structures of five model peptides Piv-Pro-Gly-NHMe (1), Piv-Pro-beta Gly-NHMe (2), Piv-Pro-beta Gly-OMe (3), Piv-Pro-delta Ava-OMe (4) and Boc-Pro-gamma Abu-OH (5) are described (Piv:pivaloyl; NHMe: N-methylamide; beta Gly:beta-glycine; OMe:O-methyl ester; delta Ava:delta-aminovaleric acid; gamma Abu:gamma-aminobutyric acid). A comparison of the structures of peptides 1 and 2 illustrates the dramatic consequences upon backbone homologation in short sequences. 1 adopts a type II beta-turn conformation in the solid state, while in 2, the molecule adopts an open conformation with the beta-residue being fully extended. Piv-Pro-beta Gly-OMe (3), which differs from 2 by replacement of the C-terminal NH group by an O-atom, adopts an almost identical molecular conformation and packing arrangement in the solid state. In peptide 4, the observed conformation resembles that determined for 2 and 3, with the delta Ava residue being fully extended. In peptide 5, the molecule undergoes a chain reversal, revealing a beta-turn mimetic structure stabilized by a C-H center dot center dot center dot O hydrogen bond.

Effects of electron correlations in conjugated organic molecules and solids

The discrepancies between the non-interacting models and experimental results for conjugated systems is highlighted in this brief review. The interacting model hamiltonians correctly give the forbidden singlet state below the optical gap in polyenes and also explain both the nonvanishing optical gap in polyacetylenes and the vanishing optical gap in symmetric cyanine dyes. The negative spin densities in polyene radicals is also understood in terms of a correlated picture. The role of electron-electron interactions in other strongly correlated systems, such as polydiacetylene and mixed and segregated stack charge transfer solids, are also briefly discussed.

Numerically Exact Study of Polarizabilities and Hyperpolarizabilities of Correlated Conjugated Organic Models

Polarizabilities and Hyperpolarizabilities of conjugated organic chains are calculated using correlated model Hamiltonians. While correlations reduce the Polarizabilities and extend the range of linear response, the Hyperpolarizabilities essentially are unaffected by the same. This explains the apparently large Hyperpolarizabilities of conjugated electronic systems.

Exact static polarizabilities of correlated finite model systems

A finite-field method for calculating exact polarizabilities of correlated conjugated model systems within the valence bond (VB) framework is presented. The correlations reduce the polarizabilities from their noninteracting values and extend the range of linearity to higher external fields. The large nonlinear polarizabilities observed in strongly correlated conjugated organic molecules cannot be directly attributed to electron correlations. The method described can be employed to calculate static polarizabilities for any desired state of a correlated system.

A simple computational model for predicting .pi.-facial selectivity in reductions of sterically unbiased ketones. Relative importance of electrostatic and orbital interactions

Various factore controlling the preferred facial selectivity in the reductions of a number of sterically unbiased ketones have been evaluated using a semiempirical MO procedure. MNDO optimized geometries do not reveal any significant ground-state distortions which can be correlated with the observed face selectivities. Electrostatic effecta due to an approaching reagent were modeled by placing a test negative charge at a fixed distance from the carbonyl carbon on each of the two faces. A second series of calculations was carried out using the hydride ion as a test nucleophile. The latter calculations effectively include orbital interactions involving the u and u* orbitals of the newly formed bond in the reaction. The computed energy differences with the charge model are generally much larger compared to those with the hydride ion. However, both models lead to predictions which are qualitatively consistent with the experimentally determined facial preferences for most of the systems. Thus, electrostatic interactions between the nucleophile and the substrate seem to effectively determine the face selectivities in these molecules. However, there are a few exceptions in which orbital interactions are found to contribute significantly and occasionally reverse the preference dictated by electrostatic effecta. The remarkable succew of the hydride model calculations, in spite of retaining the unperturbed geometries of the substrates, points to the unimportance of torsional effeds and orbital distortions associated with the pyramidalized carbonyl unit in the transition state in most of the substrates considered. Additional experimental results are reported which provide useful calibration for the present computational approach.

Direct versus kinetic exchange in multiband models for organic ferromagnetism

Multiband Hubbard and Pariser-Parr-Pople calculations have been carried out on mixed donor-acceptor (DA) stacks with doubly degenerate acceptor orbitals and nondegenerate donor orbitals at two-thirds filling. Model exact results for 2, 3, and 4 DA units show that McConnell's prediction of high-spin ground states in these systems is, in general, incorrect. The larger phase space available for the low-spin states leads to their kinetic stabilization in preference to high-spin states. However, for large electron-correlation strengths, the direct exchange dominates over the kinetic exchange resulting in a high-spin ground state

Model studies directed towards the synthesis of functionalised chiral A-ring derivatives of taxanes

Model studies, starting from the monoterpene R-carvone, directed towards the synthesis of chiral A-ring derivatives of taxanes with oxygen functionalities at C-2, 9 and 13 carbon atoms as in taxol is described.