Macromolecular nature of nanosheets of quasi‐TiO2 from (tetra‐isopropyl)orthotitanate modified by methacrylic acid

In this paper we concentrate on the general behavior of oxotitanium hydrosol, which was earlier developed by us as a precursor of the TiO₂ nanoparticles and nanocomposite. The oxotitanium hydrosol was synthesized by the chemical decomposition of a molecular complex of the methacrylic acid/(tetra‐isopropyl)orthotitanate (MAA/TIPT) by means of the hydrogen peroxide. The raw product chemical decomposition of MAA/TIPT is the colloidal suspension of the oxotitanium compound in the water. The oxotitanium compound was separated from hydrosol and identified on the basis of X‐ray and Raman spectroscopy investigations. The status of water in the hydrosol was also investigated by the Raman spectroscopy. The photophysical behaviors of the oxotitanium hydrosol on the basis of the light absorption and photoluminescence (PL) investigations are presented. The light absorption (260 nm) and PL emission (313 nm) allow us to identify the inorganic phase of hydrosol as nanosheets' crystallites of quasi‐TiO₂. Macromolecular nature of nanosheets of quasi‐TiO₂ was revealed only for a higher concentration solution of nanosheets' crystallites of quasi‐TiO₂ at the hydrosol. A macromolecular nature of nanosheets of quasi‐TiO₂ by the red shift of absorption edge and PL wavelength with increase in the concentration of the oxotitanium hydrosol as well as the formation of hydrogels and birefringence developed under an influence of mechanical shearing is evidenced. Copyright © 2009 John Wiley & Sons, Ltd.     

Pressure‐Induced Emission Enhancement of a Series of Dicyanovinyl‐Substituted Aromatics: Pressure Tuning of the Molecular Population with Different Conformations

A series of dicyanovinyl‐substituted aromatic compounds (Ar‐DCV; Ar=9‐anthracenyl, 1‐naphthyl, 1‐pyrenyl) with dual fluorescence are prepared, and their emission properties—when molecularly dispersed in a polymer medium—are investigated under pressure perturbation. The total emission intensity is enhanced drastically from ambient pressure up to 70 kbar. Emission 30–107 times more intense than that at ambient pressure is observed at higher pressure. In dual emission, the enhancement of the local excited state (LE state) is significantly different from that of the intramolecular charge‐transfer state (ICT state). The intensity of the ICT emission increases faster (30–370 times) than that of the LE emission (less than 20 times). In accordance with spectroscopic data, emission dynamics at different pressures, and computational studies on the molecular conformations of these compounds, a kinetic model is proposed to explain the effect of pressure on the emissive properties of the Ar‐DCV compounds from the point of view of pressure‐dependent populations of the species in the ground state.     

Synthesis of terpyridine ligands and their complexation with Zn2+ and Ru2+ for optoelectronic applications

A series of soluble conjugated ligands TT , FT , PT , and NT that contained terpyridyl terminal units were synthesized by Heck coupling. These ligands absorbed at 341–434 nm and emitted blue–green light, with maximum at 440–522 nm and photoluminescence quantum yields of 0.15–0.71 in solution. The double‐layer electroluminescent devices with the configuration of ITO/PEDOT/ligand FT , PT , or NT /Ca/Al exhibited a brightness of 43–63 cd/m². These ligands were further reacted with zinc(II) and ruthenium(II) ions and subsequent anion exchange to afford linear and supramolecular complexes. The photophysics of these complexes were investigated. A significant redshift of the emission maximum of the Zn complexes relative to the corresponding ligands was observed. The Ru complexes were used to fabricate photovoltaic devices with the structure ITO/PEDOT/Ru complex/P3HT:PCBM (1:1 wt/wt)/Ca/Al. The power conversion efficiency of these polymer–fullerene bulk heterojunction photovoltaic devices was up to 0.71%. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7702–7712, 2008     

Polarized Absorption,Spontaneous and Stimulated Blue Light Emission of J‐type Tetraphenylbutadiene Monocrystals

Blue amplified spontaneous emission at room temperature is demonstrated from the exposed face of the strongly emitting organic semiconductor 1,1,4,4‐tetraphenyl‐1,3‐butadiene in single crystal form. The symmetry of the crystal and calculation of lattice sums indicate the J‐type organization of the molecular transition moments. The minimum in the lowest exciton dispersion branch, from which emission takes place, is found at the edge of the Brillouin zone leading to a dominant vibronic emission since the zero‐phonon line is forbidden. The observed gain narrowed line is attributed to the vibronic replica which becomes amplified with increased pumping. The reported emission is along the normal to the exposed crystal face, important for the development of vertical cavity geometry lasers based on organic single crystals. The threshold excitation fluence of 400 μJ cm^?2 is comparable to other organic crystalline systems, even if the amplification path is much reduced as a consequence of the vertical geometry. Considering these relevant aspects, the optical characterization of this material is provided. The polarized absorption spectra are reported and the properties of the lowest‐energy excitonic state investigated. Calculation of the electronic transitions for the isolated molecule, lattice sums for the transition at lowest energy, and the symmetry of the crystal allow attributing the largest face of the samples and the observed optical bands in the spectra. Polarized time‐resolved spectra are also reported allowing to identify the intrinsic excitonic emission.     

Ultrafast Decay of the Excited Singlet States of Thioxanthone by Internal Conversion and Intersystem Crossing

The experimental ultrafast photophysics of thioxanthone in several aprotic organic solvents at room temperature is presented, measured using femtosecond transient absorption together with high‐level ab initio CASPT2 calculations of the singlet‐ and triplet‐state manifolds in the gas phase, including computed state minima and conical intersections, transition energies, oscillator strengths, and spin–orbit coupling terms. The initially populated singlet ππ* state is shown to decay through internal conversion and intersystem crossing processes via intermediate nπ* singlet and triplet states, respectively. Two easily accessible conical intersections explain the favorable internal conversion rates and low fluorescence quantum yields in nonpolar media. The presence of a singlet–triplet crossing near the singlet ππ* minimum and the large spin–orbit coupling terms also rationalize the high intersystem crossing rates. A phenomenological kinetic scheme is proposed that accounts for the decrease in internal conversion and intersystem crossing (i.e. the very large experimental crescendo of the fluorescence quantum yield) with the increase of solvent polarity.     

Characterization of the Excited States of Indigo Derivatives in their Reduced Forms

A comprehensive characterization of the electronic spectral and photophysical properties of the leuco (reduced) form of several indigo derivatives, including indigo and Tyrian Purple, with di‐, tetra‐, and hexa‐substitution, was obtained in solution. The characterization involves absorption, fluorescence, and triplet–triplet absorption spectra, together with quantitative measurements of quantum yields of fluorescence, ?_F (0.46–0.04), intersystem crossing, ?_T (0.013–0.034), internal conversion, ?_IC, and the corresponding lifetimes. The position and degree of substitution promote differences in the spectral and photophysical properties displayed by the investigated leuco derivatives. The ?_F values are about two orders of magnitude higher than those previously obtained for the corresponding keto forms. Also in contrast with the behavior found for the keto forms, the S₁～～→T₁ intersystem crossing is an efficient route for the excited‐state deactivation channel. These findings strengthen the fact that, in contrast to keto indigo where the internal conversion dominates the deactivation of the excited‐state, with leuco indigo (and derivatives), the excited state deactivation involves competition between internal conversion, triplet state formation, and fluorescence. A time‐resolved investigation of one of the compounds in glycerol showed the presence of a photoisomerization process.     

Conjugated copolymers comprised cyanophenyl‐substituted spirobifluorene and tricarbazole‐triphenylamine repeat units for blue‐light‐emitting diodes

A series of conjugated blue‐light‐emitting copolymers, PTC‐1 , PTC‐2 , and PTC‐3, comprised different ratios of electron‐withdrawing segments (spirobifluorene substituted with cyanophenyl groups) and electron‐donating segments (tricarbazole‐triphenylamines), has been synthesized. The structures of these polymers were characterized and their thermal, photophysical, electrochemical, and electroluminescence properties were measured. Incorporation of rigid spirobifluorene units into the copolymers led to blue‐shifted absorption peaks in dilute toluene solution. Cyclic voltammetric measurement indicated the bandgaps of the polymers were in the range of 2.77–2.94 eV. It was found that increasing cyanophenyl‐spirobifluorene content in the polymer backbone lowered both the HOMO and LUMO energy levels of the copolymers, which was beneficial for electron injection/transporting in the polymer layer of the device. OLED device evaluation indicated that all the polymers emitted sky blue to deep blue light when the pure polymers were used as the emissive layers in the devices with a configuration of ITO/PEDOT:PSS/polymers/CsF/Ca/Al. The devices have been optimized by doping 30 wt % PBD into the polymer layers. Among the doped devices, PTC‐2 showed the best performance with the turn‐on voltage of 3.0 V, maximum brightness of 7257 cd/m², maximum current efficiency of 1.76 cd/A, and CIE coordinates of (0.15, 0.14). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 292–301, 2010     

Imide‐functionalized naphthodithiophene based donor‐acceptor conjugated polymers for solar cells

Donor‐acceptor conjugated polymers containing a new imide‐functionalized naphthodithiophene (INDT) as the acceptor unit and a 2,2'‐bithiophene with varied substituents as the donor unit have been synthesized. The bandgaps of these polymers depend strongly on the dihedral angle of the 2,2'‐bithiophene unit. The 3,3'‐dialkoxy substitution (polymers PDOR / PBOR ) leads to near planar bithiophene conformation due to the well‐known S–O short contact, while the 3,3'‐dialkyl substitution (polymer PDR ) results in significant twisting due to the steric effect. Consequently PDOR / PBOR shows the lowest bandgap of 1.82/1.85 eV while PDR has a bandgap of 2.38 eV. Bulk‐heterojunction solar cells of the polymer/fullerene blends have been fabricated. Preliminary results show that PBOR gives the best device performance with power conversion efficiencies as high as 2.45% in air without any thermal annealing treatment, indicating the promising potential of INDT‐containing conjugated polymers for efficient solar cells. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3818–3828