A strategy for the design of molecules with large two-photon absorption cross sections, delta, was developed, on the basis of the concept that symmetric charge transfer, from the ends of a conjugated system to the middle, or vice versa, upon excitation is correlated to enhanced values of delta. Synthesized bis(styryl)benzene derivatives with donor-pi-donor, donor-acceptor-donor, and acceptor-donor-acceptor structural motifs exhibit exceptionally large values of delta, up to about 400 times that of trans-stilbene. Quantum chemical calculations performed on these molecules indicate that substantial symmetric charge redistribution occurs upon excitation and provide delta values in good agreement with experimental values. The combination of large delta and high fluorescence quantum yield or triplet yield exhibited by molecules developed here offers potential for unprecedented brightness in two-photon fluorescent imaging or enhanced photosensitivity in two-photon sensitization, respectively.
The two-photon absorption properties of a series of bis dialkylamino- or diarylamino-substituted diphenylpolyenes and bis(styryl)benzenes have been investigated. Two-photon absorption cross sections, δ, as large as 1420 × 10-50 cm4 s/photon-molecule have been observed for molecules with this general bis-donor structure. The effect of the type and length of the conjugated chain and of dialkylamino or diarylamino substitution on the position and magnitude of the peak two-photon absorptivity is reported. The transition dipole moments for the transitions between the ground state and the first excited singlet state (M ge) and between the first and second excited singlet states (M ee ‘) have been estimated using experimental data from the one- and two-photon spectra. It was found that increases in chain length result mainly in an increase in M ge, whereas the addition of donor end groups or going from diphenylpolyene- to phenylene-vinylene-type bridges leads primarily to an increase in M ee ‘. The trends in the energy of the lowest excited singlet states and in the transition moments for the diphenylpolyene series as a function of chain length are in agreement with those calculated by quantum mechanical methods. These results furnish a link between structural features in these classes of molecules and the electronic dipole couplings and state energies that control the strength of the two-photon absorption. In bis(aminophenyl)polyenes containing up to four double bonds (m) the lowest excited singlet state is a Bu state, as opposed to the case of simple polyenes and diphenylpolyenes, for which it is an Ag state for m > 2. The relationship of the state ordering in these systems with the observed values of the radiative and nonradiative decay rates is also discussed.
The dielectric permittivity and electric breakdown strength of nanocomposites comprising poly(vinylidene fluoride-co-hexafluoro propylene) and phosphonic acid surface-modified BaTiO(3) nanoparticles have been investigated as a function of the volume fraction of nanoparticles. The mode of binding of pentafluorobenzylphosphonic acid on the BaTiO(3) particles was investigated using infrared and (31)P solid-state nuclear magnetic resonance spectroscopy, and the phosphonic acid was found to form well ordered, tightly bound monolayers. The effective permittivity of nanocomposites with low volume fractions (<50%) was in good agreement with standard theoretical models, with a maximum relative permittivity of 35. However, for nanoparticle volume fractions of greater than 50%, the effective permittivity was observed to decrease with increasing nanoparticle volume fraction, and this was correlated with an increase in porosity of the spin-coated nanocomposite films. The dielectric breakdown strength was also found to decrease with increasing volume fraction of the BaTiO(3) nanoparticles, with an abrupt decrease observed around 10% and a gradual decrease for volume fractions of 20-50%. Comparison of these results with model calculations, using statistical particle packing simulations and effective medium theory for the permittivity and breakdown strength, indicates the important roles of nanoparticle percolation and porosity of the nanocomposites on the dielectric properties. The measured energy density at a field strength of 164 V/mum, well below the breakdown strength, increased to a value of 3.2 J/cm(3) as the nanoparticle volume fraction is increased to 50%, roughly in line with the trend of the permittivity. The calculated maximum energy densities indicate maximal extractable energy (7-8 J/cm(3) at 1 kHz) for two different particle volume fractions, as a result of the interplay of the dependencies of permittivity and breakdown strength on volume fraction.
Materials with high dielectric permittivity are important in electronic components such as capacitors, gate dielectrics, memories, and power-storage devices. [1][2][3][4] Conventional highpermittivity materials such as barium titanate (BT) can be processed into thin films by using chemical solution deposition yielding a relative permittivity (e r ) of about 2500 and relatively low dielectric loss but require high-temperature sintering, which is not compatible with many substrate materials.[ [7][8][9][10] Polymer/ceramic nanocomposites in which high-e r metal oxide nanoparticles such as BT [11,12] and lead magnesium niobate-lead titanate (PMN-PT) [1,13,14] are incorporated into a polymer host are of significant current interest. The combination of high-e r nanoparticles with high-dielectric-strength polymer hosts offers the potential to obtain processable highperformance dielectric materials. Simple solution processing of BT particles in a polymer host generally results in poor film quality and inhomogeneities, which are mainly caused by agglomeration of the nanoparticles. Addition of surfactants, such as phosphate esters and oligomers thereof, can improve the dispersion of BT nanoparticles in host polymers and consequently the overall nanocomposite film quality. [1,13,15] However, in such systems, residual free surfactant can lead to high leakage current and dielectric loss. [16] Thus, approaches to bind surface modifiers to BT nanoparticles via robust chemical bonds are highly desirable. Ramesh et al. have reported on the use of trialkoxysilane surface modifiers for the dispersion of BT nanoparticles in epoxy polymer hosts resulting in nanocomposites with reasonably high e r , up to 45. [12] With the objective of identifying ligands that can form stable bonds to a BT surface through coordination or condensation, we have investigated a series of different ligand functionalities. In this Communication, we report that phosphonic acid ligands effect robust surface modification of BT and related nanoparticles and that the use of particles modified with suitable phosphonic acid ligands leads to well-dispersed BT nanocomposite films with high e r and high dielectric strength.We have investigated the binding of a variety of ligands to the surface of BT nanoparticles, as the stability of the binding on the surface is vital to effective surface modification.[17] We examined the following set of ligands, each bearing an aliphatic octyl chain with a different terminal binding group: C 8 H 17 -X, where X = PO(OH) 2 (OPA), SO 2 ONa (OSA), Si(OCH 3 ) 3 (OTMOS), and CO 2 H (OCA). Trialkoxysilanes are widely used surface modifiers for silicate, indium tin oxide, and other metal oxide surfaces. Phosphonic acids have been reported to modify TiO 2 , ZrO 2 , and indium tin oxide surfaces [18][19][20] and are thought to couple to the surface of metal oxides either by heterocondensation with surface hydroxyl groups or coordination to metal ions on the surface.[18] Carboxylic acid and sulfonic acid groups may also bind to the surface ...
An internal or external electric field F can drive the chemical structure, bond order alternation, and electronic structure of linear polymethine dyes from a neutral, bond-alternated, polyene-like structure, through a cyanine-like structure, and ultimately to a zwitterionic (charge-separated) bond-alternated structure. As the structure evolves under the influence of F, the linear polarizability alpha, the first hyperpolarizability beta, and the second hyperpolarizability gamma are seen to be derivatives, with respect to F, of their next lower order polarization (for alpha) or polarizability (for beta and gamma). These derivative relations provide a unified picture of the dependence of the polarizability and hyperpolarizabilities on the structure in linear polymethine dyes. In addition, they allow for predictions of structure-property relations of higher order hyperpolarizabilities.
A series of organic salts, in which the cation has been designed to have a large molecular hyperpolarizability, has been prepared. Variation of the counterion (anion) in many cases leads to materials with large powder second harmonic generation efficiencies, the highest of which is roughly 1000 times that of a urea reference.
A two-photon-activatable photoacid generator, based on a bis[(diarylamino) styryl]benzene core with covalently attached sulfonium moieties, has been synthesized. The photoacid generator has both a large two-photon absorption cross section (delta = 690 x 10(-50) centimeter(4) second per photon) and a high quantum yield for the photochemical generation of acid (phiH+ = 0.5). Under near-infrared laser irradiation, the molecule produces acid after two-photon excitation and initiates the polymerization of epoxides at an incident intensity that is one to two orders of magnitude lower than that needed for conventional ultraviolet-sensitive initiators. This photoacid generator was used in conjunction with a positive-tone chemically amplified resist for the fabrication of a three-dimensional (3D) microchannel structure.
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