The rapid development of non-fullerene acceptors (NFAs) with strong near-infrared absorption has led to remarkably enhanced short-circuit current density () values in organic solar cells (OSCs). NFAs based on the benzotriazole (Bz) fused-ring π-core have great potential in delivering both high and decent open-circuit voltage values due to their strong intramolecular charge transfer with reasonably low energy loss. In this work, we have designed and synthesized a series of Bz-based NFAs, PN6SBO-4F, AN6SBO-4F and EHN6SEH-4F, regiospecific -alkyl engineering based on the high-performance NFA mBzS-4F that was reported previously.
View Article and Find Full Text PDFPassivating surface and bulk defects of perovskite films has been proven to be an effective way to minimize nonradiative recombination losses in perovskite solar cells (PVSCs). The lattice interference and perturbation of atomic periodicity at the perovskite surfaces often significantly affect the material properties and device efficiencies. By tailoring the terminal groups on the perovskite surface and modifying the surface chemical environment, the defects can be reduced to enhance the photovoltaic performance and stability of derived PVSCs.
View Article and Find Full Text PDFIn this work, a new phosphonium-containing cationic polyelectrolyte () has been rationally designed and developed via a facile click-chemistry type postfunctionalization, which can form complexes with highly polarizable anionic cyanines to significantly reduce the strong and random cyanine-cyanine interactions (i.e., aggregation) in the solid-state.
View Article and Find Full Text PDFWe extend the recently developed dual-arm Z-scan to increase the signal-to-noise ratio (SNR) for measuring the nonlinear refraction (NLR) of thin films on thick substrates. Similar to the case of solutes in solution, the phase shift due to NLR in a thin film can often be dominated by the phase shift due to NLR in the much thicker substrate. SNR enhancement is accomplished by simultaneously scanning a bare substrate and the film plus substrate in two separate but identical Z-scan arms.
View Article and Find Full Text PDFCarbon fiber⁻epoxy composites have become prevalent in the aerospace industry where mechanical properties and light weight are at a premium. The significant non-destructive evaluation challenges of composites require new solutions, especially in detecting early-stage, or incipient, thermal damage. The initial stages of thermal damage are chemical rather than physical, and can cause significant reduction in mechanical properties well before physical damage becomes detectable in ultrasonic testing.
View Article and Find Full Text PDFIn this paper, an electron donor-acceptor (D-A) substituted dipolar chromophore (BTPA-TCNE) is developed to serve as an efficient dopant-free hole-transporting material (HTM) for perovskite solar cells (PVSCs). BTPA-TCNE is synthesized via a simple reaction between a triphenylamine-based Michler's base and tetracyanoethylene. This chromophore possesses a zwitterionic resonance structure in the ground state, as evidenced by X-ray crystallography and transient absorption spectroscopies.
View Article and Find Full Text PDFCompounds with polarizable π systems that are susceptible to attack with nucleophiles at C-Hal (Hal = Cl, Br) bonds react with Pd(PPh3)4 to yield net oxidative addition. X-ray structures show that the resulting Pd(PPh3)2Hal groups greatly reduce intermolecular π-π interactions. The Pd-functionalized dyes generally exhibit solution-like absorption spectra in films, whereas their Hal analogues exhibit features attributable to aggregation.
View Article and Find Full Text PDFA new class of rationally designed mechanophores is developed for highly sensitive built-in strain sensors in polymer composites. These mechanophores are designed to regenerate the π-conjugation pathway between the electron donor and electron acceptor by force-induced cleavage of the covalent bond to form a fluorescent dipolar dye.
View Article and Find Full Text PDFAn understanding of structure-property relationships in cyanine dyes is critical for their design and application. Anionic and cationic cyanines can be organized into complementary cyanine salts, offering potential building blocks to modulate their intra/intermolecular interactions in the solid state. Here, we demonstrate how the structures of these complementary salts can be tuned to achieve highly ordered J-type supramolecular aggregate structures of heptamethine dyes in crystalline solids.
View Article and Find Full Text PDFThe enhanced optical nonlinearity enabled by localized plasmonic fields has been well studied for all-optical switching processing (AOSP) devices for future optical communication systems. In this work, plasmonic photonic crystals with a nonlinear polycarbonate/polymethine blend cladding layer are designed to enhance the third harmonic generation (THG) at the telecom wavelengths (~1550 nm). Due to the presence of he two-dimensional (2-D) gold nano-patch arrays with improved Q-factor and high local fields, more than 20 × of enhanced THG signals in the hybrid organic-plasmonic nanostructure are experimentally observed.
View Article and Find Full Text PDFPolymeric micelles are promising carriers for anti-cancer agents due to their small size, ease of assembly, and versatility for functionalization. A current challenge in the use of polymeric micelles is the sensitive balance that must be achieved between stability during prolonged blood circulation and release of active drug at the tumor site. Stimuli-responsive materials provide a mechanism for triggered drug release in the acidic tumor and intracellular microenvironments.
View Article and Find Full Text PDFA series of anionic polymethine dyes with different aromatic counterions are prepared to improve their compatibility as guests in an amorphous polycarbonate host. When they are used as the cladding material for silicon hybrid slot waveguides, four-wave mixing wavelength conversion and two-photon absorption-based optical-power modulation are observed. Such guest-host materials may be attractive candidates for all-optical signal-processing applications.
View Article and Find Full Text PDFThe AIE properties of two trifluoromethyl substituted distyrylbenzene model compounds were compared. The fluorescence quantum efficiency of these molecules can be modulated by tuning their subtle solid-state intermolecular interactions.
View Article and Find Full Text PDFSilicon nanowires are observed to behave as chemically modulated resistors and exhibit sensitive and fast electrical responses to vapors of common nitro explosives and their degradation by-products. The nanowires were prepared with a top-down nano-fabrication process on a silicon-on-insulator wafer. The surface of the silicon nanowires was modified by plasma treatments.
View Article and Find Full Text PDFNanostructured TiO(2)(B) thin films were found to have strong and fast chemiresistive response to nitro-aromatic and nitro-amino explosives recently. In this study, the effects of dipole moment and electron deficiency of the analyte molecules on the chemiresistive response are explored to understand the details of molecular interactions of analytes with the sensor surface which lead to charge depletion and the chemiresistive effect. It was found that the speed of the response is dominated by the polarity of the analytes and molecules with larger dipole moments produce faster responses.
View Article and Find Full Text PDFAnal Bioanal Chem
October 2010
The relationship between bacteria and host phagocytic cells is key to the induction of immunity. To visualize and monitor bacterial infection, we developed a novel bacterial membrane permeable pH sensor for the noninvasive monitoring of bacterial entry into murine macrophages. The pH sensor was constructed using 2-dicyanomethylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran (TCF) as an electron-withdrawing group and aniline as an electron-donating group.
View Article and Find Full Text PDFSix anionic pentamethine dyes with different 2,2-difluoro-4-aryl-1,3,2(2 H)-dioxaborin-6-yl termini were synthesized and isolated as tetra-n-octylammonium salts with a variety of aryl groups appended to increase conjugation beyond the dioxaborine termini. The increased conjugation was expected to decrease the energy of the lowest-lying excited state, and increase the transition dipole moment linking this state to the ground state, which would be anticipated to result in an increase in the real part of the third-order polarizability, Re(gamma). UV/Vis-NIR absorption spectroscopy indicates that the absorption maxima in DMSO vary from 691 to 761 nm, with the longest wavelength transitions observed for a derivative where the aryl group is 4-nitrophenyl.
View Article and Find Full Text PDFIncreasing complexity in bottom-up molecular designs of amorphous structures with multiple relaxation modes demands an integrated and cognitive design approach, where chemical synthesis is guided by both analytical tools and theoretical simulations. In particular, this is apparent for novel organic second-order nonlinear optical materials of self-assembling molecular glasses involving dendritic arene stabilization moieties (phenyl, naphthyl, and anthryl) with electro-optical activities above 300 pm/V. In this study, nanoscale thermo-mechanical analyses yield direct insight into the molecular enthalpic and entropic relaxation modes.
View Article and Find Full Text PDFA hydrophobic two-photon absorbing (2PA) red emitter (R) was successfully incorporated into micelles formed from two block copolymers, poly(epsilon-caprolactone)-block-poly(ethylene glycol)s, for imaging and toxicity studies. In micelles, the chromophore R exhibits a 2PA cross-section of 400 GM (1 GM = 1 x 10(-50) cm(4) s photon(-1) molecule(-1)) at 820 nm, which is among the highest values reported for red 2PA emitters. The micelles with a cationic amino moiety-containing poly(ethylene glycol) corona showed an enhancement of cell internalization and delivered the dye into the cytoplasmic regions of the mouse macrophage RAW 264.
View Article and Find Full Text PDFThis Focus Review describes molecular glasses as a new class of materials for nonlinear optical (NLO) applications, especially for electro-optic (E-O) devices. Examples of E-O molecular glasses are reviewed with a focus on the molecular design of NLO chromophores and solid-state engineering of molecular glasses. Molecular glasses based on dendrimers of multiple chromophores, molecular glass blends of chromophores, and molecular glasses based on reversible self-assembly of chromophores are introduced as promising architectures to prepare morphologically stable molecular glasses with large E-O activities and improved material properties for device applications.
View Article and Find Full Text PDF[reaction: see text] A facile synthetic route has been developed to convert an electron-rich, sterically hindered dialkylaminodienone into a conjugated dialkylaminotrienal with good yield. The derived dialkylaminotetraene-type nonlinear optical chromophores possess an all-trans conformation and can be functionalized with fluoro-dendron to provide proper shape modification for poling. Polymers doped with two examples of these chromophores in high concentrations have been poled to afford ultra-large electrooptic coefficients (r(33)) of 208 and 262 pm/V, respectively, at the measuring wavelength of 1.
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