Regiospecific N-alkyl substitution tunes the molecular packing of high-performance non-fullerene acceptors.

The rapid development of non-fullerene acceptors (NFAs) with strong near-infrared absorption has led to remarkably enhanced short-circuit current density (Jsc) values in organic solar cells (OSCs). NFAs based on the benzotriazole (Bz) fused-ring π-core have great potential in delivering both high Jsc 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, via regiospecific N-alkyl engineering based on the high-performance NFA mBzS-4F that was reported previously. The molecular packing of mBzS-4F, AN6SBO-4F, and EHN6SEH-4F single crystals was analyzed using X-ray crystallography in order to provide a comprehensive understanding of the correlation between the molecular structure, the charge-transporting properties, and the solar cell performance. Compared with the typical honeycomb single-crystal structure of Y6 derivatives, these NFAs exhibit distinctly different molecular packing patterns. The strong interactions of terminal indanone groups in mBzS-4F and the J-aggregate-like packing in EHN6SEH-4F lead to the formation of ordered 3D networks in single-crystals with channels for efficient charge transport. Consequently, OSCs based on mBzS-4F and EHN6SEH-4F show efficient photon-to-current conversions, achieving the highest power conversion efficiency of 17.48% with a Jsc of 28.83 mA cm-2.

Regulating Surface Termination for Efficient Inverted Perovskite Solar Cells with Greater Than 23% Efficiency.

Passivating 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. Here, we report a rationally designed bifunctional molecule, piperazinium iodide (PI), containing both R2NH and R2NH2+ groups on the same six-membered ring, behaving both as an electron donor and an electron acceptor to react with different surface-terminating ends on perovskite films. The resulting perovskite films after defect passivation show released surface residual stress, suppressed nonradiative recombination loss, and more n-type characteristics for sufficient energy transfer. Consequently, charge recombination is significantly suppressed to result in a high open-circuit voltage (VOC) of 1.17 V and a reduced VOC loss of 0.33 V. A very high power conversion efficiency (PCE) of 23.37% (with 22.75% certified) could be achieved, which is the highest value reported for inverted PVSCs. Our work reveals a very effective way of using rationally designed bifunctional molecules to simultaneously enhance the device performance and stability.

Cationic Polyelectrolyte for Anionic Cyanines: An Efficient Way To Translate Molecular Properties into Material Properties.

In this work, a new phosphonium-containing cationic polyelectrolyte (PE1) 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. This material design strategy enables an efficient translation of the favorable molecular properties of cyanines into macroscopic material properties. One of such complexes exhibits a very large third-order susceptibility over 10-10 esu with low nonlinear optical loss suitable for all optical signal processing.

Nonlinear refraction and absorption measurements of thin films by the dual-arm Z-scan method.

We 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. The subtraction of these signals taken simultaneously effectively cancels the nonlinear signal from the substrate, leaving only the signal from the film. More importantly, the SNR is increased since the correlated noise from effects such as beam-pointing instabilities cancels. To show the versatility of the dual-arm Z-scan method, we perform measurements on semiconductor and organic thin films, some less than 100 nm thick and with thicknesses up to 4 orders of magnitude less than the substrate.

Thermochromic Polymer Film Sensors for Detection of Incipient Thermal Damage in Carbon Fiber⁻Epoxy Composites.

Carbon 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. Thermochromic fluorescent probe molecules have the potential to sense incipient thermal damage more accurately than traditional inspection methods. We have designed a molecule which transitions from a colorless, non-fluorescent state to a colorful, highly fluorescent state when exposed to temperature⁻time combinations that can cause damage in composites. Moreover, this molecule can be dispersed in a polymer film and attached to composite parts as a removable sensor. This work presents an evaluation of the sensor performance of this thermochromic film in comparison to ultrasonic C-scan as a method to detect incipient thermal damage in one of the most widely used carbon fiber⁻epoxy composite systems. Composite samples exposed to varying thermal exposures were used to evaluate the fluorescent thermal sensor films, and the results are compared to the results of ultrasonic imaging and short-beam shear tests for interlaminar shear strength.

Rational Design of Dipolar Chromophore as an Efficient Dopant-Free Hole-Transporting Material for Perovskite Solar Cells.

In 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. Moreover, BTPA-TCNE shows an antiparallel molecular packing (i.e., centrosymmetric dimers) in its crystalline state, which cancels out its overall molecular dipole moment to facilitate charge transport. As a result, BTPA-TCNE can be employed as an effective dopant-free HTM to realize an efficient (PCE ≈ 17.0%) PVSC in the conventional n-i-p configuration, outperforming the control device with doped spiro-OMeTAD HTM.

Facile Incorporation of Pd(PPh3)2Hal Substituents into Polymethines, Merocyanines, and Perylene Diimides as a Means of Suppressing Intermolecular Interactions.

Compounds 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.

Highly Sensitive Built-In Strain Sensors for Polymer Composites: Fluorescence Turn-On Response through Mechanochemical Activation.

A 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.

Supramolecular Assembly of Complementary Cyanine Salt J-Aggregates.

An 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.

Enhanced third harmonic generation by organic materials on high-Q plasmonic photonic crystals.

The 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. The enhanced THG in the hybrid organic-plasmonic materials suggested that such extraordinary nonlinear effects can be used for AOSP devices and wavelength conversion.

Long-pulsed luminescence for the measurement of dissolved oxygen.

Thin-film luminescent sensors were used to measure dissolved oxygen in picoliter volumes for the purpose of monitoring single-cell oxygen consumption rates, and that work served as the motivation for the development of the method described here. A few different platinum porphyrin sensor materials were examined, with all measurements conducted microscopically. By employing convolution theory to understand observed responses, including an unexpected red luminescent emission from an optic, we developed a new, rapid method for the determination of exponential decay lifetime. This new method of long-pulsed luminescence offers substantially improved signal-to-noise ratios for detected signals as long as self-illumination sources are carefully controlled in the experimental set-up.

pH-dependent, thermosensitive polymeric nanocarriers for drug delivery to solid tumors.

Polymeric 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. In this work, we synthesized a series of dual pH- and temperature-responsive block copolymers containing a poly(ε-caprolactone) (PCL) hydrophobic block with a poly(triethylene glycol) block that were copolymerized with an amino acid-functionalized monomer. The block copolymers formed micellar structures in aqueous solutions. An optimized polymer that was functionalized with 6-aminocaproic acid (ACA) possessed pH-sensitive phase transitions at mildly acidic pH and body temperature. Doxorubicin-loaded micelles formed from these polymers were stable at blood pH (~7.4) and showed increased drug release at acidic pH. In addition, these micelles displayed more potent anti-cancer activity than free doxorubicin when tested in a tumor xenograft model in mice.

High-optical-quality blends of anionic polymethine salts and polycarbonate with enhanced third-order non-linearities for silicon-organic hybrid devices.

A 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.

Aggregation induced emission (AIE) of trifluoromethyl substituted distyrylbenzenes.

The 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.

Chemiresistive response of silicon nanowires to trace vapor of nitro explosives.

Silicon 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. Both hydrogen and oxygen plasma treatments can significantly improve the responses, and oxygen plasma changes the majority carrier from p- to n-type on the surface of silicon nanowire thin films. The sensitivity is found to increase when the cross-section of the nanowires decreases.

The effect of dipole moment and electron deficiency of analytes on the chemiresistive response of TiO2(B) nanowires.

Nanostructured 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. The degree of the response was found to be dominated by the electron deficiency of the analytes and molecules with greater electron deficiency produce stronger chemiresistive responses.

Tracking bacterial infection of macrophages using a novel red-emission pH sensor.

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. A piperazine moiety was used as the pH-sensitive group. Because of the strong electron-donating and -withdrawing units conjugated in the sensing moiety M, the fluorophore emitted in the red spectral window, away from the autofluorescence regions of the bacteria. Following the engulfment of sensor-labeled bacteria by macrophages and their subsequent merger with host lysosomes, the resulting low-pH environment enhances the fluorescence intensity of the pH sensors inside the bacteria. Time-lapse analysis of the fluorescent intensity suggested significant heterogeneity of bacterial uptake among macrophages. In addition, qRT-PCR analysis of the bacterial 16 S rRNA gene expression within single macrophage cells suggested that the 16 S rRNA of the bacteria was still intact 120 min after they had been engulfed by macrophages. A toxicity assay showed that the pH sensor has no cytotoxicity towards either E. coli or murine macrophages. The sensor shows good repeatability, a long lifetime, and a fast response to pH changes, and can be used for a variety of bacteria.

Using end groups to tune the linear and nonlinear optical properties of bis(dioxaborine)-terminated polymethine dyes.

Six 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. Closed-aperture Z-scan measurements at 1.3 microm in DMSO indicate that Re(gamma) varies from -2.9x10(-33) to -5.4x10(-33) esu in these systems. The largest magnitude of Re(gamma) was observed for a dye with E-4-styrylphenyl aryl groups. This result can be rationalized using a two-state expression which relates Re(gamma) to the energy and transition dipole moment of the transition from the ground state to the lowest-lying excited state. A nonamethine analogue of this compound was also synthesized and exhibits a slightly larger Re(gamma) with respect to a previously reported bis(dioxaborine)-terminated nonamethine. The extension of conjugation beyond the dioxaborine termini seems to result in an overall increase in Re(gamma). However, the effects are smaller than those found by increasing conjugation in the polymethine bridge due to reduced participation of terminal groups in the HOMO.

Utilization of micelles formed from poly(ethylene glycol)-block-poly(epsilon-caprolactone) block copolymers as nanocarriers to enable hydrophobic red two-photon absorbing emitters for cells imaging.

A 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 264.7 cells. In comparison, the dye in micelles with neutral poly(ethylene glycol) as corona could not be delivered into the cells. Cytotoxicity of the micelle-R constructs was studied using a 3-(4,5-dimethyl thiazol-2-yl)-2,5-diphenyltetrazolium bromide assay. More than 90% of the cells were viable after they were stained with the dye-containing micelles at different concentrations (dye concentrations of 2-6 muM and polymer concentrations of 0.05-0.15 mg/mL) for 16 h. This is the first reported application of a hydrophobic 2,1,3-benzothiadiazole-containing 2PA red emitter delivered into the cytoplasm of cells for bioimaging and toxicity assessment.

Molecular mobility in self-assembled dendritic chromophore glasses.

Increasing 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. Arene-perfluoroarene interactions for coarse self-assembly are found to impose three phase relaxation regimes, with intermediate regimes of 8-15 degrees C in width and apparent activation energies between 40 and 60 kcal/mol to be the most effective for poling. Energetic analyses based on intrinsic friction microscopy (IFA) identify increasing temporal stability with increasing arene size for the low-temperature regime. Electric field poling efficiency is found to be inversely proportional to entropic cooperative contributions that can make up 80% of the overall apparent relaxation energy for the high-temperature regime. The origin for the activation energies below the incipient glass transition temperature, based on complementary molecular dynamic simulations, is tied primarily to noncovalent interactions between chromophore (dipole), dendritic (quadrupole) moieties, and combinations thereof.