An aqueous solution approach has been utilized to prepare nanolaminates of TiO and ionically conductive LiO-AlO (LiAlO). This new approach utilizes low curing temperatures, resulting in fully oxidized films as demonstrated by Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy. The layered structures have been characterized by scanning electron microscopy, X-ray diffraction, and X-ray reflectivity.
View Article and Find Full Text PDFWe have synthesized a series of aza[8]cycloparaphenylenes containing one, two, and three nitrogens to probe the impact of nitrogen doping on optoelectronic properties and solid state packing. Alkylation of these azananohoops afforded the first donor-acceptor nanohoops where the phenylene backbone acts as the donor and the pyridinium units act as the acceptor. The impact on the optoelectronic properties was then studied experimentally and computationally to provide new insight into the effect of functionalization on nanohoops properties.
View Article and Find Full Text PDFRecently there has been growing interest in the role of coherence in electronic dynamics. Coherent multidimensional spectroscopy has been used to reveal coherent phenomena in numerous material systems. Here we utilize a recent implementation of coherent multidimensional spectroscopy--two-dimensional photocurrent spectroscopy--in which we detect the photocurrent from a PbS quantum dot photocell resulting from its interactions with a sequence of four ultrafast laser pulses.
View Article and Find Full Text PDFHerein we report the synthesis and characterization of a series of 6,12-diarylindeno[1,2-b]fluorenes (IFs). Functionalization with electron donor and acceptor groups influences the ability of the IF scaffold to undergo two-electron oxidation and reduction to yield the corresponding 18- and 22-π-electron species, respectively. A single crystal of the pentafluorophenyl-substituted IF can serve as an active layer in an organic field-effect transistor (OFET).
View Article and Find Full Text PDFA substantial reduction in the rate of irreversible polymer photo-oxidation was observed through the ionic stabilization of the polymer-O charge-transfer complex (CTC) in amorphous polythiophene thin films. Through the incorporation of anionic functionality containing mobile cations, it was found that CTC stability increases with increasing cation charge density. This results in an increased rate of electron transfer to molecular oxygen relative to photosensitization and reaction of O, leading to a reduction in the overall rate of polymer degradation.
View Article and Find Full Text PDFA series of 6,12-bis[(trialkylsilyl)ethynyl]indeno[1,2-b]fluorene-5,11-diones has been synthesized. X-ray crystallographic analysis of these compounds reveals that triisopropylsilyl (TIPS) substitution on the alkyne terminus affords the largest number of intermolecular π-π interactions in the solid state. Conversely, use of trialkylsilyl groups smaller or larger than TIPS furnishes a variety of crystal-packing motifs that contain fewer π-π interactions.
View Article and Find Full Text PDFAs the number of nanoparticle-based products increase in the marketplace, there will be increased potential for human exposures to these engineered materials throughout the product life cycle. We currently lack sufficient data to understand or predict the inherent nanomaterial characteristics that drive nanomaterial-biological interactions and responses. In this study, we utilized the embryonic zebrafish (Danio rerio) model to investigate the importance of nanoparticle (NP) surface functionalization, in particular as it pertains to nanoparticle stability, on in vivo biological responses.
View Article and Find Full Text PDFThree different types of oligothiophene functionalized dihydropyrene photoswitches, (A) 2-naphthoyldimethyldihydropyrenes functionalized at the 4,9-positions with oligothiophenes, (B) benzodimethyldihydropyrenes functionalized at the 4-positions with oligothiophenes and the 10(11)-position with oligothienylcarbonyl groups, and (C) benzodimethyldihydropyrenes functionalized at the 4,5-positions with oligothiophenes, were studied with the goal of using the change in pi-conjugation between the open and the closed forms of the dihydropyrene (DHP)-metacyclophane (CPD) switch to control electrical conductivity. UV-vis absorption studies were performed to measure the extent to which the attached thienyl oligomers were conjugated with the switch and the ability of the switch when opened or closed to affect conjugation. Of the three types of switches studied, those of type A showed the greatest effect.
View Article and Find Full Text PDFWe demonstrate that ionic surface functionalization is well-suited for controlling the electrochemical charging of nanoparticle assemblies. Gold nanoparticles approximately 2 nm in diameter were functionalized with between 0 and approximately 3.3 cationic thiols per particle and the coupled motion of ions and electrons during redox cycling (charging) was followed in situ using an electrochemical quartz-crystal microbalance.
View Article and Find Full Text PDFInterfaces between nanoscale and bulk electroactive materials are important for the design of electronic devices using solution-processed nanoparticles. We report that thin films of hexanethiolate-capped gold nanoparticles with a core diameter of 2.1+/-0.
View Article and Find Full Text PDFThe electrical behavior of the cationic, polyacetylene-based, conjugated ionomer, poly[(2-cyclooctatetraenylethyl)trimethylammonium trifluoromethanesulfonate], sandwiched between gold electrodes is reported. The steady-state current of this mixed ionically/electronically conducting system is assigned to be unipolar diffusive hole transport for voltages below approximately 1.4 V, giving way to bipolar migratory transport above approximately 1.
View Article and Find Full Text PDFDopant counterion diffusion has made the conjugated polymer pn homojunction a challenging target for decades. We report the electrochemical fabrication of a polyacetylene pn homojunction based on internally compensated forms where the dopant counterions are covalently bound to the polymer backbone. After drying under vacuum, the pn junction exhibits diode behavior with the ratio of the forward to reverse current at 2 V being 7.
View Article and Find Full Text PDFUnidirectional electronic current is reported for a device based on the interface between an anionically functionalized and a cationically functionalized polyacetylene. The unidirectional current in this mixed ionically/electronically conducting system is electronic but is regulated by asymmetry in the ionic processes.
View Article and Find Full Text PDFThe electrochemical characterization of thin films of the ionically functionalized polyacetylene analogues poly(tetramethylammonium 2-cyclooctatetraenylethanesulfonate) (P(A)) and poly[(2-cyclooctatetraenylethyl)trimethylammonium trifluoromethanesulfonate] (P(C)) is reported along with an electrochemical approach to the fabrication of interfaces between dissimilarly doped conjugated polymers. Such interfaces are of interest because of the central role analogous interfaces based on silicon play in conventional microelectronics. The cationically functionalized P(C) can be both oxidatively (p-type) and reductively (n-type) doped to a conductive state, whereas the anionically functionalized P(A) can only be p-type doped.
View Article and Find Full Text PDF