Phosphoryl- and phosphonium-bridged viologens as stable two- and three-electron acceptors for organic electrodes.

Low molecular weight organic molecules that can accept multiple electrons at high reduction potentials are sought after as electrode materials for high-energy sustainable batteries. To date their synthesis has been difficult, and organic scaffolds for electron donors significantly outnumber electron acceptors. Herein, we report the synthesis and electronic properties of two highly electron-deficient phosphaviologen derivatives from a phosphorus-bridged 4,4'-bipyridine and characterize their electrochemical properties. Phosphaviologen sulfide (PVS) and P-methyl phosphaviologen (PVM) accept two and three electrons at high reduction potentials, respectively. PVM can reversibly accept three electrons between 3-3.6 V vs. Li/Li+ with an equivalent molecular weight of 102 g (mol-1 e-) (262 mA h g-1), making it a promising scaffold for sustainable organic electrode materials having high specific energy densities.

Molecular Considerations for Mesophase Interaction and Alignment of Lyotropic Liquid Crystalline Semiconducting Polymers.

Intermolecular interactions in conjugated polymers influence crystallinity, self-assembly, and packing motif, factors which in turn crucially impact charge transport properties such as carrier mobility in organic electronic devices. Correlated alignment of molecular and crystalline morphologies provides direct pathways for charge carriers to follow; however, the role of intermolecular interactions in achieving this is unexplored. Herein, we synthesize a series of lyotropic liquid crystalline conjugated polymers with variable side-chain structure to lend distinct steric repulsion and van der Waals attractive forces to each mesophase. We use this to investigate the role of intermolecular interactions on mesophase alignment. The strength of intermolecular interaction for each mesophase is compared by measuring melting temperature, π-stacking distance, and the Maier-Saupe interaction parameter. In general we find that side-chain structure can impact interaction strength by varying steric repulsion and backbone attractions and that the Maier-Saupe interaction parameters correlate with higher degrees of alignment after shearing, achieving a dichroic absorbance ratio of up to 2. This observation is used to develop equilibrium processing methods for fabricating macroscopically aligned polymer substrates used in transistors, improving mobility by a factor of 3 compared to spin-coated devices.

Role of Tethered Ion Placement on Polymerized Ionic Liquid Structure and Conductivity: Pendant versus Backbone Charge Placement.

The role of ion placement was systematically investigated in imidazolium bis(trifluoromethane)sulfonimide (ImTFSI) polymerized ionic liquids (PILs) containing pendant charges and charges in the backbone (sometimes called ionenes). The backbone PILs were synthesized via a facile step growth route, and pendant PILs were synthesized via RAFT. Both PILs were designed to have nearly identical charge density, and the conductivity was found to be substantially enhanced in the backbone PIL systems even after accounting for differences in the glass transition temperature (Tg). Wide-angle X-ray scattering (WAXS) revealed an invariance in the location of the amorphous halo between the two systems, while the anion-anion correlation peak was shifted to lower scattering wavevector (q) in the backbone PILs. This indicates an increase in the correlation length of ions and is consistent with charge transport along a more correlated pathway following the polymer backbone. Due to the linear nature of the backbone PILs, crystallization was observed and correlated with changes in conductivity. Upon crystallization, the conductivity dropped, and eventually, two populations of mobile ions were observed and attributed to ions in the amorphous and near-crystallite regions. The present work demonstrates the important role of ion placement on local structure and conductivity as well as the ability of backbone PILs to be used as controllable optical or dielectric materials based on crystallization or processing history.

Evidence for the chain-growth synthesis of statistical π-conjugated donor-acceptor copolymers.

The synthesis of a series of dithienosilole-benzotriazole donor-acceptor statistical copolymers with various donor-acceptor ratios is reported, prepared by Kumada catalyst-transfer polymerization. Statistical copolymer structure is verified by (1) H NMR and optical absorption spectroscopy, and supported by density functional theory (DFT) calculations. The copolymers exhibit a single optical absorption band that lies between dithienosilole and benzotriazole homopolymers, which shifts with varying donor-acceptor content. A chain extension experiment using a partially consumed benzotriazole solution as a macroinitiator followed by addition of dithienosilole leads to the synthesis of a statistical dithienosilole-benzotriazole block copolymer from a pure benzotriazole block, demonstrating that both chain extension and simultaneous monomer incorporation are possible using this methodology.

Controlled Synthesis of Fully π-Conjugated Donor-Acceptor Block Copolymers Using a Ni(II) Diimine Catalyst.

We use a Ni(II) diimine catalyst to prepare the first examples of the controlled synthesis of electron-rich/electron-deficient all-conjugated diblock copolymers. These catalysts are able to control polymerizations of both electron-rich and electron-deficient monomers, which we attribute to strong association to both monomer types. Block copolymers are prepared by controlled chain extension, and their structure is verified by gel permeation chromatography, 1H NMR, electrochemistry, calorimetry, and atomic force microscopy.

Designing and refining Ni(II)diimine catalysts toward the controlled synthesis of electron-deficient conjugated polymers.

Electron-deficient π-conjugated polymers are important for organic electronics, yet the ability to polymerize electron-deficient monomers in a controlled manner is challenging. Here we show that Ni(II)diimine catalysts are well suited for the controlled polymerization of electron-deficient heterocycles. The relative stability of the calculated catalyst-monomer (or catalyst-chain end) complex directly influences the polymerization. When the complex is predicted to be most stable (139.2 kJ/mol), these catalysts display rapid reaction kinetics, leading to relatively low polydispersities (∼1.5), chain lengths that are controlled by monomer:catalyst ratio, controlled monomer consumption up to 60% conversion, linear chain length growth up to 40% conversion, and 'living' chain ends that can be readily extended by adding more monomer. These are desirable features that highlight the importance of catalyst design for the synthesis of new conjugated polymers.

Evolution of the electron mobility in polymer solar cells with different fullerene acceptors.

We investigate the evolution of the electron mobility of two different acceptors, [6,6]-phenyl C71 butyric acid methyl ester (PC71BM) and indene-C60 bisadduct (ICBA), in a poly(3-hexylthiophene) blend solar cell during a prolonged thermal aging process. High electron mobility does not correlate with the best device performance in our study of the P3HT:PC71BM and P3HT:ICBA systems. Very little changes are observed in the polymer crystallinity as a function of time. The evolution of the acceptor appears to be the dominant factor that leads to long-term changes in the device performance. The electron mobility evolves differently in PC71BM and ICBA systems, which highlights the importance of the fullerene molecular structure.

Template directed synthesis of plasmonic gold nanotubes with tunable IR absorbance.

A nearly parallel array of pores can be produced by anodizing aluminum foils in acidic environments. Applications of anodic aluminum oxide (AAO) membranes have been under development since the 1990's and have become a common method to template the synthesis of high aspect ratio nanostructures, mostly by electrochemical growth or pore-wetting. Recently, these membranes have become commercially available in a wide range of pore sizes and densities, leading to an extensive library of functional nanostructures being synthesized from AAO membranes. These include composite nanorods, nanowires and nanotubes made of metals, inorganic materials or polymers. Nanoporous membranes have been used to synthesize nanoparticle and nanotube arrays that perform well as refractive index sensors, plasmonic biosensors, or surface enhanced Raman spectroscopy (SERS) substrates, as well as a wide range of other fields such as photo-thermal heating, permselective transport, catalysis, microfluidics, and electrochemical sensing. Here, we report a novel procedure to prepare gold nanotubes in AAO membranes. Hollow nanostructures have potential application in plasmonic and SERS sensing, and we anticipate these gold nanotubes will allow for high sensitivity and strong plasmon signals, arising from decreased material dampening.

Potential-dependent interaction of DOPC liposomes with an octadecanol-covered Au(111) surface investigated using electrochemical methods coupled with in situ fluorescence microscopy.

The potential-controlled incorporation of DOPC liposomes (100 nm diameter) into an adsorbed octadecanol layer on Au(111) was studied using electrochemical and in situ fluorescence microscopy. The adsorbed layer of octadecanol included a small amount of a lipophilic fluorophore-octadecanol modified with BODIPY-to enable fluorescence imaging. The deposited octadecanol layer was found not to allow liposomes to interact unless the potential was less than -0.4 V/SCE, which introduces defects into the adsorbed layer. Small increases in the capacitance of the adsorbed layer were measured after introducing the defects, allowing the liposomes to interact with the defects and then annealing the defects at 0 V/SCE. A change in the adsorbed layer was also signified by a more positive desorption potential for the liposome-modified adsorbed layer as compared to that for an adsorbed layer that was porated in a similar fashion but without liposomes present in the electrolyte. These subtle changes in capacitance are difficult to interpret, so an in situ spectroscopic study was performed to provide a more direct measure of the interaction. The incorporation of liposomes should result in an increase in the fluorescence measured because the fluorophore should become further separated from the gold surface, reducing the efficiency of fluorescence quenching. No significant increase in the fluorescence of the adsorbed layer was observed during the potential pulses used in the poration procedure in the absence of liposomes. In the presence of liposomes, the fluorescence intensity was found to depend on the potential and time used for poration. At 0 V/SCE, no significant change in the fluorescence was observed for defect-free adsorbed layers. Changing the poration potential to -0.4 V/SCE caused significant increases in the fluorescence and the appearance of new structural features in the adsorbed layers that were more easily observed during the desorption procedure. The extent of fluorescence changes was found to be strongly dependent on the nature of the adsorbed layer under investigation, which suggests that the poration and liposome interaction are dependent on the quality of the adsorbed layer and its ease of poration through changes in the electrode potential.