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Organic-inorganic hybrid perovskite solar cells have demonstrated unprecedented high power conversion efficiencies in the past few years. Now, the universal instability of the perovskites has become the main barrier for this kind of solar cells to realize commercialization. This situation can be even worse for those tin-based perovskites, especially for CsSnI3, because upon exposure to ambient atmosphere the desired black orthorhombic phase CsSnI3 would promptly lose single crystallinity and degrade to the inactive yellow phase, followed by irreversible oxidation into metallic Cs2SnI6. By alloying CsSnI3 with CsPbI3, we herein report the synthesis of alloyed perovskite quantum dot (QD), CsSn1-xPbxI3, which not only can be phase-stable for months in purified colloidal solution but also remains intact even directly exposed to ambient air, far superior to both of its parent CsSnI3 and CsPbI3 QDs. Ultrafast transient absorption spectroscopy studies reveal that the photoexcited electrons in the alloyed QDs can be injected into TiO2 nanocrystals at a fast rate of 1.12 X 1011 s-1, which enables a high photocurrent generation in solar cells. [ABSTRACT FROM AUTHOR]

A thieno[3,4-b]thiophene-based electron acceptor, ATT-1, is designed and synthesized. ATT-1 exhibits a planar conjugated framework, broad absorption with a large absorption coefficient, and a slightly high LUMO energy level. Bulk-heterojunction (BHJ) solar cells based on PTB7-Th electron donor and ATT-1 electron acceptor delivered power conversion efficiencies of up to 10.07%, which is among the best performances reported for non-fullerene BHJ solar cells using PTB7-Th as the electron donor. [ABSTRACT FROM AUTHOR]

Despite the dominant position of aromatic fluorophores, we report herein the design and synthesis of quinoidal fluorophores based on rarely emissive quinoidal bithiophene. Quinoidal bitheno[3,4-fc]thiophene, QBTT-C6, consisting of cruciform-fused (E)-1,2-bis(5-hexylthiophen-2- yl)ethene and quinoidal bithiophene, shows a fluorescence quantum yield of 8.5%, 25-fold higher than that of the parent quinoidal QBT chromophore, but its maximum emission is at similar wavelengths. QBTT-Ar's featuring intramolecular charge transfer can further shift the maximum emission into the near-infrared region. The intramolecular charge transfer is programmably enhanced by tuning the substituents on the aryl groups from the electron-withdrawing trifluoromethyl to the electron-donating methoxy groups. Unexpectedly, a positive relationship between intramolecular charge transfer and fluorescence quantum yield is observed; as a result, QBTT-FL gives an unprecedentedly high fluorescence quantum yield of up to 53.1% for quinoidal oligothiophenes. With detailed photophysical and theoretical investigations, we demonstrate that the nonradiative intersystem crossing (S1 → T2) is significantly restrained in QBTT-Ar's, which can be attributed to the faster reverse intersystem crossing (T2 → S1) characteristic of a small activation energy. This work reveals the possibility for developing red/near-infrared fluorophores from the less explored quinoidal molecules because of their intrinsically narrow bandgaps. [ABSTRACT FROM AUTHOR]

Thiophene-based materials have occupied a crucial position in the development of organic electronics. However, the energy band gaps of oligo- and polythiophenes are difficult to modulate without resorting to push -pull electronic effects. We describe herein a new series of monodisperse oligo (thieno [3,4- bjthiophene) derivatives with well-defined regioregular structures synthesized efficiently by direct C-H arylation. These compounds show a unique palette of colors and amphoteric redox properties with widely tunable energy band gaps. The capacity to stabilize both cations and anions results in both anodic and cathodic electrochromism. Under excitation, these compounds can produce photoionized states able to interconvert into neutral triplet or form these through singlet exciton fission or intersystem crossing. These features arise from a progressive increase in quinoidization on a fully planar platform making the largest effective conjugation length among hetero-oligomers. Oligo(thieno[3,4-b]thiophene)s might represent the more distinctive family of oligothiophenes of this decade. [ABSTRACT FROM AUTHOR]

Due to the unique crystallinity of poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT), it is an excellent model polymer to study the structure--property relationship in organic devices, especially those relying on junctions of electron- and hole-transporting materials. Here, we report the synthesis and characterization of a series of monodisperse PBTTT oligothiophenes (n = 1-5) and systematically examine the evolution of crystalline behavior, morphology, and interaction with [6,6]-phenyl C61-butyric acid methyl ester (PCBM) as the molecular conjugation length increases. We discovered that fullerene intercalation occurs when there is enough free volume between the side chains to accommodate the fullerene molecule. The intercalation of PCBM is observed beyond BTTT-2 and longer oligomers, likely similar to that of PBTTT. Interestingly, both experiments and molecular simulations show that PCBM intercalation also appears to "catalyze" a more efficient packing of the BTTT-2 dimers. Crystal structure analysis revealed that the straight BTTT-2 side chains form one-dimensional (ID) channels that could perfectly host PCBM but, in the pure material, accommodate the interdigitated side chains from adjacent layers. In the blend with PCBM, these channels are maintained and enable the cocrystallization and intercalation of PCBM. This is the first time the actual sublattice cell of PCBM has been determined from the X-ray data, and demonstration the utility of the oligomers as model systems for their polymer counterparts. Among the organic photovoltaic devices (OPVs) made from the BTTT oligomers and [6,6]-phenyl C71-butyric acid methyl ester (PC71BM) blends, the ones containing the BTTT-2 dimer exhibit the highest performance. [ABSTRACT FROM AUTHOR]

A series of T-shaped polyphilic molecules composed of a rigid linear biphenyl core with a polar glycerol group at each end and one swallow-tail semiperfluorinated lateral chain were synthesized and their thermotropic liquid crystalline (LC) phases were investigated by X-ray diffraction, calorimetry, and microscopy. The compounds have a long alkyl spacer between the aromatic core and the fluorinated CnF2n+1 ends, where n = 4, 6, 8, and 10. Upon melting, all compounds start with lamellar LC phases, followed on heating by a rectangular columnar ribbon phase vnth clmm symmetry. Unusually, a ribbon is a flat bundle of molecular cores highly aligned parallel to the ribbon axis. On further heating, for n = 8 and 10, this phase is succeeded by a bicontinuous cubic phase with Ia3d symmetry. This is a new variant of the "gyroid" phase, with axiaDy oriented rod-like molecular cores forming the skeleton of the two infinite networks and junctions separated by exactly two molecular lengths. In this tricontinuous core-shell structure (aromaticaliphatic-perfluoroalkyl), the polar glycerol domains of appreciable size, contained vwthin the skeleton, can be considered as micellar. [ABSTRACT FROM AUTHOR]

The lipid carrier specificity of the protein N-glycosylation enzyme C. jejuni PglB was tested using a logical, synthetic array of natural and unnatural C10, C20, C30, and C40 polyisoprenol sugar pyrophosphates, including those bearing repeating cis-prenyl units. Unusual, short, synthetically accessible C20 prenols (nerylnerol 1d and geranylnerol 1e) were shown to be effective lipid carriers for PglB sugar substrates. Kinetic analyses for PglB revealed clear KM-only modulation with lipid chain length, thereby implicating successful in vitro application at appropriate concentrations. This was confirmed by optimized, efficient in vitro synthesis allowing >90% of Asn-linked β-N-GlcNAc-ylated peptide and proteins. This reveals a simple, flexible biocatalytic method for glycoconjugate synthesis using PglB N-glycosylation machinery and varied chemically synthesized glycosylation donor precursors. [ABSTRACT FROM AUTHOR]

We investigated the structure–morphology–performance relationship of diketopyrrolopyrrole (DPP)-based low band gap polymers with different donor cores in organic field effect transistors (OFETs) and organic photovoltaics (OPVs). The change in the chemical structure led to strong physical property differences, such as crystalline behavior, blend morphology, and device performance. In addition, the choice of solvents and additives enabled one to fine tune the properties of these materials in the condensed state. For instance, when thin films were processed from solvent mixtures, both in the pure polymer and in a blend, we observed an enhanced edge-on orientation and the formation of thinner and longer polymer fibrils. In the BHJ blends, processing from a solvent mixture reduced the size scale of the phase separation and promoted the formation of a fibrillar network morphology, having a polymer–PCBM mixture filling the interfibrillar regions. The characteristic length scale of the fibrillar network dictated the specific inner surface area, which directly correlated to the performance in the OPV devices. When the BHJ mixture was processed from a single solvent, a large-scale phase separated morphology was observed that was stratified, normal to the film surface. A strong scattering anisotropy was observed in the resonant soft X-ray scattering of the blends that provided insight into the packing of the polymer chains within the fibrils. The morphology and performance trend in OPVs paralleled the performance in an OFET, suggesting that similar processing conditions should be considered in OFET fabrication. [ABSTRACT FROM AUTHOR]

Through-space metal/hydrogen shift is an important strategy for transition-metal-catalyzed C–H bond activation. Here we describe the synthesis and characterization of a Rh(I) 2,6-dimethoxybenzoate complex that underwent stoichiometric rearrangement via a highly unusual 1,3-rhodium migration. This aryl-to-aryl 1,3-Rh/H shift was also demonstrated in a Rh(I)-catalyzed decarboxylative conjugate addition to form a C–C bond at a meta position instead of the ipso-carboxyl position. A deuterium-labeling study under the conditions of Rh(I)-catalyzed protodecarboxylation revealed the involvement of an ortho-methoxy group in a multistep pathway of consecutive sp³ and sp² C–H bond activations. [ABSTRACT FROM AUTHOR]

Bent-shaped rigid-core molecules with flexible chiral dendrons grafted to the outer side of the bend were synthesized and characterized by circular dichroism, differential scanning calorimetry, X-ray scatterings, and transmission electron microscopy in solution and the solid state. The bent aromatic rods based on hepta- and nonaphenylene with nitrile groups at both ends self-assemble into well-ordered hollow tubular structures in aqueous solution, while the bent rod based on heptaphenylene without nitrile groups showed no apparent aggregations in aqueous solution. In the solid state, the rigid-flexible molecules based on heptaphenylene rod without the nitrile group self-assemble into a 2D oblique columnar structure with the columnar cross-section containing two interlocked molecules. Remarkably, the rigid flexible molecules based on hepta-, nona-, and undecaphenylene with nitrile groups self-assemble into a hexagonal columnar structure with weak 3D order. A model of vesicular channel structure is proposed based on small- and wide-angle X-ray diffraction on oriented fibers, density measurement, reconstruction and simulation of electron density maps, and molecular dynamics simulation. In contrast to the hollow tubular structure found in solution, in the solid both the outside and the interior of the columns are filled by the pendant aliphatic coils. Filling of the interior of these vesicular channels is made possible by some bent rod molecules turning their obtuse apex inward. One in 7, 2 in 8, and 4 in 10 molecules are thus inverted in a column slice in compounds with hepta-, nona-, and undecaphenylene cores, respectively. These are new examples of vesicular double-segregated columnar structures recently discovered in some dendrons. [ABSTRACT FROM AUTHOR]

T-shaped bolaamphiphiles composed of abiphenyl rigid core, a semiperfluorinated lateral chain, two polar 1,2-diol groups in the terminal positions and flexible alkyl spacers connecting the poiar groups with the biphenyl core have been synthesized and investigated by polarizing microscopy, DSC and X-ray scattering. The influence of spacer length and position of the spacer on the self-assembly in liquid-crystalline phases was studied. A series of four different columnar phases (Colhex/p6mm, Colrec/p2gg, Colsqu/p4gm and Colsqu/p4mtn), representing liquid-crystalline honeycomb structures composed of cylinders having hexagonal, pentagonal, and square cross section, were found on increasing the spacer length. It is also shown that introduction of aliphatic spacers in the backbone of the T-shaped bolaamphiphiles replaces the Colrec/c2mm phase made up of rhombic cylinders with the Colsqu/p4mm phase composed of square cylinders. It also causes the 2d lattice of pentagonal cylinders to increase the symmetry from Colrec/p2ggto Colsqu/p4gm. A temperature-dependent second-order phase transition between these two pentagonal cylinder structures was observed for the first time. Beside these effects on cylinder shape and phase symmetry the flexible spacer units also lead to reduced phase transition temperatures and allow adjustment of cylinder side length to envelop a wider range of side-chain sizes. Electron density maps suggest that this may involve sacrificing some of the hydrogen bonds. [ABSTRACT FROM AUTHOR]

Two series of polyphilic molecules composed of a rigid and linear p-terphenyl core, terminated at both ends with polar glycerol groups capable of hydrogen bonding, and two branched swallow tail-type lateral chains, composed of a fluorinated and a nonfluorinated branch or two fluorinated branches, were synthesized and investigated by differential scanning calorimetry, polarizing microscopy, and X-ray diffraction (XRD) with respect to their self-assembly in thermotropic liquid crystalline (LC) phases. Hexagonal columnar phases were formed by all molecules, at least at the highest temperature. In these phases the columns are composed of a core of aromatic rods and an aliphatic shell. The aromatic rods form bundles which are rotationally averaged and lie parallel to the column long axis. This unique organization is proven by different optical and XRD methods. The aromatic and glycerol groups inside the rod bundles are segregated into alternating segments. Depending on temperature and molecular structure, long-range intercolumnar correlation of this periodicity could take place, leading to a 3D-ordered LC phase with rhombohedral R¯3m symmetry. The bundles are embedded in the matrix of the lateral chains, which is divided into fluoroalkyl- and aliphatic-rich regions. In the 2D columnar phase the fluorinated regions take the form of either straight columns running along the edges of the hexagonal Voronoi cells or, for compounds with a higher degree of fluorination, fuse to a hexagonal honeycomb enclosing the aromatic cores. In the R¯3m phase the fluorine-rich chains are preferentially found along right- and left-handed helices wound around the 31 screw axes between the main aromatic columns. [ABSTRACT FROM AUTHOR]

We report computational studies on Al[sup +](H[sub 2]O)[sub n], n = 6-9, and HAIOH+(H[sub 2]O)[sub n-1], n = 6-14, by the density functional theory based ab initio molecular dynamics method, employing a planewave basis set with pseudopotentials, and also by conventional methods with Gaussian basis sets. The mechanism for the intracluster H[sub 2] elimination reaction is explored. First, a new size-dependent insertion reaction for the transformation of AI[sup +](H[sub 2]O)[sub n] into HAIOH[sup +](H[sub 2]O)[sub n-1] is discovered for n ≥ 8. This is because of the presence of a fairly stable six-water-ring structure in Al[sup +](H[sub 2]O)[sub n] with 12 members, including the AI[sup +]. This structure promotes acidic dissociation and, for n ≥ 8, leads to the insertion reaction. Gaussian based BPW91 and MP2 calculations with 6-31 G[sup *] and 6-31G[sup **] basis sets confirmed the existence of such structures and located the transition structures for the insertion reaction. The calculated transition barrier is 10.0 kcal/mol for n = 9 and 7.1 kcal/mol for n = 8 at the MP2/6-31G[sup **] level, with zero-point energy corrections. Second, the experimentally observed size-dependent H[sub 2] elimination reaction is related to the conformation of HAIOH[sup +](H[sub 2]O)[sub n-1], instead of AI[sup +](H[sub 2]O)[sub n]. As n increases from 6 to 14, the structure of the HAIOH[sup +](H[sub 2]O)[sub n-1] cluster changes into a caged structure, with the AI-H bond buried inside, and protons produced in acidic dissociation could then travel through the H[sub 2]O network to the vicinity of the AI-H bond and react with the hydride H to produce H[sub 2]. The structural transformation is completed at n = 13, coincident approximately with the onset of the H[sub 2] elimination reaction. From constrained ab initio MD simulations, we estimated the free energy barrier for the H[sub 2] elimination reaction to be 0.7 eV (16 kcal/mol) at n = 13, 1.5 eV (35 kcal/mol) at n = 12, and... [ABSTRACT FROM AUTHOR]

Investigates the use of ab initio molecular dynamics (MD) for unimolecular decomposition. Combination of MD and molecular orbital methods; Analysis of the density functional theory-based MD method with planewave basis set and pseudopotentials; Localization of energy barrier and transition structure.

Examines the syntheses, structures and electroluminiscence of blue/green luminescent chelate compounds: Zn(2-py-in)2(THF), BPh2(2-py-in), Be(2-py-in)2, and BPh2(2-py-aza). Use of modified indole and 7-azaindole ligands in blue/green luminescent compounds synthesis; Photoluminescent and electroluminescent properties of the compounds.

The article discusses the order of 2D and 3D in columnar liquid crystal phases by bundles of Bolaamphiphiles with swallow-tail side chains. Liquid crystalline (LC) are self-assembled superstructures that combine order and mobility essential for technological applications. Two new modes of organization in columnar LC phases are studied where rod-like mesogenic units lie parallel to the column axis, thus, achieving lateral attachment of two branched swallow-tail chains to a rigid p-terphenyl unit.

The article describes the self-assembly of T-shaped ternary block molecules to obtain liquid crystalline (LC) phases, representing an array of trapezodial cylinders. According to the authors, a LC phase is obtained in polyphilic molecules based on a polygonal tiling pattern. They note that in the trapezoidal phase, not all walls of the polygonal nanocylinders are made of the same material.

The article presents a study that shows it is possible to design molecules which self-organize in a liquid-crystalline (LC) phase composed of triangular cylinders. According to the authors, the structure was obtained with the T-shaped facial amphiphilic three-block molecules in which a terphenyl unit is substituted laterally by a polar and flexible tetraethylene glycol chain, terminated by a hydrogen-bonding carboxylic acid group. Results of the study are presented and discussed.

The article examines light-driven catalytic water oxidation which occurs as the terminal step in photosystem II at the oxygen evolving complex. It is also a potential half-reaction for artificial photosynthesis and photochemical energy conversion based on water splitting. The origins of catalyst deactivation point to the evolution of a family of surface-bound catalysts for water oxidation.

The article reports the first experimental evidence that nuclear isotopic substitution of molecular sensitizers can indeed be used to control excited-state interfacial electron injection yields. The synthesis of the ruthenium ammine compounds is very similar to reported procedures for closely related compounds. The extent of the reaction was monitored by infrared spectroscopy, wherein the N-H stretching modes decreased with a concomitant increase of the N-D stretching intensity. It was found that the N-H stretching bands were essentially gone after four consecutive exchanges in MeOD.

Monodispersed conjugated oligothiophenes are receiving attention in fundamental and applied science due to their interesting optical, optoelectronic, and charge transport properties. These "low molecular weight" polymers serve as model structures for the corresponding polymer analogues, which are inherently polydispersed. Here we report the synthesis, electronic structure, molecular packing/morphology, and charge transport properties of monodispersed oligothiophenes with up to six didodecylquaterthiophene (DDQT) building block repeat units (i.e., 24 thiophene units). At the point where the effective conjugation length is reached, the electronic structure showed convergence behavior to the corresponding polymer, poly(3,3″-didodecyl-quaterthiophene) (PQT-12). X-ray crystal structure analysis of the dimer (DDQT-2) showed that terminal thiophenes exhibit syn-conformations, similar to the terminal syn-conformations observed in the trimer (DDQT-3). The dimer also exhibits a rare bending of the terminal alkyl side chains in order to prevent steric hindrance with neighboring hydrogens attached to core thiophenes. Grazing incidence X-ray scattering measurements revealed a morphology evolution from small molecule-like packing to polymer-like packing in thin films, with a morphology transition occurring near the effective conjugation length. Charge transport measurements showed a mobility increase with decreasing chain length. We correlated the molecular packing and morphology to charge transport and determined that carrier mobilities are most sensitive to crystallinity and crystal grain misorientation. This indicates that molecular weight is not a decisive factor for improved carrier mobility in the low molecular weight region, but rather the degree in crystallinity and in-plane crystal orientation. These results represent a fundamental advancement in understanding the relationship between conjugation length and carrier mobilities in oligothiophene semiconductors. [ABSTRACT FROM AUTHOR]

Two cheliform non-fullerene acceptors, DTPC-IC and DTPC-DFIC, based on a highly electron-rich core, dithienopicenocarbazole (DTPC), are synthesized, showing ultra-narrow bandgaps (as low as 1.21 eV). The two-dimensional nitrogen-containing conjugated DTPC possesses strong electron-donating capability, which induces intense intramolecular charge transfer and intermolecular π-π stacking in derived acceptors. The solar cell based on DTPC-DFIC and a spectrally complementary polymer donor, PTB7-Th, showed a high power conversion efficiency of 10.21% and an extremely low energy loss of 0.45 eV, which is the lowest among reported efficient OSCs. [ABSTRACT FROM AUTHOR]

We report a regioregular bis-pyridal[2,1,3]- thiadiazole (BPT) acceptor strategy to construct the first ambipolar pyridal[2,1,3]thiadiazole-based semiconducting polymer (PBPTV). The use of BPT unit enables PBPTV to achieve high electron affinity, low LUMO level, and extended π-conjugation. All these factors provide PBPTV with encouraging hole and electron mobilities up to 6.87 and 8.49 cm² V-1 s-1, respectively. Our work demonstrates that the BPT unit is a promising building block for designing high-performance electron-transporting semiconductors in organic electronics. [ABSTRACT FROM AUTHOR]

The absence of near-infrared (NIR) solar cells with high open circuit voltage (Voc) and external quantum efficiency (EQE) has impeded progress toward achieving organic photovoltaic (OPV) power conversion efficiency PCE > 15%. Here we report a small energy gap (1.3 eV), chlorinated nonfullerene acceptor-based solar cell with PCE = 11.2 ± 0.4%, short circuit current of 22.5 ± 0.6 mA cm-2, Voc = 0.70 ± 0.01 V and fill factor of 0.71 ± 0.02, which is the highest performance reported to date for NIR single junction OPVs. Importantly, the EQE of this NIR solar cell reaches 75%, between 650 and 850 nm while leaving a transparency window between 400 and 600 nm. The semitransparent OPV using an ultrathin (10 nm) Ag cathode shows PCE = 7.1 ± 0.1%, with an average visible transmittance of 43 ± 2%, Commission d'Eclairage chromaticity coordinates of (0.29, 0.32) and a color rendering index of 91 for simulated AM1.5 illumination transmitted through the cell. [ABSTRACT FROM AUTHOR]

A new nonfullerene small molecule with acceptor–donor–acceptor (A–D–A) structure, namely, NFBDT, based on a heptacyclic benzodi(cyclopentadithiophene) (FBDT) unit using benzo[1,2-b:4,5-b′]dithiophene as the core unit, was designed and synthesized. Its absorption ability, energy levels, thermal stability, as well as photovoltaic performances were fully investigated. NFBDT exhibits a low optical bandgap of 1.56 eV resulting in wide and efficient absorption that covered the range from 600 to 800 nm, and suitable energy levels as an electron acceptor. With the widely used and successful wide bandgap polymer PBDB-T selected as the electron donor material, an optimized PCE of 10.42% was obtained for the PBDB-T:NFBDT-based device with an outstanding short-circuit current density of 17.85 mA cm–2 under AM 1.5G irradiation (100 mW cm–2), which is so far among the highest performance of NF-OSC devices. These results demonstrate that the BDT unit could also be applied for designing NF-acceptors, and the fused-ring benzodi(cyclopentadithiophene) unit is a prospective block for designing new NF-acceptors with excellent performance. [ABSTRACT FROM AUTHOR]

We report the synthesis of a family of multifluorine substituted oligomers and the corresponding polymer that have the same backbones but different conjugation lengths and amounts of fluorine atoms on the backbone. The physical properties and photovoltaic performances of these materials were systematically investigated using optical absorption, charge mobility, atomic force microscopy, transmission electron microscopy, grazing incidence X-ray diffraction, resonant soft X-ray scattering methods, and photovoltaic devices. The power conversion efficiencies (PCEs) based on oligomers were much higher than that in the polymer. Moreover, the devices based on BIT6F and BIT10F, which have an axisymmetric electron-deficient difluorobenzothiadiazole as the central unit, gave slightly higher PCEs than those with centrosymmetric electron-rich indacenodithiophene (IDT) as the central unit (BIT4F or BIT8F). Using proper solvent vapor annealing (SVA), particularly using thermal annealing (TA) followed by SVA, the device performance could be significantly improved. Notably, the best PCE of 9.1% with a very high FF of 0.76 was achieved using the medium-sized oligomer BIT6F with the optimized film morphology. This efficiency is the highest value reported for organic solar cells from small-molecules without rhodanine terminal group. More excitingly, devices from the shortest oligomer BIT4F showed an impressively high FF of 0.77 (the highest FF value reported for solution-processed small-molecule organic solar cells). These results indicate that photovoltaic performances of oligomers can be modulated through successive change in chain-length and fluorine atoms, alternating spatial symmetric core, and combined post-treatments. [ABSTRACT FROM AUTHOR]

Solar cells fabricated using alkyl ammonium metal halides as light absorbers have the right combination of high power conversion efficiency and ease of fabrication to realize inexpensive but efficient thin film solar cells. However, they degrade under prolonged exposure to sunlight. Herein, we show that this degradation is quasi-reversible, and that it can be greatly lessened by simple modifications of the solar cell operating conditions. We studied perovskite devices using electrochemical impedance spectroscopy (EIS) with methylammonium (MA)-, formamidinium (FA)-, and MAxFA1-x lead triiodide as active layers. From variable temperature EIS studies, we found that the diffusion coefficient using MA ions was greater than when using FA ions. Structural studies using powder X-ray diffraction (PXRD) show that for MAPbI3 a structural change and lattice expansion occurs at device operating temperatures. On the basis of EIS and PXRD studies, we postulate that in MAPbI3 the predominant mechanism of accelerated device degradation under sunlight involves thermally activated fast ion transport coupled with a lattice-expanding phase transition, both of which are facilitated by absorption of the infrared component of the solar spectrum. Using these findings, we show that the devices show greatly improved operation lifetimes and stability under white-light emitting diodes, or under a solar simulator with an infrared cutoff filter or with cooling. [ABSTRACT FROM AUTHOR]

Gold nanoparticles have been prepared and surface-functionalized with a 1:1 molar mixture of a hexylthiol ligand and a chiral mesogenic ligand consisting of a cholesterylbenzoate attached via an undecylthiol spacer. Grazing incidence X-ray diffraction showed that upon annealing a columnar liquid crystal (LC) structure develops with the nanoparticles forming strings on a regular oblique 2d lattice. Synchrotron radiation circular dichroism is substantially enhanced upon the isotropic-LC transition. In the proposed structural model, layers of Au columns rotate by a small angle relative to their neighbors, with the columns winding around a helical axis. The work demonstrates that it is possible to obtain chiral LC superstructures from nanoparticles coated with chiral mesogen without the addition of a separate LC or chiral dopants. The results provide direction in the development of plasmonic metamaterials interacting selectively with circularly polarized light. [ABSTRACT FROM AUTHOR]

We designed and synthesized the DPPEZnP-TEH molecule, with a porphyrin ring linked to two diketopyrrolopyrrole units by ethynylene bridges. The resulting material exhibits a very low energy band gap of 1.37 eV and a broad light absorption to 907 nm. An open-circuit voltage of 0.78 V was obtained in bulk heterojunction (BHJ) organic solar cells, showing a low energy loss of only 0.59 eV, which is the first report that small molecule solar cells show energy losses <0.6 eV. The optimized solar cells show remarkable external quantum efficiency, short circuit current, and power conversion efficiency up to 65%, 16.76 mA/cm², and 8.08%, respectively, which are the best values for BHJ solar cells with very low energy losses. Additionally, the morphology of DPPEZnP-TEH neat and blend films with PC61BM was studied thoroughly by grazing incidence X-ray diffraction, resonant soft X-ray scattering, and transmission electron microscopy under different fabrication conditions. [ABSTRACT FROM AUTHOR]

A series of acceptor--donor--acceptor simple oligomer-like small molecules based on oligothiophenes, namely, DRCN4T-DRCN9T, were designed and synthesized. Their optical, electrical, and thermal properties and photovoltaic performances were systematically investigated. Except for DRCN4T, excellent performances were obtained for DRCN5T-DRCN9T. The devices based on DRCN5T, DRCN7T, and DRCN9T with axisymmetric chemical structures exhibit much higher short-circuit current densities than those based on DRCN6T and DRCN8T with centrosymmetric chemical structures, which is attributed to their well-developed fibrillar network with a feature size less than 20 nm. The devices based on DRCN5T/PC71BM showed a notable certified power conversion efficiency (PCE) of 10.10% under AM 1.5G irradiation (100 mW cm-2) using a simple solution spin-coating fabrication process. This is the highest PCE for single-junction small-molecule-based organic photovoltaics (OPVs) reported to date. DRCN5T is a rather simpler molecule compared with all of the other high-performance molecules in OPVs to date, and this might highlight its advantage in the future possible commercialization of OPVs. These results demonstrate that a fine and balanced modification/design of chemical structure can make significant performance differences and that the performance of solution-processed small-molecule-based solar cells can be comparable to or even surpass that of their polymer counterparts. [ABSTRACT FROM AUTHOR]

A novel electron acceptor was synthesized from one-step functionalization of the readily available indigo dye. The resulting bay-annulated indigo (BAI) was utilized for the preparation of a series of novel donor-acceptor small molecules and polymers. As revealed experimentally and by theoretical calculations, substituted BAIs have stronger electron accepting characteristics when compared to several premier electron deficient building blocks. As a result, the donor-acceptor materials incorporating BAI acceptor possess low-lying LUMO energy levels and small HOMO-LUMO gaps. In situ grazing incidence wide-angle X-ray scattering studies of the thin films of BAI donor-acceptor polymers indicated improved crystallinity upon thermal treatment. Field effect transistors based on these polymers show excellent ambipolar transporting behavior, with the hole and electron mobilities reaching 1.5 and 0.41 cm2 V-1 s-1, respectively, affirming BAI as a potent electron accepting unit for high performance organic electronic materials. [ABSTRACT FROM AUTHOR]

A bulk material comprising stacked nanosheets of nickel bis(dithiolene) complexes is investigated. The average oxidation number is —3/4 for each complex unit in the as-prepared sample; oxidation or reduction respectively can change this to 0 or -1. Refined electrical conductivity measurement, involving a single microflake sample being subjected to the van der Pauw method under scanning electron microscopy control, reveals a conductivity of 1.6 X 102 S cm-1, which is remarkably high for a coordination polymeric material. Conductivity is also noted to modulate with the change of oxidation state. Theoretical calculation and photoelectron emission spectroscopy reveal the stacked nanosheets to have a metallic nature. This work provides a foothold for the development of the first organic-based two-dimensional topological insulator, which will require the precise control of the oxidation state in the single-layer nickel bisdithiolene complex nanosheet (cf. Liu, F. et al. Nano Lett. 2013, 13, 2842). [ABSTRACT FROM AUTHOR]

Describes the proton-inverse detected deuteron nuclear magnetic resonance (NMR) spectroscopy. Sensitivity enhancement of [sup 2] NMR by an order of magnitude or more; Heteronuclear multiple-quantum coherence approach.

Most of the dynamic DNA devices are rationally constructed by utilizing toehold-mediated DNA strand displacement reactions. However, such approaches have been mainly limited to the operation with double-stranded hybridization and lack the versatility of DNA scaffold responses for additional levels of controlling DNA strand displacement reactions. Herein, we propose a toehold activation strategy based on the DNA tetraplex (G-quadruplex or i-motif), where the toehold domain is designed by attaching a complementary single-stranded segment (CS) to a G- rich/C-rich segment. Modulating G-quartet/C·C+ numbers and/or the CS lengths can easily tune the strand displacement kinetics. This scheme allows fine control of DNA strand displacement rates over 2 orders of magnitude by adjusting the concentration of various environmental stimuli. This strategy expands the rule set of designing dynamic DNA devices and will be useful in building diverse environmental stimuli- fuelled molecular devices. [ABSTRACT FROM AUTHOR]

Two series of wedge-shaped onium salts, one ammonium and the other phosphonium, having 3,4,5-tris(alkyloxy)benzyl moieties, exhibit thermotropic bicontinuous "gyroid" cubic (Cubbi) and hexagonal columnar liquid-crystalline (LC) phases by nanosegregation between ionophilic and ionophobic parts. The alkyl chain lengths on the cationic moieties, anion species, and alkyl chain lengths on the benzyl moieties have crucial effects on their thermotropic phase behavior. For example, triethyl-[3,4,5-tris(dodecyloxy)benzyl]ammonium hexafluorophosphate forms the thermotropic Ia3¯d Cubbi LC phase, whereas an analogous compound with trifluoromethanesulfonate anion shows no LC properties. Synchrotron small-angle diffraction intensities from the Ia3¯d Cubbi LC materials provide electron density maps in the bulk state. The resulting maps show convincingly that the Ia3¯d Cubbi structure is composed of three-dimensionally interconnected ion nanochannel networks surrounded by aliphatic domains. A novel differential mapping technique has been applied successfully. The map of triethyl-[3,4,5-tris(decyloxy)benzyl]ammonium tetrafluoroborate has been subtracted from that of the analogous ammonium salt with hexafluorophosphate anion in the Ia3¯d Cubbi phases. The differential map shows that the counteranions are located in the core of the three-dimensionally interconnected nanochannel networks. Changing from trimethyl- via triethyl- to tripropylammonium cation changes the phase from columnar to Cubbi to no mesophase, respectively. This sensitivity to the widened shape for the narrow end of the molecule is explained successfully by the previously proposed semiquantitative geometric model based on the radial distribution of volume in wedge-shaped molecules. The LC onium salts dissolve lithium tetrafluoroborate without losing the Ia3¯d Cubbi LC phase. The Cubbi LC materials exhibit efficient ion-transporting behavior as a result of their 3D interconnected ion nanochannel networks. The Ia3¯d Cubbi LC material formed by triethyl-[3,4,5-tris(decyloxy)benzyl]phosphonium tetrafluoroborate shows ionic conductivities higher than the analogous Ia3¯d Cubbi material based on ammonium salts. The present study indicates great potential of Cubbi LC nanostructures consisting of ionic molecules for development of transportation nanochannel materials. [ABSTRACT FROM AUTHOR]

The first simple-cubic liquid crystal was obtained by coating monodisperse Au nanoparticles (NPs) with a thick corona of amino-substituted organic dendrons. This unusual structure was determined by grazing-incidence diffraction and electron density reconstruction and explained by analyzing the radial density profile of the corona. Another novel structure is proposed for the phase preceding the cubic one: a hexagonal superlattice composed of alternating dense and sparse strings of Au NPs. [ABSTRACT FROM AUTHOR]

The article details the design a number of potent inhibitors incorporating a nonhydrolyzable Leu-Ala hydroxyethylene dipeptide isostere. It provides molecular insight into the ligand-binding site interactions of the memapsin active site. The structure-based design led to the development of very potent and highly selective memapsin 2 inhibitors.