Mechanisms and Origins of Periselectivity of the Ambimodal [6 + 4] Cycloadditions of Tropone to Dimethylfulvene.

The mechanisms and selectivities of the cycloadditions of tropone to dimethylfulvene have been investigated with M06-2X and B3LYP-D3 density functional theory (DFT) calculations and quasi-classical direct molecular dynamics simulations. The originally proposed reaction mechanism (Houk) involves a highly peri-, regio-, and stereoselective [6F + 4T] cycloaddition of tropone [4π] to dimethylfulvene [6π], followed by a [1,5] hydrogen shift, and, finally, a second [6 + 4] cycloaddition of tropone [6π] to the cyclopentadiene moiety [4π]. Paddon-Row and Warrener proposed an alternative mechanism: the initial cycloaddition involves a different [6T + 4F] cycloaddition in which fulvene acts as the 4π component, and a subsequent Cope rearrangement produces the formal [6F + 4T] adduct. Computations now demonstrate that the initial cycloaddition proceeds via an ambimodal transition state that can lead to both of the proposed [6 + 4] adducts. These adducts can interconvert through a [3,3] sigmatropic shift (Cope rearrangement). Molecular dynamics simulations reveal the initial distribution of products and provide insights into the time-resolved mechanism of this ambimodal cycloaddition. Competing [4 + 2] cycloadditions and various sigmatropic shifts are also explored.

Hole-Transporting Materials Based on Twisted Bimesitylenes for Stable Perovskite Solar Cells with High Efficiency.

A new class of hole-transport materials (HTMs) based on the bimesitylene core designed for mesoporous perovskite solar cells is introduced. Devices fabricated using two of these derivatives yield higher open-circuit voltage values than the commonly used spiro-OMeTAD. Power conversion efficiency (PCE) values of up to 12.11% are obtained in perovskite-based devices using these new HTMs. The stability of the device made using the highest performing HTM (P1) is improved compared with spiro-OMeTAD as evidenced through long-term stability tests over 1000 h.

Computational investigation of NH3 adsorption and dehydrogenation on a W-modified Fe(111) surface.

Hydrogen gas will play an important role in the future since it could be a replacement for gasoline, heating oil, natural gas, and other fuels. In previous reports ammonia (NH3), which has a high hydrogen content, provides a promising mode for the transferring and storing of hydrogen for its on-site generation. Therefore, the dehydrogenation of NH3 on a metal surface has been studied widely in the last few decades. In our study, we employed monolayer tungsten metal to modify the Fe(111) surface, denoted as W@Fe(111), and calculated the adsorption and dehydrogenation behaviors of NH3 on W@Fe(111) surface via first-principles calculations based on density functional theory (DFT). The three adsorption sites of the surface, top (T), 3-fold-shallow (S), and 3-fold-deep (D) were considered. The most stable structure of the NHx (x = 0-3) species on the surface of W@Fe(111) have been predicted. The calculated activation energies for NHx (x = 1-3) dehydrogenations are 19.29 kcal mol(-1) (for H2N-H bond activation), 29.17 kcal mol(-1) (for HN-H bond activation) and 27.94 kcal mol(-1) (for N-H bond activation), and the entire process is exothermic by 33.05 kcal mol(-1). To gain detailed knowledge of the catalytic processes of the NH3 molecule on the W@Fe(111) surface, the physical insights between the adsorbate/substrate interaction and interface morphology were subjected to a detailed electronic analysis.

High-performance organic materials for dye-sensitized solar cells: triarylene-linked dyads with a 4-tert-butylphenylamine donor.

A series of organic dyes were prepared that displayed remarkable solar-to-energy conversion efficiencies in dye-sensitized solar cells (DSSCs). These dyes are composed of a 4-tert-butylphenylamine donor group (D), a cyanoacrylic-acid acceptor group (A), and a phenylene-thiophene-phenylene (PSP) spacer group, forming a D-π-A system. A dye containing a bulky tert-butylphenylene-substituted carbazole (CB) donor group showed the highest performance, with an overall conversion efficiency of 6.70%. The performance of the device was correlated to the structural features of the donor groups; that is, the presence of a tert-butyl group can not only enhance the electron-donating ability of the donor, but can also suppress intermolecular aggregation. A typical device made with the CB-PSP dye afforded a maximum photon-to-current conversion efficiency (IPCE) of 80% in the region 400-480 nm, a short-circuit photocurrent density J(sc) =14.63 mA cm(-2), an open-circuit photovoltage V(oc) =0.685 V, and a fill factor FF=0.67. When chenodeoxycholic acid (CDCA) was used as a co-absorbent, the open-circuit voltage of CB-PSP was elevated significantly, yet the overall performance decreased by 16-18%. This result indicated that the presence of 4-tert-butylphenyl substituents can effectively inhibit self-aggregation, even without CDCA.

Hole mobility on isolated chains of poly(3-hexylthiophene) by microwave conductivity measurement.

We demonstrate a facile method to investigate intrinsic charge mobility on isolated chains of conjugated polymers by use of microwave absorption method. Hole carriers are generated on conjugated polymer chains in dilute solution by doping with the p-type dopants NOSbF(6), instead of using excitation sources of pulsed laser and electron beam as reported in the literature. The number of hole carriers can be easily estimated by doping level. Measurements on poly(3-hexylthiophene) in benzene with various doping levels from 0.1% to 3% indicate that the hole mobility can be divided into two ranges. In the doping level 0.1%-0.3%, the hole mobility maintains at the constant level 0.03 cm(2)/V s, which can be regarded as that on an isolated chain since the average number of hole carriers per chain is only around one. As the doping level is higher than 0.3%, a presence of multiple hole carriers on a chain occurs, which results in a repulsion of hole carriers and leads to a reduced hole mobility.

Investigating side chain mediated electroluminescence from carbazole-modified polyfluorene.

In molecular design of electroluminescent (EL) conjugated polymers, introducing a charge transport moiety on a side chain is found to be a promising method for balancing electron and hole fluxes in EL devices without changing the emitting color if there is no interaction between moiety and main chain. In the case of grafting a carbazole (Cz) moiety (hole transporting) on blue emitting polyfluorene, a green emission appears with intensity comparable to the blue emission, which was attributed to a possible interaction between main chain and Cz as previously reported by us. Here, a detailed study of its EL mechanism was carried out by means of time-resolved EL with the assistance of molecular simulation and thermally stimulated current measurements; exploration of how main chain segments interact with the transport moiety was performed. We found the Cz groups in Cz100PF play multiple roles: they act as (1) hole transporter to improve hole injection, (2) hole trapping site for efficient electron-hole recombination to yield blue-emitting excitons, and (3) source of green emission from electroplex formed via electric field-mediated interaction of the Cz/Cz radical cation with an electron in the nearby PF backbone. In combination, these observations suggest that integrated consideration for both intramolecular and intermolecular interactions provides a new route of molecular design of efficient EL polymers.