An unprecedented palladium-catalyzed cyanation of aromatic C-H bonds by using tertiary amine derived isocyanide as a novel cyano source was developed. Cu(TFA)(2) was used as a requisite stoichiometric oxidant. Mechanistic studies suggest that a tertiary carbon cation-based intermediate is involved following the C-N bond breakage.
All-polymer solar cells (all-PSCs) are proven to possess outstanding thermal and mechanical stabilities. However, concurrently achieving appropriate phase-separated pattern, efficient charge transportation, and adequate charge transfer between donor and acceptor components is still a challenge, and thus, only a few polymer−polymer bulk heterojunction (BHJ) blends have yielded BHJ device power conversion efficiency (PCE) values of >8%. Generally, polymer backbone substitutions may have a direct influence on the device performance. Thus, this report examines a set of wide bandgap polymer donor analogues composed of thienothiophene (TT) or thiazolothiazole (TTz) motif, and their all-PSC device performance with N2200. Results show that all-PSCs based on the imine-substituted derivative PBDT-TTz exhibit PCE values as high as 8.4%, which largely outperform the analogue PBDT-TT-based ones with PCEs of only 0.7%. This work reveals that the imine substitution in polymer backbones of PBDT-TTz not only increases the ionization potential (IP) and electron affinity (EA), narrows the optical gap (E opt ), but also has significantly impacts on the BHJ film morphologies. PBDT-TTz:N2200 BHJ blends present better miscibility, suppressed phase separation, much stronger crystallinity, and face-on ordering, which contribute to efficient exciton dissociation, charge transportation, and therefore, high-efficiency in all-PSCs. This study demonstrates that the iminesubstituted polymers composed of TTz motif, which can be easily synthesized through a facile two-step procedure, are a promising class of wide-bandgap polymer donors for efficient all-PSCs.
A new process involving copper-catalyzed aerobic C(sp(2))-H activation, followed by cycloetherification, has been developed. This reaction serves as a direct method for the preparation of multisubstituted dibenzofurans starting with o-arylphenols. The presence of a strong para-electron-withdrawing group (e.g., NO(2)) on the phenol is essential for the success of the reaction.
The vertical composition distribution of a bulk heterojunction
(BHJ) photoactive layer is known to have dramatic effects on photovoltaic
performance in polymer solar cells. However, the vertical composition
distribution evolution rules of BHJ films are still elusive. In this
contribution, three BHJ film systems, composed of polymer donor PBDB-T,
and three different classes of acceptor (fullerene acceptor PCBM,
small-molecule acceptor ITIC, and polymer acceptor N2200) are systematically
investigated using neutron reflectometry to examine how donor–acceptor
interaction and solvent additive impact the vertical composition distribution.
Our results show that those three BHJ films possess homogeneous vertical
composition distributions across the bulk of the film, while very
different composition accumulations near the top and bottom surface
were observed, which could be attributed to different repulsion, miscibility,
and phase separation between the donor and acceptor components as
approved by the measurement of the donor–acceptor Flory–Huggins
interaction parameter χ. Moreover, the solvent additive 1,8-diiodooctane
(DIO) can induce more distinct vertical composition distribution especially
in nonfullerene acceptor-based BHJ films. Thus, higher power conversion
efficiencies were achieved in inverted solar cells because of facilitated
charge transport in the active layer, improved carrier collection
at electrodes, and suppressed charge recombination in BHJ solar cells.
A transition-metal-free method for the synthesis of C6 phenanthridine derivatives by arylative cyclization of 2-isocyanobiphenyls with arylamines in one pot was developed. Mechanistic studies suggest that electrophilic aromatic substitution (SEAr) of a nitrilium intermediate and homolytic aromatic substitution (HAS) of an imidoyl radical intermediate are two competitive reaction pathways involved in the annulation step.
An efficient synthesis of 2- or 4-iododibenzofurans through CuI-mediated sequential iodination/cycloetherification of two aromatic C-H bonds in o-arylphenols has been developed. Both the preexisting electron-withdrawing groups (NO(2), CN, and CHO) and the newly introduced iodide are readily modified for a focused dibenzofuran library synthesis. Mechanistic studies and DFT calculations suggest that a Cu(III)-mediated rate-limiting C-H activation step is involved in cycloetherification.
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