Quinoidal structures incorporating expanded paraquinodimethane (p-QM) units have garnered great interest as functional organic electronic, optical, and magnetic materials. The direct use of the compact p-QM unit as an electronic building block, however, has been inhibited by the high reactivity conveyed by its biradical character. Herein, we introduce a stable p-QM variant, namely p-azaquinodimethane (p-AQM), that incorporates nitrogen atoms in the central ring and alkoxy substituents on the periphery to increase the stability of the quinoidal structure. The succinct synthesis from readily available precursors leads to regio-and stereospecific p-AQMs that can be readily integrated into the backbone of conjugated polymers. The quinoidal character of the p-AQM unit endows the resulting polymers with narrow band gaps and high carrier transport mobilities. The study of a series of copolymers employing different numbers of thiophene units revealed an unconventional trend in band gaps, which is distinct from the widely adopted donor−acceptor approach to tuning the band gaps of conjugated polymers. Theoretical calculations have shed light on the nature of this trend, which may provide a unique class of conjugated polymers with promising optical and electronic properties.
Three series of low-bandgap polymers based on a novel quinoidal paraazaquinodimethane (p-AQM) unit are devised and synthesized, enabling an in-depth study of the impact of structural factors such as polymer main chain, branching point of the side chain, and the length of the branch chains on the thin film morphologies and charge transport properties. Morphological studies reveal that the polymers composed of larger repeating units exhibit a stronger tendency to form edge-on lamella. On the other hand, altering the side chain structures of polymers with the same main chain configuration indicates that the branching point position has a more deterministic impact than the branch chain length on the interchain interactions and the crystallite orientation. These results demonstrate a compound odd-even effect of the branching point on the chain packing and morphology, which correlates well with the corresponding field effect transistor performances. The polymer with the branching point at the fourth carbon displays the highest charge carrier mobility over 1.0 cm 2 V −1 s −1 , concurrent with a bimodal texture. This study provides a comprehensive description of the correlations between polymer structures, thin film morphology, and device performances, providing a clear path to desirable bimodal thin film texture for charge transport.
To
investigate the influence of functional pendent groups on acceptor
polymers and photovoltaic properties of all-polymer solar cells (all-PSCs),
two novel acceptor polymers containing siloxane-terminated side chains
are synthesized and characterized. Increasing the content of siloxane-terminated
side chains can reduce π–π stacking distance and
improve crystalline behavior, yet lead to poorer solubility of the
acceptor polymers. By modulating the proper loadings of siloxane-terminated
side chains on the acceptor polymers, the PBDB-T:PNDI-Si25 all-PSC
attains a maximal power conversion efficiency (PCE) of 7.4% with an
outstanding fill factor of 0.68. The results provide new insights
for developing high-performance all-PSCs through functional group
engineering on the acceptor polymers, to achieve good solubility,
polymer miscibility, and blend morphology.
In this work, a new A‐D‐A type nonfullerene small molecular acceptor SiIDT‐IC, with a fused‐ring silaindacenodithiophene (SiIDT) as D unit and 2‐(3‐oxo‐2,3‐dihydroinden‐1‐ylidene)malononitrile (INCN) as the end A unit, was design and synthesized. The SiIDT‐IC film shows absorption peak and edge at 695 and 733 nm, respectively. The HOMO and LUMO of SiIDT‐IC are of −5.47 and −3.78 eV, respectively. Compared with carbon‐bridging, the Si‐bridging can result in an upper‐lying LUMO level of an acceptor, which is benefit to achieve a higher open‐circuit voltage in polymer solar cells (PSCs). Complementary absorption and suitable energy level alignment between SiIDT‐IC and wide bandgap polymer donor PBDB‐T were found. For the PBDB‐T:SiIDT‐IC based inverted PSCs, a D/A ratio of 1: 1 was optimal to achieve a power conversion efficiency (PCE) of 7.27%. With thermal annealing (TA) of the blend film, a higher PCE of 8.16% could be realized due to increasing of both short‐circuit current density and fill factor. After the TA treatment, hole and electron mobilities were elevated to 3.42 × 10−4 and 1.02 × 10−4 cm2·V−1·s−1, respectively. The results suggest that the SiIDT, a Si‐bridged fused ring, is a valuable D unit to construct efficient nonfullerene acceptors for PSCs.
Cyanide is an important acute poison in forensic sciences. Cyanide determination is in general performed in a blood sample. We have developed a gas chromatography procedure with electron capture detector and headspace equipment (GC/ECD/ HS) for the detection of cyanide und studied cyanide disiribution in various tissues in the human body, such as blood, liver, kidney, brain, urine, and stomach content. Furthermore, in a rabbit animal model, cyanide tissue distribution is determined using the developed method. A calibration curve is eonsiructed between 0.2-3 fxg/mL. R"^ -().99.'58. Linearity is lost above 3 jig/mL. The average recovery is 84.6% (n = 8. RSD 6.39%). calculated from standard addition. The limit of detection is
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.