skip to main content


Title: Single Crystal Microwires of p ‐DTS(FBTTh 2 ) 2 and Their Use in the Fabrication of Field‐Effect Transistors and Photodetectors
Abstract

Single crystal microwires of a well‐studied organic semiconductor used in organic solar cells, namelyp‐DTS(FBTTh2)2, are prepared via a self‐assembly method in solution. The high level of intermolecular organization in the single crystals facilitates migration of charges, relative to solution‐processed films, and provides insight into the intrinsic charge transport properties ofp‐DTS(FBTTh2)2. Field‐effect transistors based on the microwires can achieve hole mobilities on the order of ≈1.8 cm2V−1s−1. Furthermore, these microwires show photoresponsive electrical characteristics and can act as photoswitches, with switch ratios over 1000. These experimental results are interpreted using theoretical simulations using an atomistic density functional theory approach. Based on the lattice organization, intermolecular couplings and reorganization energies are calculated, and hole mobilities for comparison with experimental measurements are further estimated. These results demonstrate a unique example of the optoelectronic applications ofp‐DTS(FBTTh2)2microwires.

 
more » « less
NSF-PAR ID:
10047054
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Advanced Functional Materials
Volume:
28
Issue:
4
ISSN:
1616-301X
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    We present a method to use long‐range CH coupling constants to derive the correct diastereoisomer from the molecular constitution of small molecules. A set of 792JCHand3JCHvalues collected from a single HSQMBC experiment on a sample of strychnine were used in the CASE‐3D (computer‐assisted 3D structure elucidation) protocol. In addition to the most commonly used3JCHcoupling constants, the subset of 322JCHvalues alone showed an excellent degree of configuration selection. The study is mainly based on comparison of DFT‐calculated2,3JCHvalues with experimental ones, critical for the case of2JCH. But the configuration selection also works well using3JCHvalues predicted from a semi‐empirical Karplus‐based equation limited to H−C−C−C fragments. The robustness, shown using strychnine as a proof of concept, makes theJ‐based CASE‐3D analysis a viable option for the application in fields such as peptide and carbohydrate research, organic synthesis, natural‐product identification and analysis, as well as medicinal chemistry.

     
    more » « less
  2. Abstract

    We present a method to use long‐range CH coupling constants to derive the correct diastereoisomer from the molecular constitution of small molecules. A set of 792JCHand3JCHvalues collected from a single HSQMBC experiment on a sample of strychnine were used in the CASE‐3D (computer‐assisted 3D structure elucidation) protocol. In addition to the most commonly used3JCHcoupling constants, the subset of 322JCHvalues alone showed an excellent degree of configuration selection. The study is mainly based on comparison of DFT‐calculated2,3JCHvalues with experimental ones, critical for the case of2JCH. But the configuration selection also works well using3JCHvalues predicted from a semi‐empirical Karplus‐based equation limited to H−C−C−C fragments. The robustness, shown using strychnine as a proof of concept, makes theJ‐based CASE‐3D analysis a viable option for the application in fields such as peptide and carbohydrate research, organic synthesis, natural‐product identification and analysis, as well as medicinal chemistry.

     
    more » « less
  3. Abstract

    Abundant transition metal borides are emerging as substitute electrochemical hydrogen evolution reaction (HER) catalysts for noble metals. Herein, an unusual canonic‐like behavior of theclattice parameter in the AlB2‐type solid solution Cr1–xMoxB2(x= 0, 0.25, 0.4, 0.5, 0.6, 0.75, 1) and its direct correlation to the HER activity in 0.5 M H2SO4solution are reported. The activity increases with increasingx, reaching its maximum atx= 0.6 before decreasing again. At high current densities, Cr0.4Mo0.6B2outperforms Pt/C, as it needs 180 mV less overpotential to drive an 800 mA cm−2current density. Cr0.4Mo0.6B2has excellent long‐term stability and durability showing no significant activity loss after 5000 cycles and 25 h of operation in acid. First‐principles calculations have correctly reproduced the nonlinear dependence of theclattice parameter and have shown that the mixed metal/B layers, such as (110), promote hydrogen evolution more efficiently forx= 0.6, supporting the experimental results.

     
    more » « less
  4. Summary

    Factors that affect the respiration of organic carbon by marine bacteria can alter the extent to which the oceans act as a sink of atmospheric carbon dioxide. We designed seawater dilution experiments to assess the effect ofpCO2enrichment on heterotrophic bacterial community composition and metabolic potential in response to a pulse of phytoplankton‐derived organic carbon. Experiments included treatments of elevated (1000 p.p.m.) and low (250 p.p.m.)pCO2amended with 10 μmol L−1dissolved organic carbon fromEmiliana huxleyilysates, and were conducted using surface‐seawater collected from the South Pacific Subtropical Gyre. To assess differences in community composition and metabolic potential, shotgun metagenomic libraries were sequenced from low and elevatedpCO2treatments collected at the start of the experiment and following exponential growth. Our results indicate bacterial communities changed markedly in response to the organic matter pulse over time and were significantly affected bypCO2enrichment. ElevatedpCO2also had disproportionate effects on the abundance of sequences related to proton pumps, carbohydrate metabolism, modifications of the phospholipid bilayer, resistance to toxic compounds and conjugative transfer. These results contribute to a growing understanding of the effects of elevatedpCO2on bacteria‐mediated carbon cycling during phytoplankton bloom conditions in the marine environment.

     
    more » « less
  5. Abstract

    A density functional theoretical (DFT) study is presented, implicating a1O2oxidation process to reach a dihydrobenzofuran from the reaction of the natural homoallylic alcohol, glycocitrine. Our results predict an interconversion between glycocitrine and aniso‐hydroperoxide intermediate [R(H)O+O] that provides a key path in the chemistry which then follows. Formations of allylic hydroperoxides are unlikely from a1O2‘ene’ reaction. Instead, the dihydrobenzofuran arises by1O2oxidation facilitated by a 16° curvature of the glycocitrine ring imposed by a pyramidalN‐methyl group. This curvature facilitates the formation of theiso‐hydroperoxide, which is analogous to theisospecies CH2I+Iand CHI2+Iformed by UV photolysis of CH2I2and CHI3. Theiso‐hydroperoxide is also structurally reminiscent of carbonyl oxides (R2C=O+O) formed in the reaction of carbenes and oxygen. Our DFT results point to intermolecular process, in which theiso‐hydroperoxide's fate relates to O‐transfer and H2O dehydration reactions for new insight into the biosynthesis of dihydrobenzofuran natural products.

     
    more » « less