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  1. Free, publicly-accessible full text available December 27, 2023
  2. Free, publicly-accessible full text available August 8, 2023
  3. Herein, we report structural, computational, and conductivity studies on urea-directed self-assembled iodinated triphenylamine (TPA) derivatives. Despite numerous reports of conductive TPAs, the challenges of correlating their solid-state assembly with charge transport properties hinder the efficient design of new materials. In this work, we compare the assembled structures of a methylene urea bridged dimer of di-iodo TPA (1) and the corresponding methylene urea di-iodo TPA monomer (2) with a di-iodo mono aldehyde (3) control. These modifications lead to needle shaped crystals for 1 and 2 that are organized by urea hydrogen bonding, π⋯π stacking, I⋯I, and I⋯π interactions as determined by SC-XRD, Hirshfeld surface analysis, and X-ray photoelectron spectroscopy (XPS). The long needle shaped crystals were robust enough to measure the conductivity by two contact probe methods with 2 exhibiting higher conductivity values (∼6 × 10 −7 S cm −1 ) compared to 1 (1.6 × 10 −8 S cm −1 ). Upon UV-irradiation, 1 formed low quantities of persistent radicals with the simple methylurea 2 displaying less radical formation. The electronic properties of 1 were further investigated using valence band XPS, which revealed a significant shift in the valence band upon UV irradiation (0.5–1.9 eV), indicating the potential of thesemore »materials as dopant free p-type hole transporters. The electronic structure calculations suggest that the close packing of TPA promotes their electronic coupling and allows effective charge carrier transport. Our results show that ionic additives significantly improve the conductivity up to ∼2.0 × 10 −6 S cm −1 in thin films, enabling their implementation in functional devices such as perovskite or solid-state dye sensitized solar cells.« less
    Free, publicly-accessible full text available August 10, 2023

    The mm-Wave Interferometric Survey of Dark Object Masses (WISDOM) is probing supermassive black holes (SMBHs) in galaxies across the Hubble sequence via molecular gas dynamics. We present the first WISDOM study of a luminous infrared galaxy with an active galactic nuclei (AGNs): Fairall 49. We use new ALMA observations of the CO(2 − 1) line with a spatial resolution of ∼80 pc together with ancillary HST imaging. We reach the following results: (1) The CO kinematics are well described by a regularly rotating gas disc with a radial inflow motion, suggesting weak feedback on the cold gas from both AGN and starburst activity; (2) The dynamically inferred SMBH mass is 1.6 ± 0.4(rnd) ± 0.8(sys) × 108 M⊙ assuming that we have accurately subtracted the AGN and starburst light contributions, which have a luminosity of ∼109 L⊙; (3) The SMBH mass agrees with the SMBH−stellar mass relation but is ∼50 times higher than previous estimates from X-ray variability; (4) The dynamically inferred molecular gas mass is 30 times smaller than that inferred from adopting the Galactic CO-to-H2 conversion factor (XCO) for thermalized gas, suggesting low values of XCO; (5) the molecular gas inflow rate increases steadily with radius and may be as high as ∼5 M⊙ yr−1. This work highlights themore »potential of using high-resolution CO data to estimate, in addition to SMBH masses, the XCO factor, and gas inflow rates in nearby galaxies.

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  5. Free, publicly-accessible full text available May 4, 2023
  6. Free, publicly-accessible full text available February 21, 2023
  7. Free, publicly-accessible full text available February 2, 2023
  8. Absorption of electronic acceptors in the accessible channels of an assembled triphenylamine (TPA) bis -urea macrocycle 1 enabled the study of electron transfer from the walls of the TPA framework to the encapsulated guests. The TPA host is isoskeletal in all host–guest structures analyzed with guests 2,1,3-benzothiadiazole, 2,5-dichlorobenzoquinone and I 2 loading in single-crystal-to-single-crystal transformations. Analysis of the crystal structures highlights how the spatial proximity and orientation of the TPA host and the entrapped guests influence their resulting photophysical properties and allow direct comparison of the different donor–acceptor complexes. Diffuse reflectance spectroscopy shows that upon complex formation 1·2,5-dichlorobenzoquinone exhibits a charge transfer (CT) transition. Whereas, the 1·2,1,3-benzothiadiazole complex undergoes a photoinduced electron transfer (PET) upon irradiation with 365 nm LEDs. The CT absorptions were also identified with the aid of time dependent density functional theory (TD-DFT) calculations. Cyclic voltammetry experiments show that 2,1,3-benzothiadiazole undergoes reversible reduction within the host–guest complex. Moreover, the optical band gaps of the host 1·2,5-dichlorobenzoquinone (1.66 eV), and host 1·2,1,3-benzothiadiazole (2.15 eV) complexes are significantly smaller as compared to the free host 1 material (3.19 eV). Overall, understanding this supramolecular electron transfer strategy should pave the way towards designing lower band gap inclusion complexes.