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1. Assembled triphenylamine bis -urea macrocycles: exploring photodriven electron transfer from host to guests

   https://doi.org/10.1039/D1CP03000K  

   Islam, Md Faizul; Sindt, Ammon J.; Hossain, Muhammad Saddam; Ayare, Pooja J.; Smith, Mark D.; Vannucci, Aaron K.; Garashchuk, Sophya; Shimizu, Linda S. (October 2021, Physical Chemistry Chemical Physics)

   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. 

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2. Highly Efficient, Long-Lived Charge Separated States in Star-Shaped Ferrocene-Diketopyrrolopyrrole-Triphenylamine Donor-Acceptor-Donor Conjugates

   https://doi.org/doi.org/10.1002/chem.202000346  

   M. Poddar, Y. Jang (November 2020, Chemistry)

   null (Ed.)

   The significance of multiple number of donor-acceptor entities on a central electron donor in a star-shaped molecular system in improving light energy harvesting ability is reported. For this, donor-acceptor-donor type conjugates comprised up to three entities ferrocenyl (Fc)-diketopyrrolopyrrole (DPP) onto a central triphenylamine (TPA), (4-6) by the Pd-catalyzed Sonogashira cross–coupling reactions have been newly synthesized and characterized. Donor-acceptor conjugates possessing diketopyrrolopyrrole (1 to 3 entities) onto the central triphenylamine, (1-3) served as reference dyads while monomeric DPP and Fc-DPP served as control compounds. Both DPP and Fc-DPP carrying conjugates exhibited red-shifted absorption compared to their respective control compounds revealing existence of ground state interactions. Furthermore, DPP fluorescence in 4-6 was found to be quantitatively quenched while for 1-3, this property varied between 73-65% suggesting occurrence moderate amounts of excited state events. The electrochemical investigations exhibited an additional low potential oxidation in the case of Fc-DPP-TPA based derivatives (4-6) owing to the presence of ferrocene unit(s). This was in addition to DPP and TPA redox peaks. Using spectral, electrochemical and computational studies, Gibbs free-energy calculations were performed to visualize excited state charge separation (GCS) in these donor-acceptor conjugates as a function of different number of Fc-DPP entities. Formation of Fc+-DPP•--TPA charge separated states (CSS) in the case of 4-6 was evident. Using spectroelectrochemical studies, spectrum of CSS was deduced. Finally, femtosecond transient absorption spectral studies were performed to gather information on excited state charge separation. Increasing the number of Fc-DPP entities in 4-6 improved charge separation rates. Surprisingly, lifetime of the charge separated state, Fc+-DPP•--TPA was found to persist longer with an increase in the number of Fc-DPP entities in 4-6 as compared to Fc-DPP-control and simple DPP derived donor-acceptor conjugates in literature. This unprecedented result has been attributed to subtle changes in GCS and GCR and the associated electron coupling between different entities. 

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3. Pressure-regulated synthesis of Cu(TPA)·(DMF) in microdroplets for selective CO ₂ adsorption

   https://doi.org/10.1039/C8DT03812K  

   He, Xiang; Wang, Wei-Ning (January 2019, Dalton Transactions)

   The synthesis of metal–organic frameworks (MOFs) by using traditional wet-chemistry methods generally requires very long durations and still suffers from non-uniform heat and mass transfer within the bulk precursor solutions. Towards addressing these issues, a microdroplet-based spray method has been developed. In a typical spray process, an MOF's precursor solution is first atomized into microdroplets. These droplets serve as microreactors to ensure homogeneous mixing, fast evaporation, and rapid nucleation and crystal growth to form MOF particles. However, the fundamental MOF formation mechanisms by using this strategy have not been fully understood. In this work, the role of the operating pressure in the synthesis of a representative MOF ( i.e. , Cu(TPA)·(DMF); TPA: terephthalic acid, DMF: dimethylformamide) was systematically investigated. Detailed characterization showed that the pressure variations significantly affected both the morphologies and crystalline structures of Cu(TPA)·(DMF). Numerical simulations revealed that the morphology changes are mainly attributed to the variations in supersaturation ratios, which are caused by different microdroplet evaporation rates due to the regulation of operating pressure, while the crystalline structure variations are closely related to the dissociation of DMF molecules at lower operating pressures. Besides, the dissociation of DMF molecules decreased the surface area of the MOF crystals, but gave rise to massive coordinatively unsaturated metal sites, which greatly enhanced the interaction of CO 2 with the MOF crystal and thus led to improved CO 2 adsorption capacity and selectivity. The outcome of this work would contribute to the fundamental understanding of MOF synthesis using the microdroplet-based spray method. 

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4. Cooperative Supramolecular Polymerization of Triphenylamine bis‐Urea Macrocycles

   https://doi.org/10.1002/chem.202300698  

   Prakash, Rahul; Islam, Md Faizul; Kothalawala, Rajeen Madawa; Hossain, Muhammad Saddam; Smith, Mark D.; Shimizu, Linda S. (June 2023, Chemistry – A European Journal)

   Herein, we probe the hydrogen bond‐driven self‐assembly of a triphenylamine (TPA) bis‐urea macrocycle in the presence and absence of guests. Comprised of methylene urea‐bridged TPAs with exterior tridodecyloxy benzene solubilizing groups, the macrocycle exhibits concentration‐dependent aggregate formation in THF and H₂O/THF mixtures as characterized by¹H NMR and DOSY experiments. Its assembly processes were further probed by temperature‐dependent UV/Vis and fluorescence spectroscopy. Upon heating, UV/Vis spectra exhibit a hypsochromic shift in the λ_max, while fluorescence spectra show an increase in emission intensity. Conversely, the protected macrocycle that lacks hydrogen bond donors demonstrates no significant change. Thermodynamic analysis indicates a cooperative self‐assembly pathway with distinct nucleation and elongation regimes. The morphology and structure of the aggregate were elucidated by dynamic light scattering, atomic force microscopy, scanning and transmission electron microscopy. Variable temperature emission spectra were utilized to monitor the impact of guests, such as diphenylacetylene, that can be bound in the columnar channels. The findings suggest that the elongation of assemblies is influenced by the presence of these guests. In comparison, diphenyl sulfoxide, likely functioning as a chain stopper, limited the assembly size. These studies suggest that judicious selection of (co)monomers may modulate the function and utility of these supramolecular systems. 

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5. Structure and density of silicon carbide to 1.5 TPa and implications for extrasolar planets

   https://doi.org/10.1038/s41467-022-29762-y  

   Kim, D.; Smith, R. F.; Ocampo, I. K.; Coppari, F.; Marshall, M. C.; Ginnane, M. K.; Wicks, J. K.; Tracy, S. J.; Millot, M.; Lazicki, A.; et al (December 2022, Nature Communications)

   Abstract There has been considerable recent interest in the high-pressure behavior of silicon carbide, a potential major constituent of carbon-rich exoplanets. In this work, the atomic-level structure of SiC was determined through in situ X-ray diffraction under laser-driven ramp compression up to 1.5 TPa; stresses more than seven times greater than previous static and shock data. Here we show that the B1-type structure persists over this stress range and we have constrained its equation of state (EOS). Using this data we have determined the first experimentally based mass-radius curves for a hypothetical pure SiC planet. Interior structure models are constructed for planets consisting of a SiC-rich mantle and iron-rich core. Carbide planets are found to be ~10% less dense than corresponding terrestrial planets. 

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