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1. Pyridine-terminated low gap π-conjugated oligomers: design, synthesis, and photophysical response to protonation and metalation

   https://doi.org/10.1039/c8qo00963e  

   Weldeab, Asmerom O. ; Li, Lei ; Cekli, Seda ; Abboud, Khalil A. ; Schanze, Kirk S. ; Castellano, Ronald K. ( October 2018 , Organic Chemistry Frontiers)

   null (Ed.)

   Reported here is the design and synthesis of among the first pyridine terminated acceptor–donor–acceptor–donor–acceptor (A–D–A–D–A) based π-conjugated oligomers, EH_DPP_2T_Pyr ( 1 ), EH_II_2T_Pyr ( 2 ), and EH_II_1T_Pyr ( 3 ). The molecules incorporate thiophenes as electron donors, isoindigo/diketopyrrolopyrrole as electron acceptors, and are capped with pyridine, a weak electron acceptor, on both ends. All target oligomers show attractive photophysical properties, broad absorption in the visible region ( λ max = 636 nm, 575 nm, and 555 nm, for 1 , 2 , and 3 , respectively) and emission which extends to the IR region (emission λ max = 734 nm and 724 for 1 and 2 , respectively). Given the pyridine nitrogens, the optoelectronic properties of the compounds can be further tuned by protonation/metalation. All compounds show a bathochromic shift in visible absorption and fluorescence quenching upon addition of trifluoroacetic acid (TFA). Similar phenomena are observed upon addition of metals with a particularly strong response to Cu 2+ and Pd 2+ as indicated by Stern–Volmer analysis ( e.g. , for Pd 2+ ; K sv = 7.2 × 10 4 M −1 ( λ = 673 nm), 8.5 × 10 4 M −1 ( λ = 500 nm), and 1.1 × 10 5 ( λ = 425 nm) for 1 , 2 , and 3 , respectively). The selective association of the molecules to Cu 2+ and Pd 2+ is further evidenced by a color change easily observed by eye and under UV light, important for potential use in colorimetric sensing. 

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2. Formation of Stilbene Azo‐Dimer by Direct Irradiation of p‐Azidostilbene †

   https://doi.org/10.1111/php.13659  

   Osisioma, Onyinye ; Patton, Leanna J. ; Merugu, Rajkumar ; Govorov, Dmitrii ; Milbrandt, Margaret A. ; Jarus, Cassandra ; Karney, William L. ; Gudmundsdottir, Anna D. ( July 2022 , Photochemistry and Photobiology)

   Triplet arylnitrenes may provide direct access to aryl azo‐dimers, which have broad commercial applicability. Herein, the photolysis ofp‐azidostilbene (1) in argon‐saturated methanol yielded stilbene azo‐dimer (2) through the dimerization of tripletp‐nitrenostilbene (³1N). The formation of³1Nwas verified by electron paramagnetic resonance spectroscopy and absorption spectroscopy (λ_max ~ 375 nm) in cryogenic 2‐methyltetrahydrofuran matrices. At ambient temperature, laser flash photolysis of1in methanol formed³1N(λ_max ~ 370 nm, 2.85 × 10⁷ s⁻¹). On shorter timescales, a transient absorption (λ_max ~ 390 nm) that decayed with a similar rate constant (3.11 × 10⁷ s⁻¹) was assigned to a triplet excited state (T) of1. Density functional theory calculations yielded three configurations for T of1, with the unpaired electrons on the azido (T_A) or stilbene moiety (T_Tw, twisted and T_Fl, flat). The transient was assigned to T_Twbased on its calculated spectrum. CASPT2 calculations gave a singlet–triplet energy gap of 16.6 kcal mol⁻¹for1 N; thus, intersystem crossing of¹1Nto³1Nis unlikely at ambient temperature, supporting the formation of³1Nfrom T of1. Thus, sustainable synthetic methods for aryl azo‐dimers can be developed using the visible‐light irradiation of aryl azides to form triplet arylnitrenes.

    

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3. Enabling coherent BaZrO 3 nanorods/YBa 2 Cu 3 O 7−x interface through dynamic lattice enlargement in vertical epitaxy of BaZrO 3 /YBa 2 Cu 3 O 7−x nanocomposites

   https://doi.org/10.1088/1361-6668/ac4aff  

   Wu, Judy Z ; Ogunjimi, Victor ; Sebastian, Mary Ann ; Zhang, Di ; Jian, Jie ; Huang, Jijie ; Zhang, Yifan ; Gautam, Bibek ; Haugan, Timothy ; Wang, Haiyan ( February 2022 , Superconductor Science and Technology)

   Abstract One-dimensional c -axis-aligned BaZrO 3 (BZO) nanorods are regarded as strong one-dimensional artificial pinning centers (1D-APCs) in BZO-doped YaBa 2 Cu 3 O 7− x (BZO/YBCO) nanocomposite films. However, a microstructure analysis has revealed a defective, oxygen-deficient YBCO column around the BZO 1D-APCs due to the large lattice mismatch of ∼7.7% between the BZO (3a = 1.26 nm) and YBCO (c = 1.17 nm), which has been blamed for the reduced pinning efficiency of BZO 1D-APCs. Herein, we report a dynamic lattice enlargement approach on the tensile strained YBCO lattice during the BZO 1D-APCs growth to induce c -axis elongation of the YBCO lattice up to 1.26 nm near the BZO 1D-APC/YBCO interface via Ca/Cu substitution on single Cu-O planes of YBCO, which prevents the interfacial defect formation by reducing the BZO/YBCO lattice mismatch to ∼1.4%. Specifically, this is achieved by inserting thin Ca 0.3 Y 0.7 Ba 2 Cu 3 O 7− x (CaY-123) spacers as the Ca reservoir in 2–6 vol.% BZO/YBCO nanocomposite multilayer (ML) films. A defect-free, coherent BZO 1D-APC/YBCO interface is confirmed in transmission electron microscopy and elemental distribution analyses. Excitingly, up to five-fold enhancement of J c ( B ) at magnetic field B = 9.0 T// c -axis and 65 K–77 K was obtained in the ML samples as compared to their BZO/YBCO single-layer (SL) counterpart’s. This has led to a record high pinning force density F p together with significantly enhanced B max at which F p reaches its maximum value F p,max for BZO 1D-APCs at B // c -axis. At 65 K, the F p,max ∼158 GN m −3 and B max ∼ 8.0 T for the 6% BZO/YBCO ML samples represent a significant enhancement over F p,max ∼ 36.1 GN m −3 and B max ∼ 5.0 T for the 6% BZO/YBCO SL counterparts. This result not only illustrates the critical importance of a coherent BZO 1D-APC/YBCO interface in the pinning efficiency, but also provides a facile scheme to achieve such an interface to restore the pristine pinning efficiency of the BZO 1D-APCs. 

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4. High broadband photoconductivity of few-layered MoS 2 field-effect transistors measured using multi-terminal methods: effects of contact resistance

   https://doi.org/10.1039/D0NR07311C  

   Das, Priyanka ; Nash, Jawnaye ; Webb, Micah ; Burns, Raelyn ; Mapara, Varun N. ; Ghimire, Govinda ; Rosenmann, Daniel ; Divan, Ralu ; Karaiskaj, Denis ; McGill, Stephen A. ; et al ( January 2020 , Nanoscale)

   null (Ed.)

   Among the layered two dimensional semiconductors, molybdenum disulfide (MoS 2 ) is considered to be an excellent candidate for applications in optoelectronics and integrated circuits due to its layer-dependent tunable bandgap in the visible region, high ON/OFF current ratio in field-effect transistors (FET) and strong light–matter interaction properties. In this study, using multi-terminal measurements, we report high broadband photocurrent response ( R ) and external quantum efficiency (EQE) of few-atomic layered MoS 2 phototransistors fabricated on a SiO 2 dielectric substrate and encapsulated with a thin transparent polymer film of Cytop. The photocurrent response was measured using a white light source as well as a monochromatic light of wavelength λ = 400 nm–900 nm. We measured responsivity using a 2-terminal configuration as high as R = 1 × 10 3 A W −1 under white light illumination with an optical power P opt = 0.02 nW. The R value increased to 3.5 × 10 3 A W −1 when measured using a 4-terminal configuration. Using monochromatic light on the same device, the measured values of R were 10 3 and 6 × 10 3 A W −1 under illumination of λ = 400 nm when measured using 2- and 4-terminal methods, respectively. The highest EQE values obtained using λ = 400 nm were 10 5 % and 10 6 % measured using 2- and 4-terminal configurations, respectively. The wavelength dependent responsivity decreased from 400 nm to the near-IR region at 900 nm. The observed photoresponse, photocurrent–dark current ratio (PDCR), detectivity as a function of applied gate voltage, optical power, contact resistances and wavelength were measured and are discussed in detail. The observed responsivity is also thoroughly studied as a function of contact resistance of the device. 

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5. Efficient Broadband Near‐Infrared Emission in the GaTaO 4 :Cr 3+ Phosphor

   https://doi.org/10.1002/adom.202101800  

   Zhong, Jiyou ; Zhuo, Ya ; Du, Fu ; Zhang, Hongshi ; Zhao, Weiren ; You, Shihai ; Brgoch, Jakoah ( November 2021 , Advanced Optical Materials)

   Efficient broadband near‐infrared (NIR) emitting materials with an emission peak centered above 830 nm are crucial for smart NIR spectroscopy‐based technologies. However, the development of these materials remains a significant challenge. Herein, a series of design rules rooted in computational methods and empirical crystal‐chemical analysis is applied to identify a new Cr³⁺‐substituted phosphor. The compound GaTaO₄:Cr³⁺emerged from this study is based on the material's high structural rigidity, suitable electronic environment, and relatively weak electron–phonon coupling. Irradiating this new phosphor with 460 nm blue light generates a broadband NIR emission (λ_em,max = 840 nm) covering the 700–1100 nm region of the electromagnetic spectrum with a full width at half maximum of 140 nm. The phase has a high internal quantum yield of 91% and excellent thermal stability, maintaining 85% of the room temperature emission intensity at 100 °C. Fabricating a phosphor‐converted light‐emitting diode device shows that the new compound generates an intense NIR emission (178 mW at 500 mA) with photoelectric efficiency of 6%. This work not only provides a new material that has the potential for next‐generation high‐power NIR applications but also highlights a set of design rules capable of developing highly efficient long‐wavelength broadband NIR materials.

    

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