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1. A proton-responsive ligand becomes a dimetal linker for multisubstrate assembly via nitrate deoxygenation

   https://doi.org/10.1039/D0CC07886G  

   Cabelof, Alyssa C.; Carta, Veronica; Caulton, Kenneth G. (March 2021, Chemical Communications)

   null (Ed.)

   A bidentate pyrazolylpyridine ligand (HL) was installed on divalent nickel to give [(HL) 2 Ni(NO 3 )]NO 3 . This compound reacts with a bis-silylated heterocycle, 1,4-bis-(trimethylsilyl)-1,4-diaza-2,5-cyclohexadiene (TMS 2 Pz) to simultaneously reduce one of the nitrate ligands and deprotonate one of the HL ligands, giving octahedral (HL)(L − )Ni(NO 3 ). The mononitrate species formed is then further reacted with TMS 2 Pz to doubly deoxygenate nitrate and form [(L − )Ni(NO)] 2 , dimeric via bridging pyrazolate with bent nitrosyl ligands, representing a two-electron reduction of coordinated nitrate. Independent synthesis of a dimeric species [(L − )Ni(Br)] 2 is reported and effectively assembles two metals with better atom economy. 

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2. Tetrathiafulvalene-2,3,6,7-tetrathiolate linker redox-state elucidation via S K-edge X-ray absorption spectroscopy

   https://doi.org/10.1039/d3cc02325g  

   Jiang, Ningxin; Boyn, Jan-Niklas; Ramanathan, Arun; La Pierre, Henry S.; Anderson, John S. (July 2023, Chemical Communications)

   Sulfur K-edge XAS data provide a unique tool to examine oxidation states and covalency in electronically complex S-based ligands. We present sulfur K-edge X-ray absorption spectroscopy on a discrete redox-series of Ni-based tetrathiafulvalene tetrathiolate (TTFtt) complexes as well as on a 1D coordination polymer (CP), NiTTFtt. Experiment and theory suggest that Ni–S covalency decreases with oxidation which has implications for charge transport pathways. 

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3. Intermolecular and Intramolecular Interactions of the Arabidopsis Plasma Membrane Proton Pump Revealed Using a Mass Spectrometry Cleavable Cross-Linker

   https://doi.org/10.1021/acs.biochem.0c00268  

   Nguyen, Thao T.; Blackburn, Matthew R.; Sussman, Michael R. (June 2020, Biochemistry)

   null (Ed.)
4. A Layered, Piedfort-Aggregated Cu(I) Isocyanide Coordination Network Derived from an Encumbering Tritopic Linker

   https://doi.org/10.1021/acs.inorgchem.5c02312  

   Grippo, Adam M; Hernandez, Ritchie E; Gembicky, Milan; Figueroa, Joshua S (August 2025, Inorganic Chemistry)
5. Cross-linker control of vitrimer flow

   https://doi.org/10.1039/D0PY00233J  

   El-Zaatari, Bassil M.; Ishibashi, Jacob S.; Kalow, Julia A. (August 2020, Polymer Chemistry)

   Vitrimers are a class of covalent adaptable networks (CANs) that undergo topology reconfiguration via associative exchange reactions, enabling reprocessing at elevated temperatures. Here, we show that cross-linker reactivity represents an additional design parameter to tune stress relaxation rates in vitrimers. Guided by calculated activation barriers, we prepared a series of cross-linkers with varying reactivity for the conjugate addition—elimination of thiols in a PDMS vitrimer. Surprisingly, despite a wide range of stress relaxation rates, we observe that the flow activation energy of the bulk material is independent of the cross-linker structure. Superposition of storage and loss moduli from frequency sweeps can be performed for different cross-linkers, indicating the same exchange mechanism. We show that we can mix different cross-linkers in a single material in order to further modulate the stress relaxation behavior. 

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