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1. From spin-crossover to single molecule magnetism: tuning magnetic properties of Co( ii ) bis-ferrocenylterpy cations via supramolecular interactions with organocyanide radical anions

   https://doi.org/10.1039/d0tc00830c  

   Xie, Haomiao; Vignesh, Kuduva R.; Zhang, Xuan; Dunbar, Kim R. (June 2020, Journal of Materials Chemistry C)

   TCNQ (7,7,8,8-tetracyanoquinodimethane) anion-radical derivatives were used to fine tune the magnetic properties of the [Co II (Fctp) 2 ] 2+ (Fctp = 4′-(2-ferrocenyl)-2,2′:6′2′′-terpyridine) cation in the solid state. The cocrystallization of [Co II (Fctp) 2 ] 2+ with TCNQ˙ − yielded the two pseudo-polymorphic products [Co II (Fctp) 2 ] (TCNQ) 2 ( 1 ) and [Co II (Fctp) 2 ] (TCNQ) 2 ·MeCN ( 2 ) whereas the analogous reaction with TCNQF˙ − (TCNQF = 2-fluoro-7,7,8,8-tetracyanoquinodimethane) exclusively yielded [Co II (Fctp) 2 ] (TCNQF) 2 ·MeCN ( 3 ). Compound 1 exhibits slow relaxation of magnetization under an applied DC field with U eff = 19.1 K and τ 0 = 9.8 × 10 −6 s. Compounds 2 and 3 are isostructural but exhibit different spin-crossover behavior with transition temperatures of T 1/2 = 336 K and 226 K, respectively. Investigations of the solid state structures by DFT calculations indicate that the differences in magnetic properties of the cationic moiety, [Co II (Fctp) 2 ] 2+ , are induced by supramolecular interactions between [Co II (Fctp) 2 ] 2+ and tunable TCNQ˙ − /TCNQF˙ − anion-radical derivatives. 

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2. Cleavage of Carbon Dioxide C=O Bond Promoted by Nickel‐Boron Cooperativity in a PBP‐Ni Complex

   https://doi.org/10.1002/anie.202306315  

   Álvarez‐Rodríguez, Lucía; Ríos, Pablo; Laglera‐Gándara, Carlos J.; Jurado, Andrea; Fernández‐de‐Córdova, Francisco José; Gunnoe, T. Brent; Rodríguez, Amor (July 2023, Angewandte Chemie International Edition)

   Abstract The synthesis and characterization of (^tBuPBP)Ni(OAc) (5) by insertion of carbon dioxide into the Ni−C bond of (^tBuPBP)NiMe (1) is presented. An unexpected CO₂cleavage process involving the formation of new B−O and Ni−CO bonds leads to the generation of a butterfly‐structured tetra‐nickel cluster (^tBuPBOP)₂Ni₄(μ‐CO)₂(6). Mechanistic investigation of this reaction indicates a reductive scission of CO₂by O‐atom transfer to the boron atom via a cooperative nickel‐boron mechanism. The CO₂activation reaction produces a three‐coordinate (^tBuP₂BO)Ni‐acyl intermediate (A) that leads to a (^tBuP₂BO)−Ni^Icomplex (B) via a likely radical pathway. The Ni^Ispecies is trapped by treatment with the radical trap (2,2,6,6‐tetramethylpiperidin‐1‐yl)oxyl (TEMPO) to give (^tBuP₂BO)Ni^II(η²‐TEMPO) (7). Additionally,¹³C and¹H NMR spectroscopy analysis using¹³C‐enriched CO₂provides information about the species involved in the CO₂activation process. 

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3. Redox chemistry of an anionic dithiolene radical

   https://doi.org/10.1039/C8DT04989K  

   Wang, Yuzhong; Xie, Yaoming; Wei, Pingrong; Schaefer, Henry F.; Robinson, Gregory H. (March 2019, Dalton Transactions)

   The redox chemistry of the first stable anionic dithiolene radical 1˙ was investigated by both reactivity and cyclic voltammetry studies. While one-electron reduction of 1˙ by Cp 2 Co or KC 8 affords the corresponding dithiolate dimers 2 and 3 , respectively, one-electron oxidation of 1˙ by Ph 3 C + BF 4 − (or O 2 ) conveniently gives 4 , the neutral dithiolene dimer. 

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4. Electrocatalytic production of hydrogen peroxide enabled by post-synthetic modification of a self-assembled porphyrin cube

   https://doi.org/10.1039/d2qi02050e  

   Crawley, Matthew R.; Zhang, Daoyang; Cook, Timothy R. (December 2022, Inorganic Chemistry Frontiers)

   Self-assembled metallacyles and cages formed via coordination chemistry have been used as catalysts to enforce 4H + /4e − reduction of oxygen to water with an emphasis on attenuating the formation of hydrogen peroxide. That said, the kinetically favored 2H + /2e − reduction to H 2 O 2 is critically important to industry. In this work we report the synthesis, characterization, and electrochemical benchmarking of a hexa-porphyrin cube which catalyses the electrochemical reduction of molecular oxygen to hydrogen peroxide. An established sub-component self-assembly approach was used to synthesize the cubic free-base porphryin topologies from 2-pyridinecarboxaldehyde, tetra-4-aminophenylporphryin (TAPP), and Fe(OTf) 2 (OTf − = trifluoromethansulfonate). Then, a tandem metalation/transmetallation was used to introduce Co( ii ) into the porphyrin faces of the cube, and exchange with the Fe( ii ) cations at the vertices, furnishing a tetrakaideca cobalt cage. Electron paramagnetic resonance studies on a Cu( ii )/Fe( ii ) analogue probed radical interactions which inform on electronic structure. The efficacy and selectivity of the CoCo-cube as a catalyst for hydrogen peroxide generation was investigated using hydrodynamic voltammetry, revealing a higher selectivity than that of a mononuclear Co( ii ) porphyrin (83% versus ∼50%) with orders of magnitude enhancement in standard rate constant ( k s = 2.2 × 10 2 M −1 s −1 versus k s = 3 × 10 0 M −1 s −1 ). This work expands the use of coordination-driven self-assembly beyond ORR to water by exploiting post-synthetic modification and structural control that is associated with this synthetic method. 

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5. The Arizona Molecular ISM Survey with the SMT: Survey Overview and Public Data Release

   https://doi.org/10.3847/1538-4357/ad7504  

   Keenan, Ryan_P; Marrone, Daniel_P; Keating, Garrett_K; Mayer, Evan_C; Bays, Kevin; Downey, John; Dunn, Lochlann_C; Flores, Joanne_C; Folkers, Thomas_W; Forbes, David_C; et al (October 2024, The Astrophysical Journal)

   Abstract The CO(1–0) line has been carefully calibrated as a tracer of molecular gas mass. However, recent studies often favor higherJtransitions of the CO molecule, which are brighter and accessible for redshift ranges where CO(1–0) is not. These lines are not perfect analogs for CO(1–0), owing to their more stringent excitation conditions, and must be calibrated for use as molecular gas tracers. Here, we introduce the Arizona Molecular ISM Survey with the SMT, a multi-CO line survey ofz∼ 0 galaxies conducted to calibrate the CO(2–1) and CO(3–2) lines. The final survey includes CO(2–1) spectra of 176 galaxies and CO(3–2) spectra for a subset of 45. We supplement these with archival CO(1–0) spectra from xCOLD GASS for all sources and additional CO(1–0) observations with the Kitt Peak 12 m Telescope. Targets were selected to be representative of the 10⁹M_⊙≤M_*≤ 10^11.5M_⊙galaxy population. Our project emphasized careful characterization of statistical and systematic uncertainties to enable studies of trends in CO line ratios. We show that optical and CO disk sizes are on average equal, for both the CO(1–0) and CO(2–1) line. We measure the distribution of CO line luminosity ratios, finding medians (16th–84th percentile) of 0.71 (0.51–0.96) for the CO(2–1)-to-CO(1–0) ratio, 0.39 (0.24–0.53) for the CO(3–2)-to-CO(1–0) ratio, and 0.53 (0.41–0.74) for the CO(3–2)-to-CO(2–1) ratio. A companion paper presents our study of CO(2–1)'s applicability as a molecular gas mass tracer and search for trends in the CO(2–1)-to-CO(1–0) ratio. Our catalog of CO line luminosities is publicly available. 

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