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1. A new era of LMCT: leveraging ligand-to-metal charge transfer excited states for photochemical reactions

   https://doi.org/10.1039/D3SC05268K  

   May, Ann Marie; Dempsey, Jillian L (May 2024, Chemical Science)

   Ligand-to-metal charge transfer (LMCT) excited states are capable of undergoing a wide array of photochemical reactions, yet receive minimal attention compared to other charge transfer excited states. This work provides general criteria for designing transition metal complexes that exhibit low energy LMCT excited states and routes to drive photochemistry from these excited states. General design principles regarding metal identity, oxidation state, geometry, and ligand sets are summarized. Fundamental photoreactions from these states including visible light-induced homolysis, excited state electron transfer, and other photoinduced chemical transformations are discussed and key design principles for enabling these photochemical reactions are further highlighted. Guided by these fundamentals, this review outlines critical considerations for the future design and application of coordination complexes with LMCT excited states. 

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2. Mild electrochemical synthesis of metal phosphides with dibenzo-7-phosphanorbornadiene derivatives: mechanistic insights and application to proton reduction in water

   https://doi.org/10.1039/c7cc09003j  

   Shida, Naoki; Buss, Joshua A.; Agapie, Theodor (January 2018, Chemical Communications)

   Transition metal phosphide films were synthesized using a mild electrochemical method. Dibenzo-7-phosphanorbornadiene derivatives (XPA) are introduced as versatile precursors to amorphous metal phosphide electrocatalysts for proton reduction in acidic water. Homogeneous model reactions reveal distinct reactivity between XPA and nickel in different oxidation states, with Ni(0) resulting in Ni x P y formation. 

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3. Anomalous shot noise in a bad metal β-tantalum

   https://doi.org/10.1063/5.0245223  

   Szurek, Mateusz; Cheng, Hanqiao; Pang, Zilu; Zhang, Yiou; Bacsa, John; Urazhdin, Sergei (February 2025, Applied Physics Letters)

   We investigate the electronic shot noise produced by nanowires of β-Ta, an archetypal “bad” metal with resistivity near the Ioffe–Regel localization limit. The Fano factor characterizing the shot noise exhibits a strong dependence on temperature and is suppressed compared to the expectations for quasiparticle diffusion, but hopping transport is ruled out by the analysis of scaling with the nanowire length. These anomalous behaviors closely resemble those of strange metal nanowires, suggesting that β-Ta may host a correlated electron liquid. This material provides an accessible platform for exploring exotic electronic states of matter. 

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4. Correction to “From n- to p-Type Material: Effect of Metal Ion on Charge Transport in Metal–Organic Materials”

   https://doi.org/10.1021/acsami.2c05799  

   Yoon, Sungwon; Talin, A. Alec; Stavila, Vitalie; Mroz, Austin M.; Bennett, Thomas D.; He, Yuping; Keen, David A.; Hendon, Christopher H.; Allendorf, Mark D.; So, Monica C. (April 2022, ACS Applied Materials & Interfaces)

   An intriguing new class of two-dimensional (2D) materials based on metal–organic frameworks (MOFs) has recently been developed that displays electrical conductivity, a rarity among these nanoporous materials. The emergence of conducting MOFs raises questions about their fundamental electronic properties, but few studies exist in this regard. Here, we present an integrated theory and experimental investigation to probe the effects of metal substitution on the charge transport properties of M-HITP, where M = Ni or Pt and HITP = 2,3,6,7,10,11-hexaiminotriphenylene. The results show that the identity of the M-HITP majority charge carrier can be changed without intentional introduction of electronically active dopants. We observe that the selection of the metal ion substantially affects charge transport. Using the known structure, Ni-HITP, we synthesized a new amorphous material, a-Pt-HITP, which although amorphous is nevertheless found to be porous upon desolvation. Importantly, this new material exhibits p-type charge transport behavior, unlike Ni-HITP, which displays n-type charge transport. These results demonstrate that both p- and n-type materials can be achieved within the same MOF topology through appropriate choice of the metal ion. 

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5. A Guide to Troubleshooting Metal Sacrificial Anodes for Organic Electrosynthesis

   https://doi.org/10.1039/D3SC06885D  

   Ware, Skyler D.; Zhang, Wendy; Guan, Weiyang; Lin, Song; See, Kimberly A. (March 2024, Chemical Science)

   The development of reductive electrosynthetic reactions is often enabled by the oxidation of a sacrificial metal anode, which charge-balances the reductive reaction of interest occurring at the cathode. The metal... 

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