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1. Electron and Spin Delocalization in [Co 6 Se 8 (PEt 3 ) 6 ] 0/+1 Superatoms

   https://doi.org/10.1002/cphc.202300064  

   Xu, Yunyao ; Chen, Jia ; Aydt, Alexander P. ; Zhang, Lichirui ; Sergeyev, Ivan ; Keeler, Eric G. ; Choi, Bonnie ; He, Shoushou ; Reichman, David R. ; Friesner, Richard A. ; et al ( January 2024 , ChemPhysChem)

   ChemPhysChem (Ed.)

   Molecular clusters can function as nanoscale atoms/superatoms, assembling into superatomic solids, a new class of solid‐state materials with designable properties through modifications on superatoms. To explore possibilities on diversifying building blocks, here we thoroughly studied one representative superatom, Co₆Se₈(PEt₃)₆. We probed its structural, electronic, and magnetic properties and revealed its detailed electronic structure as valence electrons delocalize over inorganic [Co₆Se₈] core while ligands function as an insulated shell.⁵⁹Co SSNMR measurements on the core and³¹P,¹³C on the ligands show that the neutral Co₆Se₈(PEt₃)₆is diamagnetic and symmetric, with all ligands magnetically equivalent. Quantum computations cross‐validate NMR results and reveal degenerate delocalized HOMO orbitals, indicating aromaticity. Ligand substitution keeps the inorganic core nearly intact. After losing one electron, the unpaired electron in [Co₆Se₈(PEt₃)₆]⁺¹is delocalized, causing paramagnetism and a delocalized electron spin. Notably, this feature of electron/spin delocalization over a large cluster is attractive for special single‐electron devices.

    

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2. [Ni 30 S 16 (PEt 3 ) 11 ]: an open-shell nickel sulfide nanocluster with a “metal-like” core

   https://doi.org/10.1039/D2SC00960A  

   Touchton, Alexander J. ; Wu, Guang ; Hayton, Trevor W. ( May 2022 , Chemical Science)

   Reaction of [Ni(1,5-cod) 2 ] (30 equiv.) with PEt 3 (46 equiv.) and S 8 (1.9 equiv.) in toluene, followed by heating at 115 °C for 16 h, results in the formation of the atomically precise nanocluster (APNC), [Ni 30 S 16 (PEt 3 ) 11 ] (1), in 14% isolated yield. Complex 1 represents the largest open-shell Ni APNC yet isolated. In the solid state, 1 features a compact “metal-like” core indicative of a high degree of Ni–Ni bonding. Additionally, SQUID magnetometry suggests that 1 possesses a manifold of closely-spaced electronic states near the HOMO–LUMO gap. In situ monitoring by ESI-MS and 31 P{ 1 H} NMR spectroscopy reveal that 1 forms via the intermediacy of smaller APNCs, including [Ni 8 S 5 (PEt 3 ) 7 ] and [Ni 26 S 14 (PEt 3 ) 10 ] (2). The latter APNC was also characterized by X-ray crystallography and features a nearly identical core structure to that found in 1. This work demonstrates that large APNCs with a high degree of metal–metal bonding are isolable for nickel, and not just the noble metals. 

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3. Mild Hydrothermal Synthesis of the Complex Hafnium-Containing Fluorides Cs 2 [M(H 2 O) 6 ][Hf 2 F 12 ] (M = Ni, Co, Zn), CuHfF 6 (H 2 O) 4 , and Cs 2 Hf 3 Mn 3 F 20 Based on HfF 7 and HfF 6 Coordination Polyhedra

   https://doi.org/10.1021/acs.inorgchem.9b01958  

   Ayer, Gyanendra B. ; Klepov, Vladislav V. ; Smith, Mark D. ; zur Loye, Hans-Conrad ( September 2019 , Inorganic Chemistry)
4. Sn 4−δ B 12 Se 12 [Q x ], Q = Se, Te, a B 12 Cluster Tunnel Framework Hosting Neutral Chalcogen Chains

   https://doi.org/10.1021/acs.chemmater.0c04503  

   Chica, Daniel G. ; Spanopoulos, Ioannis ; Hao, Shiqiang ; Wolverton, Chris ; Kanatzidis, Mercouri G. ( March 2021 , Chemistry of Materials)

   null (Ed.)
5. Unusual Coexistence of Nickel(II) and Nickel(IV) in the Quadruple Perovskite Ba 4 Ni 2 Ir 2 O 12 Containing Ir 2 NiO 12 Mixed-Metal-Cation Trimers

   https://doi.org/10.1021/acs.inorgchem.8b00249  

   Ferreira, Timothy ; Heald, Steve M. ; Smith, Mark. D. ; zur Loye, Hans-Conrad ( March 2018 , Inorganic Chemistry)