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1. First Structurally Characterized Tricyanomanganate(III) and its Magnetic {Mn ^III ₂ M ^II ₂ } Complexes (M ^II = Mn, Ni)

   https://doi.org/10.1021/ic1006605  

   Tang, Minao; Li, Dongfeng; Mallik, Uma Prasad; Withers, Jeffrey R.; Brauer, Shari; Rhodes, Michael R.; Clérac, Rodolphe; Yee, Gordon T.; Whangbo, Myung-Hwan; Holmes, Stephen M. (June 2010, Inorganic Chemistry)
2. 10 ⁶ -fold faster C–H bond hydroxylation by a Co ^III,IV ₂ (µ-O) ₂ complex [via a Co ^III ₂ (µ-O)(µ-OH) intermediate] versus its Fe ^III Fe ^IV analog

   https://doi.org/10.1073/pnas.2307950120  

   Li, Yan; Abelson, Chase; Que, Lawrence; Wang, Dong (December 2023, Proceedings of the National Academy of Sciences)

   The hydroxylation of C–H bonds can be carried out by the high-valent Co^III,IV₂(µ-O)₂complex2asupported by the tetradentate tris(2-pyridylmethyl)amine ligand via a Co^III₂(µ-O)(µ-OH) intermediate (3a). Complex3acan be independently generated either by H-atom transfer (HAT) in the reaction of2awith phenols as the H-atom donor or protonation of its conjugate base, the Co^III₂(µ-O)₂complex1a. Resonance Raman spectra of these three complexes reveal oxygen-isotope-sensitive vibrations at 560 to 590 cm⁻¹associated with the symmetric Co–O–Co stretching mode of the Co₂O₂diamond core. Together with a Co•••Co distance of 2.78(2) Å previously identified for1aand2aby Extended X-ray Absorption Fine Structure (EXAFS) analysis, these results provide solid evidence for their “diamond core” structural assignments. The independent generation of3aallows us to investigate HAT reactions of2awith phenols in detail, measure the redox potential and pK_aof the system, and calculate the O–H bond strength (D_O–H) of3ato shed light on the C–H bond activation reactivity of2a. Complex3ais found to be able to transfer its hydroxyl ligand onto the trityl radical to form the hydroxylated product, representing a direct experimental observation of such a reaction by a dinuclear cobalt complex. Surprisingly, reactivity comparisons reveal2ato be 10⁶-fold more reactive in oxidizing hydrocarbon C–H bonds than corresponding Fe^III,IV₂(µ-O)₂and Mn^III,IV₂(µ-O)₂analogs, an unexpected outcome that raises the prospects for using Co^III,IV₂(µ-O)₂species to oxidize alkane C–H bonds. 

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3. Modulating optical properties through cation substitution: composition-property relationships in MI3M ^III P ₃ O ₉ N:Eu ²⁺ (M ^I = Na, K; M ^III = Al, Ga, In)

   https://doi.org/10.1039/d5qi00410a  

   Lee, Nakyung; Zeler, Justyna; Sójka, Małgorzata; Zych, Eugeniusz; Brgoch, Jakoah (April 2025, Inorganic Chemistry Frontiers)

   Developing phosphors with narrow photoluminescence emission peaks and high chromatic stability is significant for light-emitting diode (LED) technologies. This work studies the connection between composition, structure, and peak shape. 

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4. Structural and Magnetic Variations in a Family of Isoskeletal, Oximate-Bridged {Mn ^IV ₂ M ^III } Complexes (M ^III =Mn, Gd, Dy)

   https://doi.org/10.1002/chem.201706098  

   Alaimo, Alysha A.; Worrell, Anne; Gupta, Sayak Das; Abboud, Khalil A.; Lampropoulos, Christos; Christou, George; Stamatatos, Theocharis C. (February 2018, Chemistry - A European Journal)
5. Magnetic properties of two Gd ^III Fe ^III ₄ metallacrowns and strategies for optimizing the magnetocaloric effect of this topology

   https://doi.org/10.1039/D1QI00207D  

   Salerno, Elvin V.; Kampf, Jeff W.; Pecoraro, Vincent L.; Mallah, Talal (May 2021, Inorganic Chemistry Frontiers)

   Two Gd III Fe III 4 metallacrown complexes are presented and analyzed for their magnetic properties. One of these species is newly identified and exhibits a bent ring geometry as opposed to the more conventional flatter conformation of the other. Both complexes are quite similar magnetically, exhibiting antiferromagnetic exchange coupling values ca . J (Fe III –N–O–Fe III ) = −7 cm −1 and J (Gd III –O–Fe III ) = −0.7 cm −1 . When analyzed for the molecular magnetocaloric effect, maximum −Δ S m values of 7.3 J K −1 kg −1 at 3 K and at 6.1 J K −1 kg −1 at 4 K were exhibited. A detailed structural-magnetic correlation is established and an assessment of several similar magnetic metallacrowns with diverse metal combinations is given with regards to their potential magnetocaloric properties. Strategies for improving the magnetocaloric properties within the Metaln + FeIII4 family of metallacrowns are proposed regarding the ratio between coupling parameters J (Fe III –N–O–Fe III )/ J (Metal n+ –O–Fe III ). 

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