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1. Relaxation dynamics in see-saw shaped Dy( iii ) single-molecule magnets

   https://doi.org/10.1039/D0QI01007C  

   Harriman, Katie L.; Murillo, Jesse; Suturina, Elizaveta A.; Fortier, Skye; Murugesu, Muralee (December 2020, Inorganic Chemistry Frontiers)

   null (Ed.)

   Utilizing a terphenyl bisanilide ligand, two Dy( iii ) compounds [K(DME) n ][L Ar Dy(X) 2 ] (L Ar = {C 6 H 4 [(2,6- i PrC 6 H 3 )NC 6 H 4 ] 2 } 2− ), X = Cl ( 1 ) and X = I ( 2 ) were synthesized. The ligand imposes an unusual see-saw shaped molecular geometry leading to a coordinatively unsaturated metal complex with near-linear N–Dy–N (avg. 159.9° for 1 and avg. 160.4° for 2 ) angles. These compounds exhibit single-molecule magnet (SMM) behavior with significant uniaxial magnetic anisotropy as a result of the transverse coordination of the bisanilide ligand which yields high energy barriers to magnetic spin reversal of U eff = 1334 K/927 cm −1 ( 1 ) and 1278 K/888 cm −1 ( 2 ) in zero field. Ab initio calculations reveal that the dominant crystal field of the bisanilide ligand controls the orientation of the main magnetic axis which runs nearly parallel to the N–Dy–N bonds, despite the identity of the halide ligand. Analysis of the relaxation dynamics reveals a ca. 14-fold decrease in the rate of quantum tunneling of the magnetisation when X = I ( 2 ). Most notably, the relaxation times were on average 5.6× longer at zero field when the heavier group 17 congener was employed. However, no direct evidence of a heavy atom effect on the Orbach relaxation was obtained as the height of the barrier is defined by the dominant bisanilide ligand. 

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2. Conformational comparison of urea and thiourea near the CCSD ( T ) complete basis set limit

   https://doi.org/10.1002/qua.27075  

   Barlow, Kayleigh R.; Tschumper, Gregory S. (December 2022, International Journal of Quantum Chemistry)

   Abstract The global minima of urea and thiourea were characterized along with other low‐lying stationary points. Each structure was optimized with the CCSD(T) method and triple‐ζcorrelation consistent basis sets followed by harmonic vibrational frequency computations. Relative energies evaluated near the complete basis set limit with both canonical and explicitly correlated CCSD(T) techniques reveal several subtle but important details about both systems. These computations resolve a discrepancy by demonstrating that the electronic energy of the C_2vsecond‐order saddle point of urea lies at least 1.5 kcal mol⁻¹above the C₂global minimum regardless of whether the structures were optimized with MP2, CCSD, or CCSD(T). Additionally, urea effectively has one minimum instead of two because the electronic barrier for inversion at one amino group in the C_slocal minimum vanishes at the CCSD(T) CBS limit. Characterization of both systems with the same ab initio methods and large basis sets conclusively establishes that the electronic barriers to inversion at one or both NH₂groups in thiourea are appreciably smaller than in urea. CCSDT(Q)/cc‐pVTZ computations show higher‐order electron correlation effects have little impact on the relative energies and are consistently offset by core correlation effects of opposite sign and comparable magnitude. 

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3. HAA by the first {Mn( iii )OH} complex with all O-donor ligands

   https://doi.org/10.1039/d3sc01971c  

   Moore, Shawn M.; Sun, Chen; Steele, Jennifer L.; Laaker, Ellen M.; Rheingold, Arnold L.; Doerrer, Linda H. (July 2023, Chemical Science)

   There is considerable interest in MnOH x moieties, particularly in the stepwise changes in those O–H bonds in tandem with Mn oxidation state changes. The reactivity of aquo-derived ligands, {MOH x }, is also heavily influenced by the electronic character of the other ligands. Despite the prevalence of oxygen coordination in biological systems, preparation of mononuclear Mn complexes of this type with all O-donors is rare. Herein, we report several Mn complexes with perfluoropinacolate (pin F ) 2− including the first example of a crystallographically characterized mononuclear {Mn( iii )OH} with all O-donors, K 2 [Mn(OH)(pin F ) 2 ], 3. Complex 3 is prepared via deprotonation of K[Mn(OH 2 )(pin F ) 2 ], 1, the p K a of which is estimated to be 18.3 ± 0.3. Cyclic voltammetry reveals quasi-reversible redox behavior for both 1 and 3 with an unusually large Δ E p , assigned to the Mn( iii / ii ) couple. Using the Bordwell method, the bond dissociation free energy (BDFE) of the O–H bond in {Mn( ii )–OH 2 } is estimated to be 67–70 kcal mol −1 . Complex 3 abstracts H-atoms from 1,2-diphenylhydrazine, 2,4,6-TTBP, and TEMPOH, the latter of which supports a PCET mechanism. Under basic conditions in air, the synthesis of 1 results in K 2 [Mn(OAc)(pin F ) 2 ], 2, proposed to result from the oxidation of Et 2 O to EtOAc by a reactive Mn species, followed by ester hydrolysis. Complex 3 alone does not react with Et 2 O, but addition of O 2 at low temperature effects the formation of a new chromophore proposed to be a Mn( iv ) species. The related complexes K(18C6)[Mn( iii )(pin F ) 2 ], 4, and (Me 4 N) 2 [Mn( ii )(pin F ) 2 ], 5, have also been prepared and their properties discussed in relation to complexes 1–3. 

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4. Hard versus soft: zero-field dinuclear Dy( iii ) oxygen bridged SMM and theoretical predictions of the sulfur and selenium analogues

   https://doi.org/10.1039/c9dt00324j  

   Vignesh, Kuduva R.; Alexandropoulos, Dimitris I.; Dolinar, Brian S.; Dunbar, Kim R. (February 2019, Dalton Transactions)

   Two dinuclear lanthanide complexes (Gd and Dy) were prepared and characterized by X-ray, magnetic and computational methods. The Dy analogue shows SMM behavior with an energy barrier of 98.4 K in the absence of an applied dc field. Theoretical calculations were performed on model complexes which support the hypothesis that the energy barrier will increase if the soft-donor atoms S and Se are used in lieu of an O donor. 

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5. Enhanced Thomson and Unusual Nernst Coefficients in 1T‐ TiSe2 Due to Bipolar Transport and CDW Phase Transition

   https://doi.org/10.1002/eem2.12879  

   Akhanda, Md_Sabbir; Dharmasiri, Kusal_Sachithra; Das, Sree_Sourav; Louca, Despina; Zebarjadi, Mona (January 2025, ENERGY & ENVIRONMENTAL MATERIALS)

   Thermoelectric coolers utilizing the Peltier effect have dominated the field of solid‐state cooling but their efficiency is hindered by material limitations. Alternative routes based on the Thomson and Nernst effects offer new possibilities. Here, we present a comprehensive investigation of the thermoelectric properties of 1T‐TiSe₂, focusing on these effects around the charge density wave transition (≈200 K). The abrupt Fermi surface reconstruction associated with this transition leads to an exceptional peak in the Thomson coefficient of 450 μV K⁻¹at 184 K, surpassing the Seebeck coefficient. Furthermore, 1T‐TiSe₂exhibits a remarkably broad temperature range (170–400 K) with a Thomson coefficient exceeding 190 μV K⁻¹, a characteristic highly desirable for the development of practical Thomson coolers with extended operational ranges. Additionally, the Nernst coefficient exhibits an unusual temperature dependence, increasing with temperature in the normal phase, which we attribute to bipolar conduction effects. The combination of solid–solid pure electronic phase transition to a semimetallic phase with bipolar transport is identified as responsible for the unusual Nernst trend and the unusually large Thomson coefficient over a broad temperature range. 

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