We describe the synthesis of switchable spin crossover materials via mechanochemistry for the first time. Three chemically diverse spin crossover materials have been produced using solvent-free grinding. Crucially, cooperative spin transition behavior and crystallinity is retained, presenting exciting opportunities for the discovery of new materials with switchable magnetic, optical and structural properties.
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http://dx.doi.org/10.1039/c7cc06651a | DOI Listing |
J Chem Phys
January 2025
Université Paris-Saclay, UVSQ, CNRS, GEMaC, 45 Avenue des Etats Unis, 78035 Versailles, France.
Among the large family of spin-crossover (SCO) solids, recent investigations focused on polynuclear SCO materials, whose specific molecular configurations allow the presence of multi-step transitions and elastic frustration. In this contribution, we develop the first elastic modeling of thermal and dynamical properties of trinuclear SCO solids. For that, we study a finite SCO open chain constituted of successive elastically coupled trinuclear (A=B=C) blocks, in which each site (A, B, and C) may occupy two electronic configurations, namely, low-spin (LS) and high-spin (HS) states, accompanied with structural changes.
View Article and Find Full Text PDFSymmetry-breaking spin-state transitions in two of three isostructural salts of MnIII spin-crossover cations, [MnIII(3-OMe-5-NO2-sal2323)]+, with heavy anions are reported. The ReO4- salt undergoes two-step spin crossover which is coupled with a re-entrant symmetry-breaking structural phase transition between a high temperature phase (S = 2, C2/c), an intermediate ordered phase (S = 1/S = 2, P21/c), and a low temperature phase (S = 1, C2/c). The AsF6- complex undergoes an abrupt transition between a high temperature phase (S = 2, C2/c) and a low temperature ordered phase (S = 1/S = 2, P-1).
View Article and Find Full Text PDFDalton Trans
January 2025
State Key Laboratory of Fine Chemicals, Frontier Science Center for Smart Materials, School of Chemical Engineering, Dalian University of Technology, No. 2 Linggong Road, Dalian 116024, P. R. China.
Molecular materials that exhibit synergistic coupling between luminescence and spin-crossover (SCO) behaviors hold significant promise for applications in molecular sensors and memory devices. However, the rational design and underlying coupling mechanisms remain substantial challenges in this field. In this study, we utilized a luminescent complementary ligand pair as an intramolecular luminophore to construct a new Fe-based SCO complex, namely [FeLL](BF)·HO (1-Fe, L is a 2,2':6',2''-terpyridine (TPY) derivative ligand and L is 2,6-di-1-pyrazol-1-yl-4-pyridinecarboxylic acid), and two isomorphic analogs (2-Co, [CoLL](BF)·HO and 3-Zn, [ZnLL](BF)·HO).
View Article and Find Full Text PDFInorg Chem
January 2025
Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan.
Transition metal carbonyl and transition metal dinitrogen are fundamental chemical complexes in many important biological and catalytic processes. Interestingly, binding between a transition metal (TM) atom and carbonyl or dinitrogen results in spin state change. However, no study has evaluated the spin-orbit (SO) effect along the association pathway of any TM-CO or TM-N bond.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Key Laboratory of Cluster Science of Ministry of Education, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, People's Republic of China.
The integration of spin crossover (SCO) magnetic switching and electric polarization properties can engender intriguing correlated magnetic and electric phenomena. However, achieving substantial SCO-induced polarization change through rational molecular design remains a formidable challenge. Herein, we present a polar Fe(II) compound that exhibits substantial polarization change in response to a thermally regulated low-spin ↔ high-spin transition.
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