Dinuclear Fluoride Single-Bridged Lanthanoid Complexes as Molecule Magnets: Unprecedented Coupling Constant in a Fluoride- Bridged Gadolinium Compound Corredoira-Vázquez, Julio Colacio Rodríguez, Enrique The authors thank the Spanish Ministerio de Ciencia e Innovacion projects (PGC2018-102052-B-C21, PGC2018093863-B-C21, MCIN/AEI/10.13039/501100011033/FEDER "Una manera de hacer Europa") for financial support. E.C. acknowledges Junta de Andalucia for the FEDER Andalucia project A-FQM-172-UGR18. J.C.-V. also thanks Xunta de Galicia for his Ph.D. fellowship (ED481A-2018/136). The authors acknowledge computer resources, technical expertise, and assistance provided by the CSUC. The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.2c00773. Figures S1−S9 and Tables S1−S9 (PDF) https://pubs.acs.org/doi/suppl/10.1021/acs.inorgchem.2c00773/suppl_file/ic2c00773_si_001.pdf A new synthetic method allows isolating fluoride-bridged complexes Bu4N{[M(3NO(2),5Br-H3L1,1,4)](2)(mu-F)} (M = Dy, 1; M = Ho, 2; M = Gd, 3) and Bu4N{[Dy(3Br,5Cl-H3L1,2,4)](2)(mu-F)}center dot 2H(2)O, 4 center dot 2H(2)O. The crystal structures of 1 center dot 5CH(3)C(6)H(5),center dot 2 center dot 2H(2)O center dot 0.75THF, 3, and 4 center dot 2H(2)O center dot 2THF show that all of them are dinuclear compounds with linear single fluoride bridges and octacoordinated metal centers. Magnetic susceptibility measurements in the temperature range of 2-300 K reveal that the Gd-III ions in 3 are weakly antiferromagnetically coupled, and this constitutes the first crystallographically and magnetically analyzed gadolinium complex with a fluoride bridge. Variabletemperature magnetization demonstrates a poor magnetocaloric effect for 3. Alternating current magnetic measurements for 1, 2, and 4 center dot 2H(2)O bring to light that 4 center dot 2H(2)O is an SMM, 1 shows an SMM-like behavior under a magnetic field of 600 Oe, while 2 does not show relaxation of the magnetization even under an applied magnetic field. In spite of this, 2 is the first fluoride-bridged holmium complex magnetically analyzed. DFT and ab initio calculations support the experimental magnetic results and show that apparently small structural differences between 1 and 4 center dot 2H(2)O introduce important changes in the dipolar interactions, from antiferromagnetic in 1 to ferromagnetic in 4 center dot 2H(2)O. 2023-07-25T09:45:22Z 2023-07-25T09:45:22Z 2022-06-23 info:eu-repo/semantics/article Julio Corredoira-Vázquez, Cristina González-Barreira, Matilde Fondo, Ana M. García-Deibe, Jesús Sanmartín-Matalobos, Silvia Gómez-Coca, Eliseo Ruiz, and Enrique Colacio Inorganic Chemistry 2022 61 (26), 9946-9959. [DOI: 10.1021/acs.inorgchem.2c00773] https://hdl.handle.net/10481/83970 10.1021/acs.inorgchem.2c00773 eng http://creativecommons.org/licenses/by/4.0/ info:eu-repo/semantics/openAccess Atribución 4.0 Internacional American Chemical Society