Dilution-triggered SMM behavior under zero field in a luminescent Zn2Dy2 tetranuclear complex incorporating carbonato-bridging ligands derived from atmospheric CO2 fixation.
The synthesis, structure, magnetic, and luminescence properties of the Zn2Dy2 tetranuclear complex of formula {(μ3-CO3)2[Zn(μ-L)Dy(NO3)]2}·4CH3OH (1), where H2L is the compartmental ligand N,N',N″-trimethyl-N,N″-bis(2-hydroxy-3-methoxy-5-methylbenzyl)diethylenetriamine, are reported. The carbonate anions that bridge two Zn(μ-L)Dy units come from the atmospheric CO2 fixation in a basic medium. Fast quantum tunneling relaxation of the magnetization (QTM) is very effective in this compound, so that single-molecule magnet (SMM) behavior is only observed in the presence of an applied dc field of 1000 Oe, which is able to partly suppress the QTM relaxation process. At variance, a 1:10 Dy:Y magnetic diluted sample, namely, 1', exhibits SMM behavior at zero applied direct-current (dc) field with about 3 times higher thermal energy barrier than that in 1 (U(eff) = 68 K), thus demonstrating the important role of intermolecular dipolar interactions in favoring the fast QTM relaxation process. When a dc field of 1000 Oe is applied to 1', the QTM is almost fully suppressed, the reversal of the magnetization slightly slows, and U(eff) increases to 78 K. The dilution results combined with micro-SQUID magnetization measurements clearly indicate that the SMM behavior comes from single-ion relaxation of the Dy(3+) ions. Analysis of the relaxation data points out that a Raman relaxation process could significantly affect the Orbach relaxation process, reducing the thermal energy barrier U(eff) for slow relaxation of the magnetization.
Departamento de Química Inorgánica, Facultad de Ciencias, Universidad de Granada, Avenida Fuentenueva s/n, 18071 Granada, Spain.
Silvia
S
Titos-Padilla
José
J
Ruiz
Juan Manuel
JM
Herrera
Euan K
EK
Brechin
Wolfgang
W
Wersndorfer
Francesc
F
Lloret
Enrique
E
Colacio
D002245:Carbon Dioxide / Q000737:chemistry*; D002254:Carbonates / Q000737:chemistry*; D008024:Ligands; D049449:Luminescence; D059346:Magnets / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D015032:Zinc / Q000737:chemistry*
D002254:Carbonates; D008024:Ligands; D009942:Organometallic Compounds; D002245:Carbon Dioxide; D015032:Zinc