Regulating the slow magnetic relaxation behavior of two different shapes Dy₄clusters with in situ formed penta‐ and heptadentate Schiff base ligands

Abstract

The design and synthesis of clusters possessing the same number of cores but different connection methods and properties have always been difficult. Herein, we used 2‐pyridinaldehyde, 1,3‐diamino‐2‐propanol, and Dy (ClO4)3·6H2O at room temperature (RT) to obtain the cluster [Dy4(L1)4(μ2‐OH)4]·4ClO4−(1, HL1= 2‐pyridinecarboxaldehyde‐1,3‐diamino‐2‐propanol) with square Dy4O8cluster cores. Cluster1consisted of four Schiff base ligands (L1)−, four Dy(III) ions, four bridged (μ2‐OH)−, and four free ClO4−. The ligand HL1was formed by in situ Schiff base reaction with 2‐pyridinecarbaldehyde and 1,3‐diamino‐2‐propanol in the presence of Dy(III) ions. 2‐Aldehyde‐8‐hydroxyquinoline, 1,3‐diamino‐2‐propanol, and Dy (NO3)3·6H2O reacted at RT to yield a tetranuclear Dy(III) cluster [Dy4(L2)2(μ3‐OH)2(NO3)4(EtOH)2]·2CH3CN (2, H3L2= 2‐aldehyde‐8‐hydroxyquinoline‐1,3‐diamino‐2‐propanol) with butterfly‐shaped Dy4O6cluster core. Cluster2consisted of two ligands (L2)3−, four Dy(III) ions, two bridgedμ3‐OH, two end‐group‐coordinated ethanol molecules, and four bidentate‐chelated NO3−. The in situ reaction of 2‐aldehyde‐8‐hydroxyquinoline and 1,3‐diamino‐2‐propanol under Dy(III) ion‐assisted catalytic conditions provided the ligand H3L2. It is worth noting that the magnetic test showed that1is a typical single‐molecule magnet (SMM), whereas2only showed a significant frequency dependence behavior. We considered Orbach and Raman processes (τ−1=τ0−1exp(−Ueff/kBT) +CTn) to fit1and2in the high‐temperature range and obtainedUeff= 7.01 and 5.43 K andτ0= 1.18 × 10−4and 4.14 × 10−5s, respectively.

Structures and Single-Molecule Magnet Behavior of Dy3 and Dy4 Clusters Constructed by Different Dysprosium(III) Salts

“…To explore the magneto-structural correlations of tetranuclear Dy III -based SMMs, this class of complexes were summarized (Table S13). − The nuclear centers of tetranuclear Dy III complexes have various shapes such as linear, cymbiform, and parallelogram. (Figure ).…”

Manipulating Solvothermal Coordination-Catalyzed In Situ Tandem Reactions to Construct Dysprosium-Based Complexes with Different Shapes and Zero-Field SMM Behaviors

“…However, when the starting materials enter the solvothermal black-box reaction under certain temperature and pressure conditions, the reaction process trajectory of the in situ ligand formation in the reaction system is elusive. Continuously trying to find regular regulation methods to control it is necessary. − Hence, the regulation of solvothermal black-box reactions under certain temperature and pressure conditions is extremely challenging.…”