Heterometallic MnIII4Ln2 (Ln = Dy, Gd, Tb) Cross-Shaped Clusters and Their Homometallic MnIII4MnII2 Analogues
Ημερομηνία
2017Συγγραφέας
Savva, MariaSkordi, Katerina
Fournet, A. D.
Thuijs, A. E.
Christou, George
Perlepes, Spyros P.
Papatriantafyllopoulou, Constantina
Tasiopoulos, Anastasios J.
Source
Inorganic chemistryVolume
56Issue
10Pages
5657-5668Google Scholar check
Metadata
Εμφάνιση πλήρους εγγραφήςΕπιτομή
The employment of di-2-pyridyl ketone, (py)2CO, in heterometallic Mn/4f and homometallic Mn cluster chemistry has yielded six MnIII4Ln2 and two MnIII4MnII2 structurally related clusters, namely, [Mn4Ln2O2{(py)2CO2}4(NO3)2(RCO2)2(H2O)6](NO3)2 (Ln = Gd, 1, 5 Dy, 2 Tb, 3 R = Et, 1-3 Me, 5), [Mn4Dy2O2{(py)2CO2}4(NO3)4(EtCO2)2(H2O)3(MeOH)]·0.7MeOH·0.8H2O (4·0.7MeOH·0.8H2O), [Mn4Gd2O2{(py)2CO2}4(NO3)4(C6H4ClCO2)2(MeOH)2(py)2]·2MeOH (6·2MeOH), [Mn6O2{(py)2CO2}4(py)4(H2O)4](ClO4)4·4H2O (7·4H2O), and [Mn6O2{(py)2CO2}4(NO3)4(py)4] (8), where (py)2CO22- is the dianion of the gem-diol derivative of (py)2CO. The compounds possess a new type of cross-shaped structural core, which in the case of 1-6 is essentially planar, whereas in 7 and 8 it deviates from planarity. Clusters 1-6 are rare examples of Mn/4f species bearing (py)2CO or its derivatives, despite the fact that this ligand has been well-studied and proven a rich source of more than 200 metal compounds so far. Variable-temperature, solid-state direct-current and alternating-current magnetization studies were performed on complexes 1-5, 7, and 8 revealing that the dominant exchange interactions between the metal ions are antiferromagnetic and indicating ground-state spin values of S = 5 (for 1), 6 (for 5), and 2 (for 7 and 8). © 2017 American Chemical Society.