Solvothermal reactions of 1,10-phenanthroline-2,9-dicarbaldehyde dioxime (H2phendox) with FeCl3·6H2O or FeBr3 under solvothermal conditions yielded two trinuclear iron(III) clusters [FeIII3(μ3-O)(phendox)3]X·14H2O (X = Cl 1·14H2O, Br 2·14H2O) and three hexanuclear iron(III) and iron(II) clusters, [FeIII6(μ4-O)2(MeO)6X4(phendox)2]·MeOH (X = Cl 3, Br 4) and (H3O)[FeII6(μ6-Cl)(phenda)6]·6H2O (5·6H2O). The phendox2− ligand is very useful in constructing magnetically active and stable high-nuclearity metal clusters in that the phenanthroline rings and the oxime nitrogen atoms grasp the metal ions tightly while the two oxygen atoms on the oximates can link other metal centres in the shortest pairwise magnetic exchange pathway. Adjacent Fe3(μ3-O)(phendox)3+ motifs in 1 and 2 are packed by off-set π–π interactions of the aromatic rings on phendox2− to generate a 3D supramolecular architecture in the honeycomb topology and with 1D hexagonal channels in the dimension of 13 × 13 Å along the c-axis. 2 is stable upon the removal of guest molecules and the desolvated compound absorbed considerable amount of N2, CO2 and H2. 3 and 4 are isostructural. Two μ4-O2− and two phendox2− units link four metal atoms into a coplanar butterfly-shaped unit with the μ4-O2− slightly above and below the plane (±0.264 Å). The other two Fe(III) ions are capped on the alternate planes via the three bridging μ2-methoxides and accordingly form an unprecedented hexanuclear Fe(III) cluster. Furthermore, the oximes underwent hydrolysis to yield carboxylate groups and the resulted 1,10-phenanthroline-2,9-dicarboxylate link the iron atoms to form a hexanuclear cluster of 5. Magnetic studies show that the antiferromagnetic interactions are present in the Fe3O core of 2 and in the (μ6-Cl)Fe6(μ-O)12 core of 5.

Solvothermal reactions of 1,10-phenanthroline-2,9-dicarbaldehyde dioxime (H2phendox) with FeCl3·6H2O or FeBr3 under solvothermal conditions yielded two trinuclear iron(III) clusters [FeIII3(μ3-O)(phendox)3]X·14H2O (X = Cl 1·14H2O, Br 2·14H2O) and three hexanuclear iron(III) and iron(II) clusters, [FeIII6(μ4-O)2(MeO)6X4(phendox)2]·MeOH (X = Cl 3, Br 4) and (H3O)[FeII6(μ6-Cl)(phenda)6]·6H2O (5·6H2O). The phendox2− ligand is very useful in constructing magnetically active and stable high-nuclearity metal clusters in that the phenanthroline rings and the oxime nitrogen atoms grasp the metal ions tightly while the two oxygen atoms on the oximates can link other metal centres in the shortest pairwise magnetic exchange pathway. Adjacent Fe3(μ3-O)(phendox)3+ motifs in 1 and 2 are packed by off-set π–π interactions of the aromatic rings on phendox2− to generate a 3D supramolecular architecture in the honeycomb topology and with 1D hexagonal channels in the dimension of 13 × 13 Å along the c-axis. 2 is stable upon the removal of guest molecules and the desolvated compound absorbed considerable amount of N2, CO2 and H2. 3 and 4 are isostructural. Two μ4-O2− and two phendox2− units link four metal atoms into a coplanar butterfly-shaped unit with the μ4-O2− slightly above and below the plane (±0.264 Å). The other two Fe(III) ions are capped on the alternate planes via the three bridging μ2-methoxides and accordingly form an unprecedented hexanuclear Fe(III) cluster. Furthermore, the oximes underwent hydrolysis to yield carboxylate groups and the resulted 1,10-phenanthroline-2,9-dicarboxylate link the iron atoms to form a hexanuclear cluster of 5. Magnetic studies show that the antiferromagnetic interactions are present in the Fe3O core of 2 and in the (μ6-Cl)Fe6(μ-O)12 core of 5.

Two unique octa- and hendeca-nuclear dysprosium(III) clusters incorporating [Dy4(μ3-OH)4]8+ cubane units have been synthesized with the 1,10-phenanthroline-2,9-dicarbaldehyde dioxime (H2phendox) ligand and DyCl3·6H2O or Dy(OAc)3·4H2O. They are [Dy8(OH)8(phendox)6(H2O)8]Cl2(OH)2·18H2O·18MeOH (1) and [Dy11(OH)11(phendox)6(phenda)3(OAc)3](OH)·40H2O·7MeOH (2). Adjacent Dy8 in 1 or Dy11 in 2 motifs are packed by off-set π–π interactions of the aromatic rings on phendox2− to generate a 3D supramolecular architecture in the honeycomb topology and with 1D or 3D channels along the c-axis. Adsorption research shows that complex 1 has selective adsorption ability for H2O over small gas molecules (H2, N2, CO2). Complex 2 is stable upon the removal of guest molecules and the desolvated compound absorbed a considerable amount of CO2. Furthermore, the oximes underwent hydrolysis to carboxylic acid and the resulting 1,10-phenanthroline-2,9-dicarboxylate link the dysprosium atoms to form a hendecanuclear cluster of 2. Magnetic studies reveal that both clusters exhibit slow magnetic relaxation behavior, expanding upon the recent reports of the pure 4f type single-molecule magnets (SMMs).

Two unique octa- and hendeca-nuclear dysprosium(III) clusters incorporating [Dy4(μ3-OH)4]8+ cubane units have been synthesized with the 1,10-phenanthroline-2,9-dicarbaldehyde dioxime (H2phendox) ligand and DyCl3·6H2O or Dy(OAc)3·4H2O. They are [Dy8(OH)8(phendox)6(H2O)8]Cl2(OH)2·18H2O·18MeOH (1) and [Dy11(OH)11(phendox)6(phenda)3(OAc)3](OH)·40H2O·7MeOH (2). Adjacent Dy8 in 1 or Dy11 in 2 motifs are packed by off-set π–π interactions of the aromatic rings on phendox2− to generate a 3D supramolecular architecture in the honeycomb topology and with 1D or 3D channels along the c-axis. Adsorption research shows that complex 1 has selective adsorption ability for H2O over small gas molecules (H2, N2, CO2). Complex 2 is stable upon the removal of guest molecules and the desolvated compound absorbed a considerable amount of CO2. Furthermore, the oximes underwent hydrolysis to carboxylic acid and the resulting 1,10-phenanthroline-2,9-dicarboxylate link the dysprosium atoms to form a hendecanuclear cluster of 2. Magnetic studies reveal that both clusters exhibit slow magnetic relaxation behavior, expanding upon the recent reports of the pure 4f type single-molecule magnets (SMMs).