Toward Heteronuclear Molecular Re(I)-Cu(II) Boxes: Structural, Luminescent, and Magnetic Properties

The bifunctional ligands of isonicotinic acid (Py-4-COOH) and 4-pyrid-4-ylbenzoic acid (Pybz-4-COOH) instead of polypyridines were therefore reacted with (Re­(CO)₄)₃(C₃N₃S₃) (C₃N₃S₃ = cyanurate trianion), resulting in the formation of two trinuclear [(Re­(CO)₃)₃(C₃N₃S₃)­(Py-4-COOH)₃] (1) and [(Re­(CO)₃)₃(C₃N₃S₃)­(Pybz-4-COOH)₃] (2), respectively. In the meantime, both complexes 1 and 2 are connected by three bifurcated hydrogen bonds between their carboxylic acid moieties Py-4-COOH and Pybz-4-COOH to form the supramolecular trigonal-prismatic and -antiprismatic structures, respectively. It is noted that complex 1 can further react with copper­(II) nitrate upon deprotonation to give nonanuclear [(Re­(CO)₃)₃(C₃N₃S₃)­(Py-4-COO)₃]₂Cu₃(H₂O)₉ (3), where two trinuclear [(Re­(CO)₃)₃(C₃N₃S₃)­(Py-4-COO)₃] moieties are connected by three penta-coordinate copper­(II) ions, each coordinating to two carboxylates and three water molecules, to form the trigonal-prismatic structure. Surprisingly, addition of pyrazine (pz) in the synthetic process of complex 3 resulted in serendipitous isolation of a rare example of octadecanuclear {[(Re­(CO)₃)₃(C₃N₃S₃)­(Py-4-COO)₃]₂Cu₃(H₂O)₆(pz)₂}₂ (4), which can be regarded as a dimer of complex 3, connected by two bridging pz ligands. Interestingly, both complexes 3 and 4 are heteronuclear molecular Re­(I)-Cu­(II) boxes, constructed by a complex-as-a-ligand strategy. Furthermore, complexes 1 and 2 can exhibit respective low-energy luminescence at ca. 561 and 534 nm at room temperature upon photoexcitation, and complex 3 is found to display antiferromagnetic coupling of −127.68 and −134.70 cm^–1, possibly due to multiple hydrogen bonds inducing significant Cu­(II)···Cu­(II) coupling.