Functionalized Adamantane Tectons Used in the Design of Mixed-Ligand Copper(II) 1,2,4-Triazolyl/Carboxylate Metal–Organic Frameworks

Bistriazoles, 1,3-bis(1,2,4-triazol-4-yl)propane (tr2pr) and 1,3-bis(1,2,4-triazol-4-yl)adamantane (tr2ad), were examined in combination with the rigid tetratopic 1,3,5,7-adamantanetetracarboxylic acid (H4-adtc) platform for the construction of neutral heteroleptic copper(II) metal−organic frameworks. Two coordination polymers, [{Cu4(OH)2(H2O)2}{Cu4(OH)2}(tr2pr)2(H-adtc)4]·2H2O (1) and [Cu4(OH)2(tr2ad)2(H-adtc)2(H2O)2]·3H2O (2), were synthesized and structurally characterized. In complexes 1 and 2, the N1,N2-1,2,4-triazolyl (tr) and μ3-OH− groups serve as complementary bridges between adjacent metal centers supporting the tetranuclear dihydroxo clusters. The structure of 1 represents a unique association of two different kinds of centrosymmetrical {Cu4(OH)2} units in a tight 3D framework, while in compound 2, another configuration type of acentric tetranuclear metal clusters is organized in a layered 3,6-hexagonal motif. In both cases, the {Cu4(OH)2} secondary building block and trideprotonated carboxylate H-adtc3− can be viewed as covalently bound six- and three-connected nodes that define the net topology. The tr ligands, showing μ3- or μ4-binding patterns, introduce additional integrating links between the neighboring {Cu4(OH)2} fragments. A variable-temperature magnetic susceptibility study of 2 demonstrates strong antiferromagnetic intracluster coupling (J1 = −109 cm−1 and J2 = −21 cm−1), which combines for the bulk phase with a weak antiferromagnetic intercluster interaction (zj = −2.5 cm−1).

1,2-Bis(2-benzimidazolyl)-1,2-ethanediol, a chiral, tridentate, facially coordinating ligand

The ligand 1,2-bis(1H-benzimidazol-2-yl)-1,2-ethanediol, 1, and its methylated derivative 2 are readily synthesized from tartaric acid, and act as chiral, facially coordinating tridentate ligands, forming complexes of composition ML2 with octahedral transition metals. The copper(II) complexes show distorted 4 + 2 coordination with benzimidazoles occupying the equatorial sites and alcohol functions weakly binding in the axial sites. Nickel(II) complexes in three different states of protonation show regular octahedral geometry with the alcohols mutually cis. Deprotonation of the coordinated alcohol produces little structural change but the monodeprotonated complex forms a hydrogen bonded dimer. Magnetic measurements show the hydrogen bonded bridge to offer a pathway for weak antiferromagnetic coupling. UV-Visible spectroscopy shows the ligand to have a field intermediate between water and pyridine. The diastereoselectivity of complexation depends on the geometry: nickel(II) shows a weak preference for the homochiral complex, whereas copper(II) forms almost exclusively homochiral complexes.