Nonanuclear Coordination Compounds Featuring {M₉L₁₂}⁶⁺ Cores (M = Ni^II, Co^II, or Zn^II; L = 1,2,3‐Benzotriazolate)

Abstract

Syntheses, characterization, and magnetic properties of three nonanuclear coordination compounds with the molecular formulae [Ni 9 (bta) 12 (NO 3 ) 6 (MeOH) 6 ]·4THF (1) (btaH = 1,2,3-benzotriazole; THF = tetrahydrofuran), [Co 9 (bta) 12 (MeOH) 18 ]-[(NO 3 ) 6 ]·9C 6 H 6 (C 6 H 6 = benzene) (2), and [Zn 9 (Me 2 bta) 12 -(CH 3 COO) 6 ]·3DMF (Me 2 btaH = 5,6-dimethyl-1,2,3-benzotriazole; DMF = N,NЈ-dimethylformamide) (3) are presented. The solid-state structures of all the compounds were determined by single-crystal X-ray structure analysis revealing the presence of structurally similar {M 9 L 12 } 6+ cores (M = Ni II , Co II , or Zn II ; L = 1,2,3-benzotriazolate) in which the metal centers are bridged by µ 3 -benzotriazolates. The charges of the cationic {M 9 L 12 } 6+ moieties in 1 and 3 are balanced by six nitrate and acetate anions coordinated to the peripheral metal atoms, respectively, whereas 2 is a cationic metal complex with six noncoordinated nitrate counterions in the crystal lattice. All the metal centers in each compound are hexa-

Bioinspired chemistry at MOF secondary building units

“…In both materials, SBUs are Kuratowski clusters, which feature a central octahedral zinc(II) with six bridging azolate ligands and four peripheral tetrahedral zinc(II) sites with an exchangeable X-ligand. 36 The peripheral zinc(II) site is structurally and electronically similar to the active site in CA; it features an N 3 ZnX coordination environment comprised of three triazolate nitrogen donors, which are electronically similar to histidines. In addition to their structural mimicry, these materials also engage in reactivity that functionally mimics CA.…”

Metal–organic frameworks in Germany: From synthesis to function

“…It is noted that up to now the structures of intermediate oligomeric species are largely unknown if the simple vtz − ligand is employed. However, using larger benzotriazolate ligands, discrete nonanuclear coordination compounds can be isolated representing oligomeric species from the fusion of Kuratowski-type building units [113,114]. Lastly, the review on metal-triazolate frameworks would be rather incomplete without mentioning a series of europium-containing triazolate framework structures reported by K. Müller-Buschbaum et al [115,116,117], among which [Eu(II)(bta) 2 ], is topologically equivalent to the cubic metal-triazolates.…”

Recent advances in the coordination chemistry of benzotriazole-based ligands

“…Further efforts [32] (6). Instead of pyrazine, the authors employ a very large excess of Hbta during the synthetic procedure, with metal:ligand ratios of 1:4 and 1:8 respectively.…”