Synthesis, Thermal Stability, and Magnetic Properties of a Manganese(II) Coordination Framework Containing Bistriazolate Ligands

Abstract

By combining a bistriazole ligand, [1,2,3]triazolo-[4,5-f ]benzotriazole-4,8(2H,6H)-dione (H 2 C 6 N 6 O 2 ), and Mn(II) cations in water, we prepared a Mn(II) coordination framework having an unexpected structure. As revealed by single-crystal Xray analysis, the compound crystallizes in the monoclinic crystal system in the space group P2 1 /n and forms a 2D layered structure. The complex formula is [Mn 3 (C 6 N 6 O 2 ) 2 (OH) 2 (H 2 O) 4 ], and [a]

Cooperative Interactions with Water Drive Hysteresis in a Hydrophilic Metal–Organic Framework

“…Previous syntheses of nonporous MOFs using benzobistriazolequinone (BBTQ 2– ) have utilized the conjugate base under aqueous hydrothermal conditions. , We hypothesized that conditions mimicking those used in the synthesis of isoreticular Ni 2 Cl 2 BBTA, which utilize a neutral ligand in an organic solvent, would prevent the formation of metal–ketone coordination bonds and form the desired hexagonal phase (Figure ). Reaction of H 2 BBTQ with NiCl 2 in acidic N , N -dimethylformamide gives rise to a crystalline, turquoise-colored material with the desired structure type.…”

“…These bands correspond to the quinhydrone charge-transfer excitation and hydroquinone π−π* excitation, respectively. 15 It is difficult to quantify precisely the ratio of quinone to hydroquinone as the equilibrium constant between quinone− hydroquinone and quinhydrone is not known, and 13 C-ssNMR spectra do not exhibit any features (likely due to paramagnetic broadening by spin polarization from the nickel sites). However, given that the quinhydrone band grows monotonically with temperature, we expect that the quinone content outnumbers hydroquinone (ideally at an equal quinone− hydroquinone content, the quinhydrone band would reach a maximum and decrease in intensity after hydroquinone exceeds quinone content).…”

Synthesis, Thermal Stability and Magnetic Properties of an Interpenetrated Mn(II) Triazolate Coordination Framework

“…1,2,3-Triazolate based coordination compounds and especially metal-organic frameworks (MOFs) recently gained increasing attention owing to various physical phenomena and potential applications like e. g. drug delivery, [1] catalytic reactions, [2] kinetic trapping of gases, [3,4] H 2 /D 2 quantum sieving [5] and CO 2 binding, [6] which were shown for bistriazolate MOFs featuring Kuratowski-type secondary building units (SBUs). Other bistria-zolate-based frameworks were investigated for catalysis, [7] gas binding, [8][9][10] chirality, [11] magnetic behaviour, [12] or even electrical and proton conductivity. [13,14] Single triazolate ligands tend to form Kuratowski complexes, [15] which were recently proven to give interesting chromophores [16] or building blocks for the assembly of metal hydrogen-bonded organic frameworks [17] via functionalization of the ligand backbones.…”

Strong CO2 Chemisorption in a Metal–Organic Framework with Proximate Zn–OH Groups

“…Linker design provides the most obvious means of accessing new benzotriazolate frameworks with Kuratowski-type SBUs and short intercluster Zn···Zn distances. Notably, compared to carboxylate-based materials, only a relatively small number of benzotriazolate linkers and MOFs have been reported, and none are isoreticular analogues of CFA-1. − The bibta 2– linkers in CFA-1 adopt two different conformations ( syn and anti ), and those in the syn conformation are responsible for enforcing the short intercluster Zn E ···Zn E distances. Thus, we hypothesized that a slightly elongated linker variant with a single atom spacer between benzotriazole groups might maintain the necessary length and conformational flexibility to yield a new framework with short intercluster separation for cooperative CO 2 chemisorption.…”