Solvent-Assisted Control of Metal-Organic Nanotube Size and Morphology.

While intensive studies have focused on the synthesis and characterization of new metal-organic nanotube (MONT) structures, the lack of size and morphology control remains an obstacle in broadening applications for this class of materials. Herein, we demonstrate control of MONT crystallite size and morphology by tuning polarity and the protic/aprotic nature of solvents, including dimethylformamide, N-methyl-2-pyrrolidone, ethanol, and 2-methyltetrahydrofuran, for the isostructural syntheses of two MONTs. Through a combination of transmission electron microscopy, powder X-ray diffraction, and selected area electron diffraction, we find that MONT crystallite sizes can be tuned while maintaining control over the relative dispersity without significantly altering the underlying crystal structure.

Statistical copolymer metal organic nanotubes.

Metal-organic nanotubes (MONTs) are 1-dimensional crystalline porous materials that are formed from ligands and metals in a manner identical to more typical 3-dimensional metal-organic frameworks (MOFs). MONTs form anisotropically in one dimension making them excellent candidates for linker engineering for control of chemical composition and spacing. A novel series of MONTs was synthesized utilizing a mixture of 1,2,4-ditriazole ligands containing both a fully protonated aryl moiety and its tetrafluorinated analog in ratios of, 0 : 1, 1 : 4, 1 : 1, 4 : 1, and 1 : 0, respectively. All MONTs were characterized by both bulk and nanoscale measurements, including SCXRD, PXRD, ssNMR and TEM, to determine the resulting co-polymer architecture (alternating, block, or statistical) and the ligand ratios in the solid materials. All characterization methods point towards statistical copolymerization of the materials in a manner analogous to 3D MOFs, all of which notably could be achieved without destructive analytical methods.

Correction: 'Redox-mediated carbon monoxide release from a manganese carbonyl-implications for physiological CO delivery by CO releasing moieties' (2021), by Barrett et al.

[This corrects the article DOI: 10.1098/rsos.211022.][This corrects the article DOI: 10.1098/rsos.211022.].

Redox-mediated carbon monoxide release from a manganese carbonyl-implications for physiological CO delivery by CO releasing moieties.

The dynamics of hydrogen peroxide reactions with metal carbonyls have received little attention. Given reports that therapeutic levels of carbon monoxide are released in hypoxic tumour cells upon manganese carbonyls reactions with endogenous H2O2, it is critical to assess the underlying CO release mechanism(s). In this context, a quantitative mechanistic investigation of the H2O2 oxidation of the water-soluble model complex fac-[Mn(CO)3(Br)(bpCO2)]2-, (A, bpCO2 2- = 2,2'-bipyridine-4,4'-dicarboxylate dianion) was undertaken under physiologically relevant conditions. Characterizing such pathways is essential to evaluating the viability of redox-mediated CO release as an anti-cancer strategy. The present experimental studies demonstrate that approximately 2.5 equivalents of CO are released upon H2O2 oxidation of A via pH-dependent kinetics that are first-order both in [A] and in [H2O2]. Density functional calculations were used to evaluate the key intermediates in the proposed reaction mechanisms. These pathways are discussed in terms of their relevance to physiological CO delivery by carbon monoxide releasing moieties.