Unexpected transformation of mono- to bis-macrobicyclic dimethylglyoximate framework in a chloroform solution: Photochemical, MALDI-TOF MS and X-ray diffraction studies

Flexible Co(II)-and Ni(II)-Based Cationic 2D Metal–Organic Frameworks Based on a Charge-Neutral (O,O)-Donor Bridge

“…The Co-O(odabco) bond lengths are 2.040(2) Å and 2.1238(18) Å. These values fit well to the typical bond lengths' range for octahedral Co(II) complexes with different N-oxides, nitroxyl radicals, and oxime ligands [53][54][55][56][57][58][59][60]. The Co-O(DMF) bond length is 2.156(2) Å.…”

Synthesis, crystal polymorphism and spin crossover behavior of adamantylboron-capped cobalt(ii) hexachloroclathrochelate and its transformation into the CoIIICoIICoIII-bis-macrobicyclic derivative

“…Another, even more unexpected, bis-cage product of a prolonged crystallization of the thiopheneboron-cross-linked tris-dimethylglyoximate cobalt( ii ) monoclathrochelate (see the ESI, Scheme S2‡) from its chloroform–heptane solution is described. 32 This hexakis-dimethylglyoximate Co III Co II Co III -bis-clathrochelate was a product of its side chemical transformations resulting from the reactions with phosgene and radical species, formed by the photoinduced oxidation of chloroform in the course of a slow evaporation of the corresponding solution. The latter process proceeded under an air atmosphere ( i.e.…”

“…in the presence of air oxygen) deposited for a long time under sunlight irradiation. The results of the performed 32 detailed photochemical studies upon irradiation of this solution under various experimental conditions allowed us to suggest that the most probable pathway to the aforementioned hexakis-dimethylglyoximate bis-clathrochelate, shown in Scheme S2 ‡ is based on the photoinitiated oxidation of CHCl 3 with O 2 . So, to the best of our knowledge, only three examples of the XRD-characterized mixed-valence cobalt bis-clathrochelates have been described in the literature to date (vide supra).…”

“…Dalton Transactions described. 32 This hexakis-dimethylglyoximate Co III Co II Co IIIbis-clathrochelate was a product of its side chemical transformations resulting from the reactions with phosgene and radical species, formed by the photoinduced oxidation of chloroform in the course of a slow evaporation of the corresponding solution. The latter process proceeded under an air atmosphere (i.e.…”

Unexpected Side Products of Chemical Transformations in Cobalt(II) Pseudoclathrochelates: An X‐Ray Diffraction Study

“…A possible reason for such a transformation, as previously proposed for a related cobalt(II) clathrochelate, is a photoinitiated radical oxidation of the chloroform molecules with air oxygen resulting in reactive species (CoCl 2 , HCl and radicals) that cause a re‐capping of the H‐bonded pseudomacrobicyclic ligand of 2 (Scheme ) to produce a stable cobalt(II) complex 1 (Figure ).…”