Host–Guest Conversion: Transformation of Diiodomethane within 1D-Ensemble Suprachannels into Triiodide–Iodine Channel via Photoreaction

Abstract

Self-assembly of ZnBr 2 with 2,7-bis(isonicotinoyloxy)naphthalene (L) yields one-dimensional (1D) zigzag chains of [ZnBr 2 L] composition. This 1D chain ensemble forms unique suprachannels of 4.0 × 4.2 Å 2 size via weak C−H•••π and π•••π interactions. A 350 nm ultraviolet irradiation affects host−guest conversion. Diiodomethane molecules within the suprachannel structure of CHCl 3 • CH 2 I 2 @[ZnBr 2 L] were transformed into an unprecedented triiodide−iodine channel skeleton, HL + @[I 3 •I 2 ] − . Specifically, two clear, quasi-reversible redox peaks were observed at +0.33 and +0.70 V versus Ag/AgCl in the anodic scan and at +0.19 and +0.62 V in the cathodic scan in acetonitrile for HL + @[I 3 •I 2 ] − .

Halide Photoredox Chemistry

“…A large body of literature has described the formation of halogen atoms, such as Cl • , ,,− Br • , ,,,,,,,− ,,,,,,− and I • , ,,,,,,,,− in water or organic solvents. In pulse radiolysis, Cl • is formed by reaction with SO 4 • or HO • that are generated by electron beam ...…”

In Situ Two-Step Crystallization: Transformation of Kinetic Crystals into Thermodynamic Crystals

“…Development of new methodology for task-specific coordination polymers is a great challenge in the field of petrochemicals industry, anion exchanges, separation science, confined catalysis, chemo-sensors, and harmful molecule adsorption. − Recent advanced synthetic methods such as photoreaction, polymorphism, anion exchange, and metal exchange, etc. have been advanced for desirable transformation of coordination frames formed via self-assembly of central metal ions as angle components with appropriate multidentate ligands as spacers. − A noteworthy conceptual feature is that one-dimensional (1D) molecular frames have easy changeability along with low entropy relative to two-dimensional (2D) and three-dimensional (3D) frames . The delicate solubility-difference of 1D may play a significant role in the transformation of the products. ,, In particular, some flexible tridentate ligands possessing noninnocent angles and conformational nonrigidity have produced such interesting scientific results. ,, In this context, unusual in situ two-step crystallization for 1D coordination polymerization via the self-assembly of Ag­(I) ions with a flexible N -donor tridentate ligand (L) in the mother liquor is reported.…”

“…have been advanced for desirable transformation of coordination frames formed via self-assembly of central metal ions as angle components with appropriate multidentate ligands as spacers. − A noteworthy conceptual feature is that one-dimensional (1D) molecular frames have easy changeability along with low entropy relative to two-dimensional (2D) and three-dimensional (3D) frames . The delicate solubility-difference of 1D may play a significant role in the transformation of the products. ,, In particular, some flexible tridentate ligands possessing noninnocent angles and conformational nonrigidity have produced such interesting scientific results. ,, In this context, unusual in situ two-step crystallization for 1D coordination polymerization via the self-assembly of Ag­(I) ions with a flexible N -donor tridentate ligand (L) in the mother liquor is reported. This communication reports a conceptually advanced synthetic method in self-assembly reaction.…”