Suprachannels via a Molecular Array of 2D Networks: Solvent Effects, Anion Exchange, and Physicochemical Properties of Silver(I) Complexes Bearing <i>N</i>,<i>N</i>′,<i>N</i>″‑Tris(2-pyridinylethyl)-1,3,5-benzenetricarboxamide

The solvent effects on suprachannel formation via a molecular array of 2D networks were studied. The basic structure of the [Ag₃L₂]­(X)₃ (X^– = NO₂^–, NO₃^–) 2D network consists of hexagonal (Ag₆L₆) motifs formed via self-assembly of Ag­(I) with <i>C</i>₃-tridentate <i>N</i>-donors. The 2D networks are arranged in an eclipsed mode in aqueous solution, thus forming suprachannels (5.2 × 7.3 Ų, 6.2 × 7.7 Ų) of [Ag₃L₂(H₂O)₂]­(X)₃, whereas they are arranged in a staggered <i>abab</i>... mode in nonaqueous solution, thus forming semisuprachannels (3.1 × 5.1 Ų) of [Ag₃(NO₃)₂L₂]­(NO₃). The suprachannel structure of [Ag₃L₂(H₂O)₂]­(NO₃)₃ is soluble in methanol; contrastingly, the semisuprachannel structure of [Ag₃(NO₃)₂L₂]­(NO₃) is insoluble in that solvent. In the present study, significant differences in molecular recognition and anion exchangeability between [Ag₃L₂(H₂O)₂]­(NO₃)₃ and [Ag₃(NO₃)₂L₂]­(NO₃) were found

Host–Guest Chemistry of 1D Suprachannels and Dihalomethane Molecules: Metallacyclodimeric Ensembles Consisting of Zinc(II)-2,7-bis(nicotinoyloxy)naphthalene Complexes

Self-assembly of ZnX₂ (X = Cl, Br, and I) with 2,7-bis­(nicotinoyl­oxy)­naphthalene (L) as a hemicircular bidentate ligand containing a chromophore moiety yields a systematic metallacyclodimeric unit, [ZnX₂(L)]₂. These basic skeletons constitute, via interdigitated π···π interactions, a unique columnar ensemble forming a suprachannel. This can then be employed as an unusual “diiodomethane within the suprachannel” host–guest system, CH₂I₂@​[ZnX₂(L)]₂. Specifically, the suprachannel significantly stabilizes the CH₂I₂ molecules in the order [ZnI₂(L)]₂ > [ZnBr₂(L)]₂ > [ZnCl₂(L)]₂. This suprachannel has significant halogen effects on the photoluminescence (PL), thermal properties, and host–guest inclusion

Suprachannel as a Radical Trap: Crystal Structure of Single Carbon Radicals

We report proof-of-concept experiments on the unprecedented crystal structure of an iodomethyl radical (·CH₂I) nestled within an ensemble’s suprachannel via single crystal-to-single crystal photoreaction without destruction of the suprachannel. The trapped nonconjugated carbon radical was additionally confirmed by EPR, ¹³C MAS, UPS, and Raman spectra