Use of Silver(I) and Copper(II) Ions to Assist the Self-Assembly of Polyrotaxanes Incorporating Symmetrical α,α′,δ,δ′-Tetramethyl-cucurbit[6]uril

Three one-dimensional methyl-substituted cucurbituril-based polyrotaxanes, [Ag(H 2 O)(C4N3)(TMeQ[6])](NO 3 )3H 2 O ( 1 ), [Cu(H 2 O) 2 Cl 2 (C4N4)(TMeQ[6])]2H 2 O ( 2 ), and [Ag 2 (H 2 O) 3 (C4N4)(TMeQ[6])]2(NO 3 )14H 2 O ( 3 ) have been prepared with N, N ′-bis(3-pyridylmethyl)-1,4-butanediamine (C4N3) and N, N ′-bis(4-pyridylmethyl)-1,4-butane diamine (C4N4), incorporating a symmetrical α,α′,δ,δ′-tetramethyl-cucurbit[6]uril (TMeQ[6]) using methods assisted by silver(I) and copper(II) ions. X-ray diffraction analyses reveal that all three polyrotaxanes have basically 1D linear chain structures with different shapes. However, the π···π stacking of the protruded pyridyl ring of the guest is observed and leads to the formation of two-dimensional networks in compound 1 . Unlike most cases in which a metal ion coordinates to both of the terminal pyridyl nitrogen atoms of two neighboring pseudorotaxanes, the silver ion coordinates to only one terminal pyridyl nitrogen atom and simultaneously coordinates to two carbonyl oxygen atoms of the neighboring Q[6], leading to the formation of the 1D supramolecular chain in compound 3 .