Symmetrically Related Construction and Optical Properties of Two Noncentrosymmetric 3D Iodides of d(10) Cation (Cu(+), Ag(+)) Based on the N-Benzylpyridinium and Its Supramolecular Interactions.

Two noncentrosymmetric compounds, namely, [N-Bz-Py]2[Cu6I8] (1) and [N-Bz-Py]4[Ag9I13] (2) (N-Bz-Py(+) = N-benzylpyridinium), with three-dimensional open frameworks, were synthesized solvothermally via in situ benzylation of pyridine. 1 is constructed from 3-connected Cu3I7 secondary building units (SBUs) with chiral (10,3)-a topology, while the occluded N-Bz-Py(+) forms a complementary supramolecular (10,3)-a net via π-π interactions. 2 is characteristic of acentric connections of trimeric Ag3I8 and hexamer Ag6I12 SBU, while N-Bz-Py(+) in the channels aggregates into asymmetrically supramolecular chains via π-π interactions. Remarkable structural correlations imply the unique amplification and transfer of asymmetric information from V-shaped N-Bz-Py(+) to organic supramolecular nets and inorganic frameworks, which are confirmed by their second harmonic generation responses. Adsorption spectra reveal their semiconductive nature (2.52 eV for 1 and 3.02 eV for 2) and interesting reversible thermochromism for 1 based on the intermolecular charge transfer.