| Abstract
| - Hybrid layered [DAMS+][Ag5I6-] was prepared through a step-by-step mechanochemical synthesis, allowing us to elucidate the sequence of the ordering process in the growth of the crystalline framework. The first step is the intralayer guest self-organization into J-aggregates, and the second step is the building up of a macroscopic ordering, thus producing a macroscopic polarity responsible for the material's high SHG. The same synthetic route was successfully applied to [DAZOP+][Ag5I6-] and [DAES+][Ag5I6-].
- The inorganic−organic hybrid layered material of stoichiometry [DAMS+][Ag5I6-], characterizedby a strong SHG activity, has been prepared mechanochemically by room-temperature ball-milling amixture of AgI and [DAMS+][I-], eventually followed by a moderate heating. By means of electronicabsorption spectra, XRPD, and second harmonic generation (SHG) experiments we proved that theintralayer ordering of the [DAMS+] nonlinear optical chromophores into J-aggregates precedes theinterlayer one, on the whole producing, by a sequential process, the “macropolarity” responsible for thestrong SHG. The mechanochemical approach was shown to be of general use, as it was successfullyapplied to the synthesis of the analogous [DAMS+][Cu5I6-], [DAZOP+][Ag5I6-], and [DAES+][Ag5I6-]materials.
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