Preparation of Hybrid Ordered Inorganic–Organic Mesostructures from an Asymmetrically Bridged Organic Precursor Containing Both Silanolate and Phosphonate

Abstract

Novel hybrid inorganic–organic mesostructures were hydrothermally prepared from pseudo-boehmite and an organic precursor containing both silanolate and phosphonate groups in the presence of cationic surfactants. The solid-state NMR revealed that aluminum species are mainly connected with phosphonate groups in the formed 2D hexagonal mesostructures.

Mesoporous Zirconium Phenylenesiliconate‐phosphonate Hybrids with Ordered Lamellar Nanostructures

“…The ethyl ester of the para ‐PPS isomer 4‐(EtO) 2 OPC 6 H 4 Si(OEt) 3 ( p PPS‐E) was prepared according to our previous report,5 and the high‐boiling‐point crude product was purified by distillation in a Kugelrohr apparatus.…”

“…3‐BrC 6 H 4 Si(OEt) 3 was prepared according to a literature procedure 24. Compound m PPS‐E was prepared basically by using the procedure for the para isomer,5 as follows: P(OEt) 3 (3.32 g, 21 mmol) was added dropwise over 2 h to a suspension of 3‐[BrC 6 H 4 Si(OEt) 3 ] (5.06 g, 16 mmol) and NiBr 2 (0.361 g, 17 mmol) in mesitylene (1 mL) at 140 °C, and formed ethyl bromide was collected in a cooling trap. After the addition was complete, the reaction mixture was stirred at the same temperature for 1 h. The solvent and the unreacted starting materials were removed in vacuo.…”

“…Our interest is focused on the use of such asymmetrically linked organic units to form inorganic–organic hybrid ordered nanostructures. Recently, we succeeded in the preparation of novel 2D hexagonally ordered organic–inorganic hybrid mesostructures APS‐15 and ZrPS‐1a6 (originally denoted as ZPS but hereafter changed to ZrPS to avoid confusion with zinc‐containing compounds) that contained 4‐[O 3 PC 6 H 4 SiO 3 ] ( p PPS) units with aluminum or zirconium sources, respectively, in the presence of alkyltrimethylammonium bromide (C n TAB; n =12–18; n =16 unless otherwise stated) surfactants. This asymmetrically linking molecular component has not been used before as a main building unit for hybrid mesostructures as far as we are aware.…”

“…In contrast, organophosphonateg roups tend to form stable PÀOÀMb onds with metali ons, as mentioned above, whereas PÀOÀPa nd PÀOÀSi bondsa re generally known to be unstableu nder hydrothermal conditions. The use of buildingb locks with both siliconate and phosphonatef unctionalities in mesoporous materials can induceu nprecedented nanostructures in the pore walls, which leads to unique properties because of the different preferences of these functionalities for connectivity.O ur interest is focused on the use of such asymmetrically linked organic units to form inorganic-organic hybrid ordered nanostructures.R ecently,w e succeeded in the preparation of novel 2D hexagonally ordered organic-inorganic hybrid mesostructures APS-1 [5] and ZrPS-1a [6] (originally denoted as ZPS but hereafter changed to ZrPS to avoid confusion with zinc-containing compounds) that contained 4-[O 3 PC 6 H 4 SiO 3 ]( pPPS) units with aluminum or zirconium sources, respectively,i nt he presence of alkyltrimethylammonium bromide (C n TAB; n=12-18; n=16u nless otherwise stated)s urfactants. This asymmetrically linkingm olecular component has not been used before as am ain buildingu nit for hybridm esostructuresa sf ar as we are aware.…”

Further Understanding of the Reactivity Control of Bisphosphonates to a Metal Source for Fabricating Highly Ordered Mesoporous Films

“…There have been no papers on the successful synthesis of mesostructured metal phosphonates by using bisphosphonate compounds bridged with asymmetric organic groups. Only one study on as urfactant-assisted synthesis by using an asymmetric compound like diethylphosphatophenyltriethoxysilane, (EtO) 2 OP-C 6 H 4 -Si(OEt) 3 ,h as been found, [52][53][54] but the reactivities of both ends (PÀOEt and SiÀOEt) of the molecule are quite different and thus it would be difficultt oo btain highly ordered mesoporousm aterials. In the NMR spectra of the partially acidified bisphosphonate having amide groups ( Figure S1 in the SupportingI nformation), we cannota ssign all signals due to its asymmetrics tructure.…”