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Preparation of Siloxane‐Based Microporous Crystals from Hydrogen‐Bonded Molecular Crystals of Cage Siloxanes
Author(s) -
Sato Naoto,
Kuroda Yoshiyuki,
Wada Hiroaki,
Shimojima Atsushi,
Kuroda Kazuyuki
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201804441
Subject(s) - silanol , microporous material , siloxane , hydrogen bond , materials science , intermolecular force , silylation , cage , porosity , hydrothermal circulation , chemical engineering , crystallography , chemistry , molecule , organic chemistry , composite material , catalysis , polymer , mathematics , combinatorics , engineering
Controlled assembly of siloxane‐based building blocks provides a rational approach toward designed architectures of silica‐based porous materials. Here, a non‐hydrothermal method to prepare microporous crystals from cage‐type oligosiloxanes is reported. The crystals formation occurs through an ordered assembly assisted by hydrogen bonds and subsequent intermolecular connection by silylation. Cage siloxanes with a double‐four ring (D4R) structure were modified with dimethylsilanol groups. Intermolecular hydrogen bonding of the dimethylsilanol groups led to the formation of a pillared‐layer structure consisting of D4R units. A new crystalline microporous material retaining the original ordered arrangement was realized by bridging adjacent cages within the crystals by direct silylation of the silanol groups with trichlorosilane. The use of this silylating agent created microporous crystals containing Si−H groups, proving the advantages of the proposed concept.