Structural Diversity in Metal−Organic Frameworks Built from Rigid Tetrahedral [Si(p-C₆H₄CO₂)₄]⁴⁻ Struts

Abstract

The silicon-based connector

Siloxane-based linkers in the construction of hydrogen bonded assemblies and porous 3D MOFs

“…3,4 We have been interested for some time in the synthesis of highly branched organosilicon linkers and their use in the assembly of MOFs, largely due to their synthetic accessibility compared to their carbon-centred analogues. [5][6][7][8][9][10] However, despite the siloxane linkage (Si-O-Si) being ubiquitous in many classes of materials including zeolites, 11,12 periodic mesoporous organosilicas, 13,14 POSS hybrids and other porous materials, 15,16 we were surprised to find that there has been little interest in siloxane-based linkers [17][18][19][20][21] for MOFs, and that their incorporation into a porous 3D MOF has not been reported to date. We have thus recently focussed upon the development of siloxane-based polycarboxylates, and report herein the synthesis of the novel pseudooctahedral hexa(4-carboxyphenyl)disiloxane molecule (L1-H 6 ), its unusual hydrogen bonded network assembly and its application in the preparation two new MOF materials.…”

2D Oligosilyl Metal–Organic Frameworks as Multi‐state Switchable Materials

“…Oligosilanes, molecules with Si−Si bonds, are a class of hybrid inorganic‐organic materials with remarkable light absorption and charge transport properties that uniquely combine flexibility and strong light absorption, a property that inspired us to construct 2D MOFs based on oligosilyl linkers. While organosilicon species have been previously used in MOF formation, the organic linker usually contains a single Si atom, which precludes access to properties inherent to σ‐conjugated extended oligosilanes.…”

A Zr metal–organic framework based on tetrakis(4-carboxyphenyl) silane and factors affecting the hydrothermal stability of Zr-MOFs

“…Although, the Zr-MOF based on the tetrakis(4-carboxyphenyl) methane (TCPM) (MOF-841) have been reported by Yaghi et al, only water adsorption of MOF-841 was investigated, which is one of the top performers among the 11 Zr-MOFs and other 11 porous solids. 31 1 and MOF-841 have the same topology. 31 1 and MOF-841 have the same topology.…”