“…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.…”