Design and Synthesis of Porous Coordination Polymers with Expanded One‐Dimensional Channels and Strongly Lewis‐Acidic Sites

Abstract New porous coordination polymers (PCPs) consisting of La^III cations and thiophene‐based tritopic organic linkers, La‐ThBTB and La‐PhBTTc, are synthesized and structurally characterized. While these La‐PCPs exhibit the same type of one‐dimensional hexagonal channels, their thermal and chemical stability vary significantly with respect to each other, thus demonstrating the crucial importance of the design of the skeletal structure of the organic linker. Because of the large channel sizes and strong Lewis acidity of these La‐PCPs, the catalytic activity in the Lewis‐acid‐catalyzed cyanosilylation of carbonyl compounds shows among the highest reported so far for PCPs.