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Interestingly, introducing a guest molecule to the system can adjust the phase transition process and effectively stabilize the honeycomb structure of BTB. The flexibility associated with the porous networks renders it a dynamic supramolecular template for guest binding.Density functional theory calculations were performed to investigate the catalyst-controlled selective functionalization of indoles with vinyl diazoacetates. The detailed reaction mechanism was established, and different roles of carboncation or carbene intermediates in defi