Post-Synthesis Modification of the Aurivillius Phase Bi₂SrTa₂O₉ via In Situ Microwave-Assisted “Click Reaction”

Abstract

A new strategy for the functionalization of layered perovskites is presented, based on the in situ post-synthesis modification of a prefunctionalized phase by copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC). The microwave-assisted protonation and grafting of an alkyne alcohol provides the alkyne-functionalized precursor within a few hours, starting from BiSrTaO. The subsequent microwave-assisted in situ "click reaction" allows the post-synthesis modification of the precursor within ∼2 h, providing a layered perovskite functionalized by an alcohol-grafted 1,4-disubstituted-1H-1,2,3-triazole. Two compounds are described here, bearing an aliphatic and an aromatic substituent, which illustrates the general application of the method. This work opens new perspectives for the functionalization of layered perovskites, going beyond mere insertion/grafting reactions, and thus broadens the design possibilities and the range of applications of these hybrid systems.

Microwave-assisted functionalization of the Aurivillius phase Bi2SrTa2O9: diol grafting and amine insertion vs. alcohol grafting

“…This downfield shift indicates unambiguously the formation of the covalent bond C–O–Ta in the reaction products. 10 , 13 , 19 , 27…”

“… 1 , 10 – 15 Very recently, several reports have underlined the considerable progress offered by microwave activation for the functionalization of such layered perovskites, notably in terms of speed of the reactions. 6 , 16 – 18 In addition, apart from classical insertion or grafting reactions, 16 – 18 microwave-assisted post-synthesis modification 19 and exfoliation 20 have also been reported.…”

“…Until now, there is one single report of grafting reaction in the protonated form of an Aurivillius phase. 19 …”

Rapid Exfoliation and Surface Tailoring of Perovskite Nanosheets via Microwave‐Assisted Reactions

“…Rapid microwave‐assisted (MA) methods have been found to be effective for organic modification of bulk layered perovskites . Herein we extend microwave methods to both the rapid exfoliation and post‐exfoliation surface‐modification of perovskite nanosheets.…”

“…[70,71,134,135] Rapid microwave-assisted (MA) methods have been found to be effective for organicm odification of bulk layered perovskites. [136][137][138][139] Herein we extend microwave methods to both the rapid exfoliation and post-exfoliation surface-modification of perovskite nanosheets. MA reactions allow exfoliations and subsequents urfacem odifications to be carried out in as little as 1h,r espectively.E xfoliation utilizes the protonated doublelayered Dion-Jacobson perovskite (HLnNb 2 O 7 ;L n = La, Pr) where reactions with TBAOH quickly lead to dispersed materials.…”