Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 20, Pages 11370-11377Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202016395
Keywords
enantioselective reaction; on-surface reactions; post-functionalization; scanning tunneling microscopy; supramolecular polymers
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Funding
- National Natural Science Foundation of China [21925201, 91845110]
- Shanghai Municipal Science and Technology Major Project [2018SHZDZX03]
- Natural Science Foundation of Shanghai [20ZR1414200]
- Programme of Introducing Talents of Discipline to Universities [B16017]
- Program of the Shanghai Committee of Sci. Tech [18520760700]
- Program for Eastern Scholar Distinguished Professor
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This study achieved the on-surface post-functionalization of supramolecular polymers on gold surfaces, and discovered an enantioselective on-surface reaction induced by the chirality of the supramolecular polymers. Mechanistic analysis and DFT calculations revealed high enantioselectivity during the addition of ICBP to the chiral SP intermediate.
Although post-functionalization is extensively used to introduce diverse functional groups into supramolecular polymers (SPs) in solution, post-functionalization of SPs on surfaces still remains unexplored. Here we achieved the on-surface post-functionalization of two SPs derived from 5,10,15-tri-(4-pyridyl)-20-bromophenyl porphyrin (Br-TPyP) via cross-coupling reactions on Au(111). The ladder-shaped, Cu-coordinated SPs preformed from Br-TPyP were functionalized through Heck reaction with 4-vinyl-1,1 '-biphenyl. In the absence of Cu, Br-TPyP formed chiral SPs as two enantiomers via self-assembly, which were functionalized via divergent cross-coupling reaction with 4-isocyano-1,1 '-biphenyl (ICBP). Surprisingly, this reaction was discovered as an enantioselective on-surface reaction induced by the chirality of SPs. Mechanistic analysis and DFT calculations indicated that after debromination of Br-TPyP and the first addition of ICBP, only one attack direction of ICBP to the chiral SP intermediate is permissive in the second addition step due to the steric hindrance, which guaranteed the high enantioselectivity of the reaction.
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