10.1002/anie.202008415
Angewandte Chemie International Edition
RESEARCH ARTICLE
Wang, S. Zhang, Y. Chen, Z. Zhang, S. Ma, Chem. Soc. Rev. 2020, 49,
708-735.
It is well-known that the crystalline materials as heterogeneous
catalysts have a strong tendency to aggregate in solution, which
inevitably cause retarded mass transfer, reduced interfacial area
and consecutively hampered catalytic capability in liquid phase
catalysis.26 The well dispersed system provides us a routine to
solve such problem once in combination with the metal
nanoparticles/clusters for liquid-phase catalytic reaction. Here,
the CC3R-immobilized Rh cluster for AB methanolysis reaction
was employed as a model test. The Rh/CC3R-Ptriaz (particle
size: 1.1 ± 0.2 nm) shows a turnover frequency (TOF) of 278 min-
1 (Figure 5c, e), which is comparable to the highest activity among
the cage immobilized catalysts for AB methanolysis reaction
(304.4 min-1 for Ru NPs@PCC-2 catalyst).5a, 27 Such activity is 1.9
times higher than that of the CC3R without Ptriaz (TOF: 150 min-
1, particle size: 1.9 ± 0.5 nm) (Figure 5d, e), or 21 times higher
than support-free Rh catalyst with aggregated particles (TOF: 13
min-1) (Figure S22&23). Since the cage and PIL are inert to the
reaction (Figure S24&25), such enhanced activity could be
reasonably assigned to the enhanced dispersibility in solution as
well as the smaller size of Rh clusters, which would facilitate the
mass transfer between the Rh and reactants.
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Conclusion
In
conclusion,
kinetically
promoted
room-temperature
crystallization of several imine-linked open organics by 1,2,4-
triazolium PIL as a simple additive is reported. The active C-5
proton in 1,2,4-triazolium units serving as acid together with the
strong solvation power of polyelectrolytes can jointly catalyze the
reaction and precipitate out the formed crystalline products
without deteriorating their crystallinity. This previously
undiscovered mechanism is important and will inspire porous
materials community to expedite the research progress of open
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Acknowledgements
J. K. S. acknowledges Starting Grant from Beijing Institute of
Technology (3100011181910). J. Y. is grateful for financial
support from the ERC Starting Grant NAPOLI-639720 from
European Research Council, Stockholm University Strategic fund,
Swedish Research Council grant 2018-05351, Dozentenpreis
15126 from Verband der Chemischen Industrie e.V. (VCI) in
Germany, and the Wallenberg Academy Fellow program (KAW
2017.0166) in Sweden. Q. Z. acknowledges the funding from
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National Natural Science Foundation of China (Grant No.
21703172). Dr. W. Y. Zhang is acknowledged for providing poly(4-
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Keywords: Poly(ionic liquid)
• Open organic material •
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