Chem p. 3374 - 3384 (2020)
Update date:2022-08-17
Topics:
Baik, Mu-Hyun
Cho, Dasol
Dhamija, Avinash
Hwang, In-Chul
Hwang, Wooseup
Kim, Ikjin
Kim, Kimoon
Kim, Seungha
Kim, Younghoon
Ko, Young Ho
Koo, Jaehyoung
Lee, Hochan
Mukhopadhyay, Rahul Dev
Song, Hayoung
Due to the existing challenges in the synthesis of covalently linked large organic cages, the potential benefits of such gigantic structures have been less explored, comparatively. Here, we present a one-pot, template-free strategy to construct a porphyrin-based gigantic organic cage P12L24, built with 12 square-shaped porphyrins (P) and 24 bent linkers (L). Single crystal X-ray analysis of P12L24 revealed a cuboctahedron structure with a diameter of ~5.3 nm reminiscent of the COPII protein with a cuboctahedral geometry. To the best of our knowledge, it represents the largest, pure organic synthetic cage reported so far. By virtue of its large voids facilitating mass transport of substrates, 3a efficiently catalyzes the photooxidation of dihydroxynaphthalene derivatives in a heterogeneous setting, corroborating the benefits of these structures. Additionally, we demonstrate the insertion of a linear guest molecule into Zn-metallated cage Zn-3b in solution, which may facilitate the synthesis of multivariate gigantic cages in the future. A bottom-up self-assembly process has been a promising tool to mimic structurally complex natural architectures, e.g., the bacteriochlorophyll-based macrocyclic arrays in natural light-harvesting systems and gigantic hollow assemblies, such as ferritin, COPII cage, and other viral capsids. Nevertheless, there is still a long way to go before we can astutely program multiple building blocks to form predesigned structures. In this context, the reported examples related to atomically precise multiporphyrinic arrays and cages are limited by their tedious synthesis, poor yield and solubility, atomic-scale characterization, and small-sized cavities. Here, we report a strategy to synthesize gigantic porphyrinic cages (~5.3 nm) with 36 components and demonstrate its potential applications in processes such as heterogeneous photocatalysis and guest encapsulation. Our strategy may establish a cornerstone toward the construction of higher level, covalently bonded multiporphyrinic molecular containers. Porphyrin-based 3D molecular architectures encompassing a confined internal void have comparatively been less explored, despite their potential benefits. Here, we report a rational one-pot, template-free strategy for constructing a 5.3 nm porphyrin-based gigantic organic cage P12L24, which is reminiscent of the structure of COPII protein cuboctahedral cages. To the best of our knowledge, this is the largest purely organic cage reported so far. P12L24 efficiently catalyzes the photooxidation of dihydroxynaphthalene derivatives, thereby confirming the benefit of these gigantic structures with mesoscopic channels. Furthermore, we demonstrate the insertion of a long pillar linker (~4 nm in length) into Zn-P12L24 in solution. We believe that our strategy may establish a new direction toward the construction of higher level, covalently bonded multiporphyrinic cages.
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