Chemical mimicry of viral capsid self-assembly via corannulene-based pentatopic tectons

Abstract

Self-assembly of twelve pentatopic tectons, which have complementary edges or can be linked using either digonal or trigonal connectors, represents the optimal synthetic strategy to achieve spherical objects, such as chemical capsids. This process requires conditions that secure uninterrupted equilibria of binding and self-correction en route to the global energy minimum. Here we report the synthesis of a highly soluble, deca-heterosubstituted corannulene that bears five terpyridine ligands. Spontaneous self-assembly of twelve such tectons with 30 cadmium(II) cations produces a giant icosahedral capsid as a thermodynamically stable single product in high yield. Nuclear magnetic resonance (NMR) methods, mass spectrometry analyses, small-angle X-ray scattering, transmission electron microscopy, and atomic force microscopy indicate that this spherical capsid has an external diameter of nearly 6 nm and shell thickness of 1 nm, in agreement with molecular modeling. NMR and liquid chromatography evidences imply that chiral self-sorting complexation generates a racemic mixture of homochiral capsids.

Multidimensional Mass Spectrometry Assisted Metallo-Supramolecular Chemistry

“…1 Among various noncovalent driving forces, metal-ligand coordination plays a vital role in the self-assembly of metallosupramolecules with both structural and functional sophistication, benefitting from the high directionality and predictable feature of coordination bonds. [2][3][4][5][6] As a result, metallo-supramolecular chemistry has witnessed an explosion in building up a myriad of artificial supramolecular architectures, including polygons, [7][8][9][10][11] knots, [12][13][14][15] links, [16][17][18][19] fractals, [20][21][22] as well as Platonic, [23][24][25][26][27] Archimedean, [28][29][30][31][32][33][34] and Goldenberg polyhedrons, 35,36 etc. And these complexes show great potentials among different fields, including catalysis, [37][38][39][40][41][42][43][44][45][46] nano-elect...…”

Pseudo-5-Fold-Symmetrical Ligand Drives Geometric Frustration in Porous Metal–Organic and Hydrogen-Bonded Frameworks

“…12,16 Several strategies exist for the introduction of C5 symmetry in organic building blocks, [17][18][19][20] as these are used for the synthesis of large cage coordination compounds, 19,[21][22][23][24] or as metal nodes for the synthesis of quasicrystal approximants. 25 As introducing C5-symmetry can be synthetically challenging, 20,26 instead we designed a pseudo-C5 symmetrical ligand based on a pyrrole core (see method section, Figure S2). The pseudo-C5 symmetric linker containing pendant carboxylic acid groups, 1,2,3,4,5-penta (4-(benzoic acid))pyrrole (pLH5; Figure 1) was reacted with copper(II) ions with the intention of creating the C4 -symmetric paddlewheel motif.…”

Self-sorting assembly of artificial building blocks

“…25 Very recently, self-sorting systems with fantastic properties have been reported for controlling the final products in reversible reactions, 26 fabricating hierarchical micro-structures, 27,28 separating isomer mixtures, 29 enhancing the proliferation and survival of cells, 30 tissue engineering, 31 and various other fields. 6,32–36…”