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. 2022 Jan 26;144(3):1106-1112.
doi: 10.1021/jacs.1c11536. Epub 2022 Jan 11.

Templation and Concentration Drive Conversion Between a FeII12L12 Pseudoicosahedron, a FeII4L4 Tetrahedron, and a FeII2L3 Helicate

Dawei Zhang  1   2 , Quan Gan  2   3 , Alex J Plajer  2   4 , Roy Lavendomme  5 , Tanya K Ronson  2 , Zifei Lu  2 , Jesper D Jensen  6 , Bo W Laursen  6 , Jonathan R Nitschke  2
Affiliations

Templation and Concentration Drive Conversion Between a FeII12L12 Pseudoicosahedron, a FeII4L4 Tetrahedron, and a FeII2L3 Helicate

Dawei Zhang et al. J Am Chem Soc. .

Abstract

We report the construction of three structurally distinct self-assembled architectures: FeII12L12 pseudoicosahedron 1, FeII2L3 helicate 2, and FeII4L4 tetrahedron 3, formed from a single triazatriangulenium subcomponent A under different reaction conditions. Pseudoicosahedral capsule 1 is the largest formed through subcomponent self-assembly to date, with an outer-sphere diameter of 5.4 nm and a cavity volume of 15 nm3. The outcome of self-assembly depended upon concentration, where the formation of pseudoicosahedron 1 was favored at higher concentrations, while helicate 2 exclusively formed at lower concentrations. The conversion of pseudoicosahedron 1 or helicate 2 into tetrahedron 3 occurred following the addition of a CB11H12- or B12F122- template.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
(a) Subcomponent self-assembly of FeII12L12 pseudoicosahedron 1, with cutout showing the meridional metal coordination geometry. (b) PM7-optimized molecular model of pseudoicosahedron 1. Carbon atoms for the three distinct ligand arms about one of the mer-vertices have been colored cyan, green, and orange, respectively. (c) Model of 1 in space-filling mode, to show the porosity. Carbon atoms of the three triazatriangulenium ligands surrounding a large pore of 1 have been colored cyan, green, and orange, respectively.
Figure 2
Figure 2
(a) 1H DOSY NMR spectrum (500 MHz, 298 K, CD3CN) of pseudoicosahedron 1. The labeled peaks correspond to the imine and methoxy groups are highlighted in Figure 1a. (b) ESI-mass spectrum of 1.
Figure 3
Figure 3
Schematic drawing of 2′ (a) and X-ray crystal structure of (ReO4–)2⊂2′ (b). Disorder, noncentrally bound counterions, and solvent of crystallization are omitted for clarity.
Figure 4
Figure 4
Interconversion between pseudoicosahedron 1, helicate 2, and tetrahedron 3, showing PM7-optimized molecular models of each with the cavity volumes outlined in green mesh. Pseudoicosahedron 1 and helicate 2 interconverted following a change in ligand concentration. Addition of CB11H12– or B12F122– to assembly 1 or 2 drove the formation of tetrahedron 3, with the template anion bound inside the cavity.
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