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. 2020 May 20;142(20):9152-9157.
doi: 10.1021/jacs.0c03798. Epub 2020 May 6.

Transformation Network Culminating in a Heteroleptic Cd6L6L'2 Twisted Trigonal Prism

Dawei Zhang  1 , Tanya K Ronson  1 , Lin Xu  1   2 , Jonathan R Nitschke  1
Affiliations

Transformation Network Culminating in a Heteroleptic Cd6L6L'2 Twisted Trigonal Prism

Dawei Zhang et al. J Am Chem Soc. .

Abstract

Transformations between three-dimensional metallosupramolecular assemblies can enable switching between the different functions of these structures. Here we report a network of such transformations, based upon a subcomponent displacement strategy. The flow through this network is directed by the relative reactivities of different amines, aldehydes, and di(2-pyridyl)ketone. The network provides access to an unprecedented heteroleptic Cd6L6L'2 twisted trigonal prism. The principles underpinning this network thus allow for the design of diverse structural transformations, converting one helicate into another, a helicate into a tetrahedron, a tetrahedron into a different tetrahedron, and a tetrahedron into the new trigonal prismatic structure type. The selective conversion from one host to another also enabled the uptake of a desired guest from a mixture of guests.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
Network of transformations between architectures 1–8, showing the X-ray crystal structures of helicate FeII2L31b (a), which is the FeII analogue of CdII2L31a, and (b) TfO–⊂3. For the crystal structures, disorder, unbound counterions, hydrogen atoms, and solvent of crystallization are omitted for clarity.
Figure 2
Figure 2
(a) Subcomponent self-assembly of Cd6L6L′28 and the aromatic region of its 1H DOSY spectrum (400 MHz, 298 K, CD3CN). The three imine peaks of 8 are marked with solid black circles (●). For a full structural assignment, see Figure S67. (b, c) Crystal structure of 8 with (b) and without (c) the two bound triflate anions. Disorder, additional counterions, peripheral R groups on the E residues, hydrogen atoms, and solvent of crystallization are omitted for clarity. Only the N atoms of the free amines are colored blue, with the rest of symmetry-equivalent ligands being colored magenta, black, and cyan. CdII centers are yellow, which are connected by yellow lines to their nearest neighbors. Average CdII–CdII distances are labeled in (a).
Figure 3
Figure 3
Schematic representation of selective uptake of either triflate or cyclohexane upon structural transformations.
See this image and copyright information in PMC

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