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. 2023 Sep 6;145(35):19164-19170.
doi: 10.1021/jacs.3c04228. Epub 2023 Aug 23.

Hetero-Diels-Alder Reaction between Singlet Oxygen and Anthracene Drives Integrative Cage Self-Sorting

Yuchong Yang  1 , Tanya K Ronson  1 , Dingyu Hou  2 , Jieyu Zheng  1 , Ilma Jahović  1 , Kai Hong Luo  2 , Jonathan R Nitschke  1
Affiliations

Hetero-Diels-Alder Reaction between Singlet Oxygen and Anthracene Drives Integrative Cage Self-Sorting

Yuchong Yang et al. J Am Chem Soc. .

Abstract

A ZnII8L6 pseudocube containing anthracene-centered ligands, a ZnII4L'4 tetrahedron with a similar side length as the cube, and a trigonal prism ZnII6L3L'2 were formed in equilibrium from a common set of subcomponents. Hetero-Diels-Alder reaction with photogenerated singlet oxygen transformed the anthracene-containing "L" ligands into endoperoxide "LO" ones and ultimately drove the integrative self-sorting to form the trigonal prismatic cage ZnII6LO3L'2 exclusively. This ZnII6LO3L'2 structure lost dioxygen in a retro-Diels-Alder reaction after heating, which resulted in reversion to the initial ZnII8L6 + ZnII4L'4 ⇌ 2 × ZnII6L3L'2 equilibrating system. Whereas the ZnII8L6 pseudocube had a cavity too small for guest encapsulation, the ZnII6L3L'2 and ZnII6LO3L'2 trigonal prisms possessed peanut-shaped internal cavities with two isolated compartments divided by bulky anthracene panels. Guest binding was also observed to drive the equilibrating system toward exclusive formation of the ZnII6L3L'2 structure, even in the absence of reaction with singlet oxygen.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
(a) Self-assembly and structural transformation of pseudocubic cage 1 and tetrahedral cage 2 from tetramine A and triamine B, respectively. (b) Construction of trigonal prismatic cage 3 and its transformation into cage 4 via hetero-Diels–Alder reaction with photogenerated 1O2. (c) Schematic illustrating how the ligands panel the faces of cages 1–4.
Figure 2
Figure 2
(a) X-ray structure of cage 1 (Zn, yellow; N, blue; O, red; C, gray; H, white). DFT-minimized structures of (b) trigonal prismatic cages 3 and (c) 4. (d) DFT-minimized structure of pseudocubic 5.
Figure 3
Figure 3
Interacting system of cages before and after reaction of 1 with 1O2. (a) The reaction between 1 and 2 led to an equilibrium mixture containing 1, 2, and 3; (b) 1 reacted reversibly with in situ generated 1O2 to form 5, (c) which in turn reacted with 2 to form only 4; (d) treatment of the equilibrium mixture of 1–3 with 1O2 gave only 4; both processes (b) and (d) were reversible following thermal retro-cycloaddition. (e) The reversibility of process (d) is charted over five cycles.
Figure 4
Figure 4
(a) Cavity volumes of 1, 3, 4, and 5, outlined in deep blue mesh. (b) Guest molecules G1–G5 were encapsulated by both 3 and 4 (binding constants of guests G1–G5 with 4 are given below), whereas G6 was encapsulated only by 5 (binding constants of G6⊂5 are given below). (c) G1 induced conversion from 1 and 2 to form exclusively G1⊂3. (d) G6 was taken up and released as a result of the reversible 1O2-mediated transformation of 1 to 5.
See this image and copyright information in PMC

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