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. 2023 Aug 23;145(35):19164–19170. doi: 10.1021/jacs.3c04228

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

Yuchong Yang †, Tanya K Ronson †, Dingyu Hou ‡, Jieyu Zheng †, Ilma Jahović †, Kai Hong Luo ‡, Jonathan R Nitschke †,*
PMCID: PMC10485901  PMID: 37610128

Abstract

graphic file with name ja3c04228_0005.jpg

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.

Self-sorting processes in chemical systems1 enable multiple structures to form from a common pool of subunits, thereby potentially exercising their functions in parallel within the same solution. Understanding these processes can shed light on the complex self-assembly pathways in natural systems,1a as well as enable the design of chemical systems that serve useful purposes.2 Artificial self-sorting systems have been developed where subunits are bound together by hydrogen bonds,3 metal–ligand coordination,4 aromatic stacking interactions,5 and electrostatic attraction.6

Coordination cages can be produced in self-sorting systems where selectivity is driven by thermodynamic and geometric parameters.7 These cages can undergo structural changes in response to different stimuli,8 such as post-assembly modification.9

As shown in Figure 1, ZnII8L6 pseudocubic cage 1 and ZnII4L′4 tetrahedral cage 2 self-assembled from trigonal subcomponent A and anthracene-centered tetragonal subcomponent B, respectively. As a consequence of the matching side lengths of A and B, mixing of solutions of 1 and 2 led to the emergence of a third cage, trigonal prismatic 3,7a in equilibrium with the other two.

Figure 1.

Figure 1

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(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.

Singlet oxygen (1O2) reacted with the anthracene-containing B residues within both 1 and 3 to generate the hetero-Diels–Alder endoperoxide product.10 This post-assembly modification9 impacted the relative stabilities of the members of the system by favoring the oxidized trigonal prismatic cage 4 and, thus, tilting the system toward integrative self-sorting.1a,1b,6 This modified trigonal prism 4 was observed to thermally revert to the precursor system following retro-Diels–Alder extrusion of O2 thermally, thus allowing for reversible switching between the mixed and integratively self-sorted states of the system.

The bulky anthracene panels of trigonal prismatic coordination cages 3 and 4 separated the internal cavity into two isolated compartments. Neutral guest molecules were encapsulated in the trigonal prisms 3 and 4, but not in pseudocube 1 or only weakly in tetrahedron 2.11a Reaction with 1O2 thus set in motion a cascade of events that resulted in guest binding as the system of cages reconfigured.

In the absence of 1O2, the strong binding of adamantane within 3 also reconfigured the 1 + 2 ⇌ 2 × 3 equilibrium. This binding stabilized 3, favoring its formation. Adamantane binding thus served as an alternative signal, which triggered the system to integratively self-sort.

Cages 1 and 2 were synthesized individually via subcomponent self-assembly, as shown in Figure 1a, where dynamic coordinative (N→Zn) and covalent (C=N) bonds formed during the same overall process. Subcomponent A was synthesized from commercially available anthracene-9,10-diboronic acid bis(pinacol) ester (Supporting Information, Section 2.1). The reaction of A (6 equiv) with zinc(II) bis(trifluoromethanesulfonyl)imide [Zn(NTf2)2, 8 equiv] and 2-formylpyridine (24 equiv) in acetonitrile at 70 °C produced ZnII8L6 cubic cage 1. Electrospray ionization mass spectrometry (ESI-MS) confirmed the ZnII8L6 composition (Figure S11 and S12), in line with diffusion-ordered spectroscopy (DOSY) NMR measurements (Figure S10), which provided a hydrodynamic radius of 20.9 Å. The reaction of commercially available subcomponent B (4 equiv) with 2-formylpyridine (12 equiv) and Zn(NTf2)2 (4 equiv) provided cage 2, following published procedures.11

Single crystals of cage 1 suitable for analysis by X-ray diffraction were obtained by the slow diffusion of diethyl ether into an acetonitrile solution. The solid-state structure (Figure 2a) revealed six anthracene ligands bridging eight octahedral ZnII centers in an S6-symmetric framework, with four metal centers adopting a Λ configuration, and the other four adopting a Δ configuration.12 Within cage 1, the metal–metal distances between adjacent vertices range from 14.8 to 16.4 Å. The bulky anthracene panels protrude into the cage cavity and leave only a small cavity volume of 9.0 Å3, as calculated using MoloVol13 (Figure S116).

Figure 2.

Figure 2

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(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.

Cages 1 and 2 were mixed in acetonitrile and heated at 65 °C for 24 h. The formation of trigonal prismatic cage 3 was observed through integrative self-sorting1b in equilibrium with the narcissistic products 1 and 2 (Figure 1). The presence of all three products was confirmed by 1H NMR, DOSY spectra (Figures S14, S15), and ESI-MS (Figures S16, S17). Two-dimensional NMR techniques provided structural information consistent with a D3-symmetric trigonal prismatic framework for cage 3 (Figures S54–S57). DFT calculations were undertaken using the Gaussian 16 program14 to obtain an energy-minimized structure for cage 3 shown in Figure 2c. This structure gave conformations of the three bulky anthracene panels that projected inward, which separated the internal cavity into two isolated compartments.

We then investigated the [4 + 2] hetero-Diels–Alder reaction between anthracene and 1O2 involving both anthracene-based cubic cage 1 and the self-sorted system containing cages 1, 2, and 3. Pioneering work employing this reaction in supramolecular structures was conducted by Smith and co-workers.15 The groups of Stang,16 Shionoya,17 and Bibal18 have explored structural transformations of host organic molecular capsules and 2D metallo-macrocycles with changes of their binding affinities via this [4 + 2] hetero-Diels–Alder reaction. Building upon this work, cage 1 was mixed with the previously reported17 photosensitizer methylene blue (MB, 0.05 equiv) in acetonitrile. This solution was irradiated (λmax = 630 nm) for 2 h at room temperature under air (Figure 1). After irradiation, the anthracene moieties of the cages were found to have reacted to form endoperoxides, thereby generating the oxidized cubic cage 5, as shown in Figure 3b. ESI-MS and 1H NMR analyses confirmed a complete 1 → 5 transformation (Figures S28, S36, S37). Comparison of the 1H NMR spectra of cages 1 and 5 revealed the same number of signals but with different chemical shift values (Figures S3, S28), which implied that the S6 symmetry of the framework was maintained. The structure of cage 5 was further confirmed by 2D NMR spectroscopy (Figures S31–S35), and it was also minimized by DFT calculation (Figure 2b, see the Supporting Information, Section 7).

Figure 3.

Figure 3

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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.

Next, we applied the same oxidation conditions to a mixture of cages 1–3. All anthracene panels in this self-sorting system also underwent complete transformation into endoperoxides after irradiation. The hetero-Diels–Alder reaction triggered integrative self-sorting, thereby resulting in the exclusive formation of oxidized trigonal prismatic cage 4, the formulation of which was confirmed by 1H NMR and ESI-MS (Figures S18, S26, S27). DFT geometry minimization provided a structure for oxidized trigonal prismatic cage 4 (Figure 2c) that was again consistent with 2D NMR spectra (Figures S21–25), which reflected the C3 point symmetry.

We also attempted to construct oxidized cages 4 and 5 by first treating subcomponent A with 1O2. However, the oxidized subcomponent A not only took a much longer time (10 h) under irradiation for oxidation to approach completion but also underwent thermal decomposition during cage assembly (Figures S38, S39). The endoperoxide moiety thus appears to be more stable when incorporated into a coordination cage.

As the cycloaddition reaction between 1O2 and anthracene is thermally reversible,16,18 we studied the recovery of parent cage 1 from oxidized 5 (Figure S40). This transformation occurred after heating 5 in acetonitrile above its atmospheric boiling point (caution!) at 120 °C under microwave irradiation for 2 h. Trigonal prismatic cage 4 also underwent deoxygenative retro-cycloaddition to transform back into the initial mixture of 1–3 following microwave heating. After five cycles of photooxygenation/cycloreversion, NMR integration indicated that 84% of the oxidized trigonal prism was formed relative to the amount initially present (Figures 3e, S42). We infer that the high temperature (120 °C) reached during the microwave reaction may result in partial product decomposition.

Oxidized trigonal prismatic cage 4 also assembled directly from a mixture of tetrahedral cage 2 and oxidized cubic cage 5 (Figures 3c, S41). We infer that the addition of 1O2 stabilized oxidized cage 4 relative to 3, which rendered the 2 + 5 → 2 × 4 transformation more thermodynamically favorable than the corresponding 1 + 2 → 2 × 3 process.

Variable temperature 1H NMR measurements were used to construct a van’t Hoff plot from which thermodynamic parameters were obtained19 for the 1 + 2 ⇌ 2 × 3 equilibrium (Figure S43). Conversion into 3 was an endothermic and entropically favored process, with ΔH = 48.35 ± 1.61 kJ mol–1 and ΔS = 150.6 ± 4.7 J K–1 mol–1 (Figure S44).

By contrast, the 2 + 5 → 2 × 4 transformation (Figure 3d) was found not to be reversible between 25 and 65 °C, which was consistent with the high thermodynamic stability of 4 relative to 2 and 5 (Figure S45). The relative energetic favorability of structure 4 was also supported by DFT calculations (Figures S113, S114). DFT energy-minimized structures also suggested that the bent anthracene endoperoxide moieties reduced hindrance inside the cage to further stabilize cage 4 (Figure S112).

The host–guest properties of trigonal prismatic cages 3 and 4 were then investigated (Figure 4). Notably, empty cage 4 was obtained directly through post-assembly modification with 1O2, whereas empty cage 3 could not be purified because of its equilibration with cages 1 and 2. In cages 3 and 4, the bulky anthracene units were designed to separate the internal cavity into two isolated compartments, which resembles a “peanut” structure.20 The internal cavity volumes were calculated by MoloVol13 to be 309 and 279 Å3 for 3 and 259 and 226 Å3 for 4, respectively (Figures 4a, S115). Cages 3 and 4 both bound a series of alkanes, including adamantane (G1) and norbornane (G2) in slow exchange on the NMR time scale (Figures S48, S58, S75, S81). Encapsulation was further confirmed by DOSY NMR (Figures S51, S59, S76, S82), where the encapsulated guest and host were observed to diffuse at the same rate. Intriguingly, some terpenoid natural products, such as (1S)-(−)-camphor (G3), verbenone (G4), and (−)-beta pinene (G5), which are similar in size to norbornane, were also observed to encapsulate within both 3 and 4 (Figures 4b, S63, S67, S70, S87, S93, S99) and also in slow exchange on the NMR time scale. These host–guest interactions were additionally confirmed by NOESY NMR, ESI-MS analysis, and isothermal titration calorimetry (ITC) (Figures S52–S104).

Figure 4.

Figure 4

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(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.

Host–guest binding between G1–G5 with cages 3 and 4 is relatively weak. The binding constants between guests G1–G5 and 4 were determined through ITC. The titrations of guests G1–G3 with 4 were fitted using a two-sequential-binding sites model in keeping with the two internal cavities of 4. The binding constants were calculated to be K1 = (2.18 ± 0.19) × 104 M–1 and K2 = (3.68 ± 0.25) × 103 M–1 (2·G1⊂4); K1 = (1.22 ± 0.40) × 104 M–1 and K2 = (7.75 ± 0.73) × 102 M–1 (2·G2⊂4); and K1 = (1.14 ± 0.10) × 103 M–1 and K2 = (7.70 ± 0.79) × 101 M–1 (2·G3⊂4). Because of the weaker binding between guests G4 and G5 with 4, only a single binding event could be observed in ITC. The binding constants of G4⊂4 and G5⊂4 were calculated to be (2.01 ± 0.74) × 101 M–1 and (3.75 ± 0.23) × 102 M–1, respectively. These single-guest bindings of G4⊂4 and G5⊂4 were also supported by ESI-MS analysis, as shown in Figures S95 and S101.

Synthetic receptors have been shown to adjust their binding sites to better bind guests.8b Thus, we also studied guest-encapsulation-induced structural transformation in the equilibrium mixture of cages 1, 2, and 3. The addition of G1 to this mixture prompted re-equilibration, which resulted in the formation of only cage 3 containing G1 (Figure 4c). 1H NMR integrations indicated the formation of the host–guest complex 2·G1⊂3, which was also confirmed by ESI-MS, with no signals observed corresponding to cages 1 and 2. The host–guest complex 2·G1⊂3 was characterized by 2D NMR spectroscopy (Figures S55–S57).

Entropy changes associated with guest encapsulation may help drive the reconfiguration of the system. The freeing of solvent from the cavity of a cage provides an entropic driving force for guest binding. The entropy change associated with guest binding within 3 could, thus, result in the stabilization of heteroleptic 3 as opposed to homoleptic 2 and 1, which bind guest G1 at best weakly (for 2).11a

The host–guest properties of pseudo-cubic cages 1 and 5 were also investigated. In 1, the bulky anthracene moieties were oriented toward the center of the structure, thereby effectively occupying the internal cavity volume, which was calculated to be only 9 Å3 using MoloVol13 (Figure 4a), precluding guest encapsulation. However, cycloaddition between 1O2 and the anthracene panels in cage 5 brought about a substantial expansion of the internal cavity volume to 1449 Å3. Consequently, the guest hexadecahydropyrene (G6) was complexed by 5 with a low binding constant of 43.5 ± 2.01 M–1, whereas no binding of this guest by 1 was observed (Figures S105, S107–S110). The reversible hetero-Diels–Alder reaction could, thus, be used to regulate G6 uptake and release, as shown in Figures 4d and S111.

The use of the reversible cycloaddition of 1O2 to anthracene to reconfigure a self-sorting system may, thus, open new possibilities for signal transduction within systems of cages involving guest uptake and release. The incorporation of enantiopure anthracene ligands may also enable the dynamic control of the chirotopic internal cavities of these coordination cages for potential applications of enantioselective guest recognition and separation.21

Acknowledgments

This study was supported by the European Research Council (695009) and the UK Engineering and Physical Sciences Research Council (EPSRC, EP/T031603/1, EP/P027067/1, EP/T015233/1, and EP/X035875/1). J.Z. acknowledges the Cambridge Trust and Newnham College for Ph.D. funding. I.J. is grateful to the Cambridge Trust and Magdalene College Cambridge for a Cambridge Trust & Magdalene Leslie Wilson Scholarship. We thank the Department of Chemistry NMR facility, University of Cambridge, for performing some NMR experiments and the Diamond Light Source (UK) for synchrotron beamtime on I19 (CY21497). We also thank Dr. Andrew W. Heard and Dr. Jack A. Davies for useful discussions.

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.3c04228.

  • Experimental procedures, NMR characterizations, mass spectrometry data, volume calculations, DFT calculations, and X-ray crystallographic data (PDF)

The authors declare no competing financial interest.

Supplementary Material

ja3c04228_si_001.pdf (12.8MB, pdf)

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