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. 2023 Mar 22;14(15):4143-4151.
doi: 10.1039/d3sc00886j. eCollection 2023 Apr 12.

Control of the assembly of a cyclic hetero[4]pseudorotaxane from a self-complementary [2]rotaxane

Adrian Saura-Sanmartin  1 , Tomas Nicolas-Garcia  1 , Aurelia Pastor  1 , David Quiñonero  2 , Mateo Alajarin  1 , Alberto Martinez-Cuezva  1 , Jose Berna  1
Affiliations

Control of the assembly of a cyclic hetero[4]pseudorotaxane from a self-complementary [2]rotaxane

Adrian Saura-Sanmartin et al. Chem Sci. .

Abstract

The synthesis of a ditopic interlocked building-block and its self-assembly into a cyclic dimer is reported herein. Starting from a thread with two recognition sites, a three-component clipping reaction was carried out to construct a bistable [2]rotaxane. A subsequent Suzuki cross-coupling reaction allowed the connection of a second ring to that of the rotaxane, affording a self-complementary ditopic system. NMR studies were carried out to identify a cyclic hetero[4]pseudorotaxane as the main supramolecular structure in solution. Its assembly is the result of a positive cooperativity operating in the hydrogen-bonding-driven assembly of this mechanically interlocked supramolecule, as revealed by computational studies. The increase of the polarity of the solvent allows the disruption of the intercomponent interactions and the disassembly of the hetero[4]pseudorotaxane into the two interlocked units. The disassembly of the cyclic dimer was also achieved through a Diels-Alder reaction over the fumaramide binding site of the thread, triggering the translational motion of the entwined macrocycle to an adjacent glycylglycine-based station and precluding the supramolecular dimerization. The competitive molecular recognition of a guest molecule by one of the self-templating counterparts of the dimer also led to the controlled disassembly of the hetero[4]pseudorotaxane.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Fig. 1
Fig. 1. Evolution of an interlocked ditopic monomer towards their potential supramolecular self-assembled structures: molecular lasso, [cn]daisy chains, lineal dimers or trimers and oligomers.
Scheme 1
Scheme 1. Synthesis of: (a) [2]rotaxane 2; and (b) macrocycle 4. Reaction conditions: (i) N1,N3-bis[4-(aminomethyl)benzyl]isophthalamide, 5-bromoisophthaloyl dichloride, Et3N, CHCl3, 25 °C, 4 h; (ii) bis(pinacolato)diboron, Pd(dppf)Cl2 (5 mol%), AcOK, dioxane, 90 °C, 24 h.
Scheme 2
Scheme 2. Synthesis of rotaxane 5. Reaction conditions: (i) Pd(dppf)Cl2 (20 mol%), K3PO4, dioxane, 100 °C, 24 h.
Fig. 2
Fig. 2. 1H NMR spectra (400 MHz, CDCl3, 298 K) of: (a) thread 1; (b) [2]rotaxane 2; (c) hetero[4]pseudorotaxane 5·5. See lettering in Scheme 1. Signals related to the fumaramide station are highlighted in red. Signals related to the GlyGly station are highlighted in green. Signals related to the diamide macrocycle are highlighted in purple. Signals related to the tetraamide macrocycle are highlighted in light blue. See lettering in Scheme 1.
Fig. 3
Fig. 3. Solvent-dependent assembly–disassembly of the ditopic rotaxane 5: (a) schematic representations of the assembly and disassembly of 5; (b) 1H NMR spectra of 5 in DMSO-d6 (400 MHz, 298 K). See lettering in Scheme 1. Signals related to the fumaramide station are coloured in red. Signals related to the GlyGly station are coloured in green. Signals related to the diamide macrocycle are coloured in purple. Signals related to the tetraamide macrocycle are coloured in light blue. Signals of residual water and the DMSO-d6 coloured in light grey. See lettering in Scheme 1.
Fig. 4
Fig. 4. Mass spectra (MALDI-TOF) of ditopic rotaxane 5. Inset: (a) calculated; (b) superposition of calculated and experimental; (c) experimental of rotaxane 5 in its dimeric form [2M + Na]+.
Fig. 5
Fig. 5. Computational models at DFT level in CHCl3 (BP86-D3/def2-SVP) of: (a) [2]rotaxane 5; (b) cyclic hetero[4]pseudorotaxane (dimer 5·5); (c) diagram for visually comparing the binding energies of the monomer 5, the cooperatively self-assembled dimer 5·5 and that of the double of binding energy of the monomer 5. Both calculated structures are the lowest energy ones; ΔEbind: variation of the binding energy calculated as the difference between the energy of the complex minus the energy of all separated molecules that formed it (of the conformer with the lowest energy). For clarity the hydrogen atoms have been removed. Note that in the cyclic dimer 5·5, one of the molecules is colored in grey and the second one in dark blue. For clarity the diamide macrocycle is colored in purple in monomer 5.
Fig. 6
Fig. 6. Controlled disassembly and assembly of the dimer 5·5 by a reversible chemical modification. Partial spectra (600 MHz, CDCl3, 298 K) of: (a) thread Cp-1; (b) bromo-derived rotaxane Cp-2; (c) rotaxane Cp-5. Reaction conditions: (i) cyclopentadiene, DMSO, 80 °C, 16 h, 48%; (ii) 235 °C, 0.5 mm Hg, 30 min, ∼41%. Signals related to the Diels–Alder adduct are coloured in orange (for clarity, only one diastereoisomer is drawn). Signals related to the GlyGly station are coloured in green. Signals related to the diamide macrocycle are coloured in purple. Signals related to the tetraamide macrocycle are coloured in light blue.
Fig. 7
Fig. 7. Disassembly of the dimer 5·5 by competitive recognition events: (a) schematic representations of the disassembly of 5·5 in the presence of the N-oxide derivative 6; (b) partial 1H NMR spectra (400 MHz, CDCl3, 298 K) of 5 during the addition of an increasing amount of the N-oxide 6. See lettering in Scheme 1. Signals related to the fumaramide station are coloured in red. Signals related to the GlyGly station are coloured in green. Signals related to the N-oxide 6 are coloured in orange.
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