Observation of Rare Tri⁶Di⁹ Imine Cages Using Highly Fluorinated Building Blocks

Abstract

The first synthesis of organic Tri ⁶ Di ⁹ cages is presented. Two structurally distinct Tri ⁶ Di ⁹ cages were synthesised by combining a highly fluorinated aldehyde with two ditopic amines. Although the pure compounds could not be isolated despite many attempts, the information obtained is critical for the future design of large supramolecular structures. Computational and experimental methods indicate that the addition of perfluorinated aromatic linkers in the assembly of porous organic cages opens up new possibilities for influencing the reaction pathway towards rare and unknown structures.

Key words

organic cage compounds - imine cages - dynamic covalent chemistry - fluorine

Publication History

Received: 17 October 2022

Accepted after revision: 09 November 2022

Accepted Manuscript online:
11 November 2022

Article published online:
13 December 2022

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• 14 General procedure: Synthesis of the cage mixture Tri ⁴ Di ⁶ and Tri ⁶ Di ⁹: Aldehyde 1 (303.20 mg, 0.50 mmol, 1.00 equiv) was dissolved in dry CHCl₃ (60 mL) and (R,R)-1,2-diaminocyclohexane 2 (79.90 mg, 0.75 mmol, 1.50 equiv) dissolved in 60 mL CHCl₃ was added dropwise to the reaction mixture. The resulting solution was stirred at room temperature for 3 days, during which a bright yellow colour developed. Half of the solvent was evaporated under reduced pressure at room temperature, and n-hexane was added to the solution, resulting in the precipitation of a bright yellow solid. The solid was isolated by filtration and washed with n-hexane to yield Tri ⁴ Di ⁶ in a mixture with the larger Tri ⁶ Di ⁹ cage (216.90 mg, 60‍%) as a yellow solid. ¹H NMR (600 MHz, CDCl₃) [δ in ppm] 8.43 (s, 12 H, CHN), 7.65 (s, 12 H, Ar-H), 3.53 (s, 12 H, CH-N), 1.91 (s, 48 H, CH₂ -cyhex). ¹⁹F NMR (282 MHz, CDCl₃) [δ in ppm] −142.69 – −143.39 (m, 24F, F_inner ), −143.75 (tt, J = 25.4, 13.1 Hz, 24F, F_outer ). Due to the very poor solubility, no ¹³C NMR spectrum could be recorded. DOSY: Diffusion coefficient D = 2.65 × 10⁻¹⁰ m² s⁻¹. MALDI MS: [Tri ⁴ Di ⁶+H]⁺ calculated: 2893.625 m/z, found: 2893.660 m/z; [Tri ⁶ Di ⁹+H]⁺ calculated: 4339.940 m/z, found: 4339.788 m/z. FT-IR (ATR): ν̃(cm⁻¹) = 2933.73, 2860.43, 2358.94, 2158.35, 1643.35, 1602.85, 1494.83, 1471.69, 1423.47, 1388.75, 1346.31, 1301.95, 1199.72, 1176.58, 1091.71, 1033.85, 991.41, 968.27, 927.76, 891.11, 858.32, 800.46, 777.31, 721.38, 700.16, 677.01, 632.65, 609.51.