Phenyl-Linked Anthracene-Based Macrocycles with Geometrically Tunable Optical Properties

Abstract

Anthracene has been widely explored because of its intrinsic photophysical and photochemical properties. Here, two novel anthracene-based macrocycles (1 and 2) were designed and synthesized with para- and meta-phenylene spacers. X-ray crystallographic analysis demonstrates that compound 1 with para-phenylene spacers adopts a nearly planar structure, while compound 2 with meta-phenylene spacers displays a V-shaped geometry. The photophysical properties of the resultant macrocycles, which are structural isomers, are well studied using photoluminescence spectra and time-resolved absorption spectra, which are further corroborated by density functional theory calculations. The optical properties of these two novel macrocycles can be finely tuned via their geometries.

Key words

anthracene - macrocycles - geometrically - optical properties - fluorescence

• References And Notes

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• 45 Synthetic procedure for compound 2: A suspension of compound 6 (75 mg, 0.123 mmol), compound 4 (67.8 mg, 1.2 equiv, 0.147 mmol), tetrakis(triphenylphosphine)palladium (28 mg, 0.2 equiv, 0.025 mmol), and potassium carbonate (68 mg, 4.0 equiv, 0.492 mmol) in potassium carbonate (12 mL) and H₂O (2 mL) was degassed by three freeze–pump–thaw cycles. The reaction mixture was heated at 80 °C overnight under nitrogen. After cooling to room temperature, the mixture was extracted with dichloromethane and washed with water. The organic layer was dried over anhydrous magnesium sulfate. The solvent was removed under vacuum and the residue was purified by silica gel column chromatography using hexane/dichloromethane (30/1, v/v) as eluent to give the macrocycle compound 30,32-dimesityl-4,6:10,14:18,20:24,28-tetra(metheno)tetrabenzo[a,d,k,n][20]annulene (2, 57 mg, 63%) as a white solid. ¹ H NMR (400 MHz, methylene chloride-d2): δ 8.26 (s, 2 H), 7.61–7.57 (m, 2 H), 7.55–7.44 (m, 10 H), 7.43–7.32 (m, 8 H), 7.18 (s, 2 H), 7.14 (s, 2 H), 2.49 (s, 6 H), 1.82 (s, 6 H), 1.71 (s, 6 H). ¹³ C NMR (101 MHz, methylene chloride-d2): δ 141.1, 140.9, 137.4, 137.3, 135.8, 134.8, 131.1, 130.9, 129.5, 128.6, 128.4, 128.3, 128.2, 125.9, 125.4, 125.1, 124.2, 20.9, 19.7, 19.6. HRMS (ESI): m/z [M] ⁺ Calcd for C₅₈H₄₅ 740.3443; Found 740.3498. mp: >350 °C. IR: 2964.8, 2925.4, 2851.6, 1445, 1086, 889.4, 825.4, 751.6, 702.5, 623.7 cm ⁻¹
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