Thermodynamic-Dominated Stereoselective Gridization of Molecular Nanolinkage Based on Fluorenes

Abstract

The path-selectivity and stereoselectivity of gridization pathways into fluorene-based drawing hand grids (DHGs-F) are precisely modulated through tuning acid conditions and side-chain effects. BF₃·OEt₂ supports the realization of the gridization path (rac-DHG1-F, yield: 82%, meso-DHG1-F, yield: 11%). On the contrary, CF₃SO₃H will lead to the enhancements in polymerization pathways (about 85% yield). When the side chain is a methoxyl group, rac-DHG1-F and meso-DHG1-F will be obtained. However, when the side chain is a group without an oxygen atom, only rac-DHGs-F can be obtained (de = 100%). Moreover, through excitonic physical properties, rac-DHGs-F exhibits a more π-electronic delocalization, potentially serving as the intriguing tactic strategy to modulate the optoelectronic properties.

Key words

stereoselectivity - Friedel–Crafts - gridization - nanogrids - nanolinkages

Publication History

Received: 18 January 2022

Accepted after revision: 01 April 2022

Accepted Manuscript online:
01 April 2022

Article published online:
12 May 2022

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• 28 Synthesis of DHG1-F The compound DHG1-F was prepared by using MC1 (0.200 g, 0.415 mmol), BF₃·Et₂O (10 equiv) dissolved in 83.2 mL DCM. The reaction mixture was stirred at r.t. for 15 min, quenched with KOH aqueous solution. The mixture was extracted over three times with DCM, the organic layer was dried over MgSO₄, filtered, and the solvent was removed under reduced pressure. Purification by silica gel column chromatography (petroleum ether–DCM = 1:1) to afford rac-DHG1-F (0.134 g, 70%) and meso-DHG1-F (0.037 g, 19%) as white powders. MALDI-TOF-MS: m/z calcd for C₆₈H₅₀N₂O₂: 926.39 [M⁺]; found: 926.68. rac-DHG1-F: ¹H NMR (400 MHz, CDCl₃): δ = 8.66 (s, 2 H), 8.39 (s, 2 H), 8.11 (s, 2H), 7.74–7.72 (d, J = 8.0 Hz, 2 H), 7.50–7.48 (d, J = 7.6 Hz, 2 H), 7.44–7.40 (m, 4 H), 7.35–7.29 (m, 6 H), 7.17–7.14 (d, J = 8.4 Hz, 6 H), 6.98–6.95 (d, J = 8.8 Hz, 3 H), 6.74–6.72 (d, J = 8.8 Hz, 3 H), 6.56–6.54 (d, J = 8.0 Hz, 2 H), 3.70 (s, 6 H), 3.48 (4 H), 1.26 (6 H). ¹³C NMR (100 MHz, CDCl₃): δ = 158.3, 152.2, 151.7, 140.3, 139.9, 139.5, 139.3, 139.2, 138.2, 135.6, 129.7, 128.9, 127.1, 126.8, 124.2, 124.1, 124.0, 123.8, 123.6, 122.6, 122.1, 120.6, 119.9, 116.4, 113.8, 108.1, 106.9, 65.1, 55.0, 36.6, 13.3. MALDI-TOF-MS: m/z calcd. For C₆₈H₅₀N₂O₂: 926.39 [M⁺]; found: 926.68. meso-DHG1-F: ¹H NMR (400 MHz, CDCl₃): δ = 8.75 (s, 2 H), 8.32 (s, 2 H), 7.97 (s, 2 H), 7.86–7.80 (m, 4 H), 7.67–7.63 (t, J = 6.4 Hz, 4 H), 7.59–7.56 (d, J = 8.5 Hz, 2 H), 7.53–7.51 (d, J = 7.2 Hz, 2 H), 7.46–7.40 (dd, J = 14.6, 8.7 Hz, 4 H), 7.36–7.33 (t, J = 8.3 Hz, 2 H), 7.30–7.28 (d, J = 7.0 Hz, 2 H), 6.75–6.73 (d, J = 8.9 Hz, 4 H), 6.57–6.55 (d, J = 10.2 Hz, 4 H), 4.41–4.35 (q, J = 8.4 Hz, 4 H), 3.63 (s, 6 H), 1.44–1.42 (t, J = 6.4 Hz, 6 H). ¹³C NMR (100 MHz, CDCl₃): δ = 151.7, 139.9, 139.3, 133.9, 129.1, 127.4, 126.7, 126.2, 123.3, 121.6, 119.8, 113.3, 108.2, 107.4, 64.1, 55.1, 37.7, 13.8. MALDI-TOF-MS: m/z calcd for C₆₈H₅₀N₂O₂: 926.39 [M+]; found: 926.56.