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

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Phenyl-Linked Anthracene-Based Macrocycles with Geometrically Tunable Optical Properties Published online: 2020-12-22 336 Organic Materials M.-G. Rong et al. Short Communication Phenyl-Linked Anthracene-Based Macrocycles with Geometrically Tunable Optical Properties Ming-Guang Ronga Junting Wanga Kam-Hung Lowa Junzhi Liu*a a Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. China [email protected] 23–38 Received: 30.10.2020 fascinating cyclic structures. In 2007, Toyota and cow- Accepted after revision: 11.11.2020 orkers reported the synthesis of the cyclic 1,8-anthrylene- DOI: 10.1055/s-0040-1721729; Art ID: om-20-0037sc ethynylene dimer with two acetylene linkers (Figure 1) License terms: through the Sonogashira coupling.39–41 In 2016, the same © 2020. The Author(s). This is an open access article published by Thieme under the group demonstrated the synthesis of a novel π-conjugated terms of the Creative Commons Attribution-NonDerivative-NonCommercial License, macrocyclic compound consisting of six 2,7-anthrylene units permitting copying and reproduction so long as the original work is given appropriate 26,27 credit. Contents may not be used for commercial purposes, or adapted, remixed, by Ni-mediated Yamamoto coupling (Figure 1). A macro- transformed or built upon. (https://creativecommons.org/licenses/by-nc-nd/4.0/) cyclic diphenylanthracene dimer was successfully synthe- sized by Iyoda et al. using the electron-transfer oxidation of Abstract Anthracene has been widely explored because of its intrinsic Lipshutz cuprate in 2018 (Figure 1).42 Although these photophysical and photochemical properties. Here, two novel anthra- cene-based macrocycles (1 and 2) were designed and synthesized with achievements made progress, the synthesis of smaller macro- para- and meta-phenylene spacers. X-ray crystallographic analysis cycleswithanthraceneunitsstillremainsachallenge,suchasa demonstrates that compound 1 with para-phenylene spacers adopts a phenyl-linked 1,8-anthracene dimer, due to the high strain at meta nearly planar structure, while compound 2 with -phenylene spacers the 1,8-position and the rigid π-frame of anthracene. displays a V-shaped geometry. The photophysical properties of the Herein, we demonstrated the synthesis of two novel resultant macrocycles, which are structural isomers, are well studied using photoluminescence spectra and time-resolved absorption anthracene-based macrocycles with para-andmeta-phenyl- spectra, which are further corroborated by density functional theory ene linkers: the structural isomers 1 and 2 (Scheme 1). The calculations. The optical properties of these two novel macrocycles can chemical structures of 1 and 2 are unambiguously confirmed fi be nely tuned via their geometries. by X-ray crystallographic analysis. The anthracene units in 1 Key words anthracene, macrocycles, geometrically, optical proper- macrocycle adopt a nearly planar structure, while the ties, fluorescence Introduction Toyota, 2007 and 2019 Well-defined π-conjugated macrocycles have attracted considerable attention from researchers because they not onlyaretheoreticallyand experimentally interesting, but they also demonstrate potential applications in carbon-based nanoelectronics.1–8 In particular, the cyclo-p-phenylenes have been well developed during the past decade, due to their unique structures, optoelectronic properties, and supramolecular host–guest behavior.9–15 Anthracene is a Toyota, 2016 and 2018 versatile synthon that is widely used to synthesize attractive 5 10 4 and functional molecules in organic electronics, due to its 6 3 molecular panel-like shape and excellent photophysical 7 2 – properties.16 22 Moreover, the feasibility of chemical modifi- Iyoda, 2018 891 cationoftherigidanthracenebackbonemakesanthraceneand Figure 1 Examples of anthracene-based macrocycles. its derivatives very useful building blocks for the synthesis of © 2020. The Author(s). Organic Materials 2020, 2, 336–341 Georg Thieme Verlag KG, Rüdigerstraße 14, 70469 Stuttgart, Germany ! ~ 337 Organic Materials M.-G. Rong et al. Short Communication I Bpin Bpin Br [Pd(PPh ) ] [Pd(PPh3)4] 3 4 K CO K2CO3 2 3 THF/H O Dioxane/H2O 2 Br Br o 60 oC 5 80 C 1 45% 65% B2Pin2 PdCl2(dppf)2 Cl Cl AcOK/DMF Bpin Bpin 34140 oC I 42% Br Bpin Bpin [Pd(PPh ) ] 3 4 [Pd(PPh3)4] K CO 2 3 K2CO3 Dioxane/H O 2 THF/H2O o Br Br 60 C 6 80 oC 2 73% 63% Scheme 1 Synthetic routes toward anthracene-based macrocycles 1 and 2. anthracene units in 2 possess a slightly curved geometry due the yield of 45% and 73%, respectively. Finally, the anthracene- to its highly twisted geometry (Figure 2). Interestingly, the based macrocycles 1 and 2 were successfully obtained structural isomers 1 and 2 demonstrate totally different through the Suzuki coupling of 5 and 6 with compound 4 in optical and electronic properties. The maximum absorption excellent yields of 65% and 63%, respectively. The chemical and fluorescence peaks of 2 are blue-shifted compared to structures of 1 and 2 were fully characterized by 1Hand13C those of compound 1 due to the highly strained structure, NMR measurements (Figures S3-S14) and the high-resolution which leads to the decreased conjugation in 2. Accordingly, mass spectroscopy (Figures S15-S21).44,45 the photoluminescence quantum yield (QY; ΦPL)of2 (22%) is The crystals of macrocycles 1 and 2 were grown by slow lower than that of 1 (41%) both in solution and solid evaporation of their solution in methanol/toluene and film film films (in 40 wt% PMMA, 1: ΦPL ¼ 22%; 2: ΦPL ¼ 8%). hexane/dichloromethane, respectively, allowing characteri- However, the fluorescence lifetimes of 1 (τ ¼ 6.15 ns) and 2 zation of their structural features by X-ray single crystal (τ ¼ 6.19 ns) are comparable with each other. Thereby, our analysis. The anthracene groups in macrocycle 1 possess a work reported herein is particularly attractive because it not nearly planar geometry, in which the phenyl rings twist out only allows the synthesis of highly strained macrocycles with of the anthracene plane with a dihedral angle of 58.62° 1,8-anthracene units, but also provides the possibility to fine- (Figure 2a, b). In the solid state of macrocycle 2, the tune their optoelectronic properties by controlling the anthracene units and phenyl rings twist each other with the geometry. dihedral angles of 72.55° to 79.89° (Figure 2c, d). Interest- ingly, due to the high strain in macrocycle 2, the anthracene units also slightly twist out of the plane with a dihedral Results and Discussion angle of 4.48° (Figure 2d), which is similar to those of the 1,8-disubstituted anthracene compounds in the literature.46 The synthetic routes toward anthracene-based macro- Due to the presence of the sterically hindered mesityl cycles 1 and 2 are depicted in Scheme 1. The key building block groups and the twisted para-(1) and meta-(2) phenylene 1,8-diborate-10-mesitylanthracene (4) was synthesized spacers, no intermolecular π–π stacking interaction can be from 1,8-dichloro-10-mesitylanthracene (3)43 through the formed between the adjacent anthracene moieties palladium-catalyzed Miyaura borylation reaction with bis (Figures S1 and S2). (pinacolato)diboron in 42% yield. Subsequently, the selective The electrochemical behaviors of macrocycles 1 and 2 in Suzuki coupling of compound 4 with 1-bromo-4-iodobenzene anhydrous dichloromethane (CH2Cl2) were investigated by or 1-bromo-3-iodobenzene afforded compounds 5 and 6 in means of cyclic voltammetry; the results are depicted © 2020. The Author(s). Organic Materials 2020, 2, 336–341 ! ~ 338 Organic Materials M.-G. Rong et al. Short Communication Figure 2 X-ray crystal structures of macrocycles 1 and 2. All the hydrogen atoms and solvent molecules are omitted. (a, b) Top and side views of 1. (c, d) Top and side views of 2. Figure 4 Calculated molecular orbitals and energy diagrams of 9- Figure 3 UV-vis absorption (a) and fluorescence (b) spectra of 9- mesitylanthracene (a), 1 (b), and 2 (c). À mesitylanthracene, 1 and 2 in toluene (concentration: 5 Â 10 5 M). (c) Fluorescence spectra of 9-mesitylanthracene, 1 and 2 in 40 wt% PMMA thin film. (d) Cyclic voltammetry of 1 and 2 measured in CH Cl (0.1 M 2 2 À 1 2 n-Bu4NPF6) at the scan rate of 50 mV/s. 5.53 eV for and , respectively. In addition, the experi- mental results are well supported by the density functional theory calculations (Figure 4). In comparison with 9- mesitylanthracene (Figure 4a), the energy gaps in Figure 3d. Macrocycle 1 showed two reversible oxidation of macrocycles 1 and 2 are smaller than that of monomer processes at the onset potential of 1.20 and 1.23 V vs. Fcþ/Fc 9-mesitylanthracene due to the π-expanded conjugation. The (Figure 3d), respectively. For macrocycle 2,whichexhibiteda HOMO and LUMO in macrocycle 1 with para-phenylene similar pattern to compound 1, two reversible oxidation spacers are mainly localized on the anthracene units and processes were observed with the onset potential of 1.12 partially on the para-phenylene linkers (Figure 4b). In and 1.21 V vs. Fcþ/Fc (Figure 3d), respectively. Accordingly, contrast, the HOMO and LUMO of macrocycle 2 with meta- the HOMO energy levels are estimated to be À5.45 and phenylene spacers are fully localized over the anthracene © 2020. The Author(s). Organic Materials 2020, 2, 336–341 ! ~ 339 Organic Materials M.-G. Rong et al. Short Communication groups, owing to the interruption of conjugation by the both in solution and solid state. The fluorescence lifetimes of meta-phenylene spacers, as well as the deplanarization 9-mesitylanthracene, 1,and2 are similar, reaching τ ¼ 7.02, (Figure 4c). Accordingly, the energy gap of macrocycle 2 6.15, and 6.19 ns, respectively. Cal (ΔEg ¼ 3.44 eV) is larger than that of its structural isomer 1 The excited-state nature of macrocycles 1 and 2 was Cal (ΔEg ¼ 3.32 eV), with a lower HOMO and a higher LUMO examined by nanosecond time-resolved absorption (ns-TA) (Figure 4).
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