Tunable Heck–Mizoroki Reaction of Dibromonaphthalene Diimide

Oct 25, 2017 - Rational design of coplanar NDI-based conjugated molecules was achieved by covalently connecting naphthalene diimide (NDI) units with a...
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Tunable Heck−Mizoroki Reaction of Dibromonaphthalene Diimide with Aryl Ethylenes: Design, Synthesis, and Characterization of Coplanar NDI-Based Conjugated Molecules Chunling Gu,*,†,‡ Yangxiong Li,†,‡ Lu Xiao,†,‡ Hongbing Fu,†,§ Dong Wang,† Liang Cheng,†,‡ and Li Liu*,†,‡ †

Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China ‡ University of Chinese Academy of Sciences, Beijing 100049, China § Beijing Key Laboratory for Optical Materials and Photonic Devices, Department of Chemistry, Capital Normal University, Beijing 100048, China S Supporting Information *

ABSTRACT: Rational design of coplanar NDI-based conjugated molecules was achieved by covalently connecting naphthalene diimide (NDI) units with aryl (Ar) groups through vinylene (V) linkers via Heck−Mizoroki reaction. Two series of products, diolefination products (ArVNDIVAr) and hydroxylated and mono-olefination products (HONDIVAr), can be obtained, respectively, in moderate to excellent yields (45−90%) under controlled conditions, in which catalyst and base play the key roles. Density functional theory calculation discloses the outstanding planarity of the two types of products. Large bathochromic shifts are observed in both the absorbance and photoluminescence spectra of the HONDIVAr (144 and 229 nm) and ArVNDIVAr (180 and 242 nm) π-systems. Bathochromic shifts can be adjusted within the broad wavelength range by introducing 4′substituents, either electron-withdrawing group (NO2) or electron-donating group (NMe2), in the phenyl group of aryl ethylenes. ArVNDIVArs show bigger bathochromic shifts than HONDIVArs.

D

materials with improved optoelectronic properties.3,11 Recently, Liu et al. reported that when the thiophene units in polymer NDI-T-benzothiadiazole (B)-T (PNBT) was replaced by selenophene (S), the obtained polymer PNBS exhibited an ultrahigh electron mobility up to 8.5 cm2 V−1 s−1 and excellent air-stability.12 High-performance all-polymer solar cells with 7.7% power conversion efficiency (PCE) was achieved by NDIselenophene copolymer blended with benzodithiophene (BDT)-thieno[3,4-b]thiophene (TT) copolymer (PBDTTFTTE).7a However, compared to other D−A conjugated molecules, such as diketopyrrolopyrrole (DPP), poor planarity between NDIs and aryls (e.g., thiophene, the dihedral angle is about 45°) weakens both the intramolecular charge transfer (ICT) and the interchain π−π stacking in the solid state, thus carrier transport along conjugated chains as well as the interchain charge transport are limited.13 Therefore, NDIbased conjugated molecules with better coplanarity might be desirable.14 Great efforts have been made to achieve such kinds of planarized NDI compounds. Marder et al. reported that the

onor (D)/acceptor (A) moieties play an important role in advanced functional materials.1 In this context, electron-poor aromatic units have been developed to meet the increasing demand in the development of high-performance organic electronic and optoelectronic materials.2 Among them, naphthalene diimide (NDI) is one of the most widely studied electron-accepting species. 3 The appeal of this simple chromophore stems from its planarity, high electron affinity, and excellent thermal and photochemical stability, as well as the multiple synthetic handles for extending conjugation or tuning functionality.4 As a result, NDI-based π-conjugated molecules are being applied extensively as dyes, pigments, sensors, aggregates, and organic semiconductors.5 The NDI-based conjugated chains endow the molecules with good electron mobility,4a which has been applied in transistors,6 non-fullerene polymer solar cells,7 diode transport,8 batteries,9 and recently in perovskite solar cells.10 Ever since the brilliant work reported by Facchetti that showed the NDI-T (thiophene) copolymer P(NDI-T2) was ambient stable electron transport material, intense efforts have been made by a number of groups to extend the π-conjugated system of the NDI molecule, generating considerable new © 2017 American Chemical Society

Received: August 24, 2017 Published: October 25, 2017 12806

DOI: 10.1021/acs.joc.7b02140 J. Org. Chem. 2017, 82, 12806−12812

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The Journal of Organic Chemistry planarized NDI-based polymers, which were synthesized via Sonogashira coupling of terminal alkynes with NDI-Br2, show electron transport ability.15 Recently, Briseno and Russell et al. reported that BiNDI, which was composed of two NDI moieties linked via a vinylene donor unit, was the best NDIbased small molecule acceptor with ambient stable electron mobility.16 Heeney et al. reported the synthesis of NDIethylene copolymers and Sommer et al. reported the synthesis of NDI-Fu2 polymer to approach new planarized structure involving NDI.17 However, those planarized NDIs were achieved via Stille reaction mostly, which suffered from several drawbacks: (1) tedious synthesis of metal-activated reagents; (2) moisture- and air-sensitive of the organotin reagents used; (3) formation of toxic byproducts. Such drawbacks hinder the large-scale synthesis as well as the practical application of NDIbased optoelectronic materials.18 Therefore, the search for an economically attractive synthesis alternative to Stille crosscoupling is of crucial importance to obtain conjugated NDIs. The Heck−Mizoroki (H−M) reaction, which is one of the most widely used C−C bond-forming methods of contemporary synthesis,19 is useful to covalently connect two aryl groups through V linkers to give a coplanar extended π-system with readily available reagents. Its advantages, such as nonsensitivity to water, no need for thoroughly deoxygenated solvent, and a wide range of functional groups tolerance, make reactions easy to handle. This synthetic method, in contrast to Stille coupling, does not involve organometallic reagents such as stannyl derivatives. As a consequence, the H−M reaction represents an economically attractive and ecologically benign alternative to Stille coupling strategies described above. We have reported the synthesis of NDI-based polymer to achieve ambient stable ambipolar transport materials as well as acceptor materials for all-polymer organic solar cells by introducing benzothiadiazole and vinyl moieties into the backbone of P(NDI-T2).20 Herein, we extend our study of NDI-based D−A materials by developing a novel strategy to construct coplanar D−π−A−π−D molecules via the H−M reaction of 2,6-dibromonaphthalene diimide (NDIBr2) with aryl ethylenes. Under the optimized conditions, the hydroxylated and mono-olefination product (HONDIVAr) or diolefination product (ArVNDIVAr), could be obtained in moderate to high yields. The conjugated backbones of both types of products are proven to be highly coplanar by density functional theory (DFT) calculation. The optoelectronic property of both kinds of products is characterized. It is determined that ArVNDIVAr with 4′-substituents in the phenyl group of aryl vinylene possesses a bigger conjugated system. Initially, the reaction of NDIBr2 1 with styrene 2a was investigated using Pd(PPh3)4 as the catalyst (10 mol %) and K2CO3 (3 equiv) as the base in toluene at 110 °C. A mixture of diolefination product 4a (ArVNDIVAr) and hydroxylated and mono-olefination product 3a (HONDIVAr, which was observed in the analogous reaction of NDIBr2 with furan, instead of aryl ethylenes21) was detected (3a/4a = 5.5:1) in 71% yield (Table 1, entry 1). Then the solvent was screened (entries 2−4). It turned out that, when the reaction was carried out in dimethylacetamide (DMAc) and DMF, 4a was almost undetectable, whereas the yield of 3a was increased to 84% (entries 3 and 4). An attempt to improve the yield of 3a was performed by heating and cooling the reaction system; however, neither of the efforts was found to be valid (entries 5 and 6, Table 1). When tris(dibenzylideneacetone)dipalladium [Pd 2 (dba) 3 ] and di-μ-bromobis(tri-tert-butylphosphino)-

Table 1. Optimization of Heck−Mizoroki Reaction of Dibromonaphthalene Diimide 1 with Aryl Ethylenes 2a

yield (%)b a

entry

[Pd]

B

S

T (°C)

3a

4a

1 2 3 4 5 6 7 8 9 10 11 12 13 14c

Pd(PPh3)4 Pd(PPh3)4 Pd(PPh3)4 Pd(PPh3)4 Pd(PPh3)4 Pd(PPh3)4 Pd2(dba)3 PdBr2(PtBu3)2 Pd(PPh3)4 Pd(PPh3)4 Pd(PtBu3)2 PdBr2(PtBu3)2 Pd(PtBu3)2 Pd(PtBu3)2

K2CO3 K2CO3 K2CO3 K2CO3 K2CO3 K2CO3 K2CO3 K2CO3 DIPEA Cy2NMe Cy2NMe Cy2NMe Cy2NMe Cy2NMe

toluene DMSO DMAc DMF DMF DMF DMF DMF DMF DMF DMAc DMAc DMAc DMAc

110 110 110 110 90 130 110 110 110 110 110 110 90 90

60 33 44 84 56 57 58 45 9 0 0 0 0 0

11 11 0 0 0 0 37 30 20 20 68 70 82 85

a

Reaction conditions: 1 (0.1 mmol), 2a (0.2 mmol), [Pd] (10 mol %), base (B) (3.0 equiv), solvent (S) (2 mL), temperature (T), N2, 24 h. b Determined by 1NMR using 1,3,5-trimethoxybenzene as the internal standard. c1/2a = 1:4, S (4 mL).

dipalladium(I) [PdBr2(PtBu3)2] were used as catalyst for the reaction of 1 with 2a, the products were still a mixture of 3a and 4a, and the yield of 3a was a little higher than that of 4a. For enhancing the yield of 4a, we tried to decrease the alkalinity of the reaction system to avoid the generation of hydroxylation of the bromo substituent. To our delight, when organic base N,N-diisopropylethylamine (DIPEA) was used instead of K2CO3, the major product was switched from 3a to 4a, with the ratio of 4a/3a = 20:9 (entry 9). N,N-Dicyclohexylmethylamine (Cy2NMe) further suppressed the formation of 3a, and 4a was obtained exclusively but in low yield (20%) (entry 10). Remarkable increase in the yield of 4a (up to 70%) was observed when the catalyst, Pd(PPh3)4, was replaced by bis(tritert-butylphosphino)dipalladium [Pd(P t Bu 3 ) 2 ] and PdBr2(PtBu3)2 (entries 11 and 12), and the reaction medium was changed to DMAc. Finally, the yield of 4a was successfully increased to 82% at a lower reaction temperature of 90 °C (entry 13). When the ratio of 1 and 2a was improved to 1:4, the yield of 4a was slightly increased to 85% (entry 14). Thus, the syntheses of 3a and 4a can be controlled under the different optimized reaction conditions, catalyst, base, and reaction solvent and temperature (entries 4 and 13). Under the different optimized reaction conditions for the synthesis of 3a or 4a, we investigated the substrate scope of 4′substituted aryl ethylenes 2a−2i. The isolated yields of HONDIVArs and ArVNDIVArs products are listed in detail in Scheme 1. For the syntheses of HONDIVAr compounds bearing either the electron-withdrawing or electron-donating groups in the 4′-position of the phenyl ring of aryl group (3a− 3i), good to excellent yields (61−90%) were reached. Alternatively, ArVNDIVArs products (4a−4i) were obtained in moderate to good yields (45−83%) under different optimized conditions. Structures of both HONDIVArs and 12807

DOI: 10.1021/acs.joc.7b02140 J. Org. Chem. 2017, 82, 12806−12812

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The Journal of Organic Chemistry Scheme 1. Heck−Mizoroki Reaction of Dibromo Naphthalene Diimide 1 with Aryl Ethylenes 2a−j

Figure 1. DFT-calculated (B3LYP/6-31G(d)) molecular geometries and molecular orbitals. (a) Molecular geometry of 3h, (b) molecular geometry of 4h, (c) highest occupied molecular orbital (HOMO) of 4h, and (d) lowest unoccupied molecular orbital (LUMO) of 4h.

(Figure 2a and see Supporting Information Table S1). For products comprising donor and acceptor units, the absorption

ArVNDIVArs were established by HRMS and 1H NMR and 13 C NMR spectroscopy in CDCl3. The two protons of the V linker show up as two doublets at 8.5−8.7 and 7.3−7.8 ppm with a coupling constant of 16.3 Hz, by which the configuration of formed double bond is deduced as trans (see Supporting Information 1H NMR spectra of 4b and 3a). The hydroxyl groups of HONDIVArs (3a−3i) show up as a sharp singlet over 12.7 ppm in the 1H NMR as a result of intramolecular Hbonding to the neighboring imide oxygen (see Supporting Information 1H NMR spectrum of 3a). To gain insight into the structure−photophysical property relationship, geometry optimization was performed through DFT. The calculation discloses the outstanding planarity of ArVNDIVArs, which is in accordance with our prospect. The dihedral angles between the NDI core and the neighboring vinyl unit in 3h and 4h are calculated to be 12°, which are much smaller than that typically in NDI-T2 (around 45°) (Figure 1a,b). Meanwhile, the molecule planarity of 4g and 4a is similar to that of 3h and 4h (see Supporting Information, Figure S1). There is almost no torsion angle between V units and the adjacent aryl groups (the dihedral angle is about 2°). Different from the poor coplanar molecule constructed from NDI directly linked to two triphenylamines,22 the good planarity of 4h enables the delocalization of HOMO over the whole molecular backbone (Figure 1c). The LUMO of 4h are mainly localized on the NDI backbone due to its strong electron-deficient property (Figure 1d). Tunable optical absorption in a wide range and PL spectra over the entire visible spectral region were obtained for both HONDIVAr and ArVNDIVAr π-systems by introducing a 4′substituent in aryl ethylene either an electron-withdrawing group (e.g., NO2) or electron-donating group (e.g., NMe2), whereas ArVNDIVArs exhibited wider range tunable spectra

Figure 2. (a) Photograph of 3a−3i and 4a−4i in chloroform solution under white light (first row) and UV lamp (λ = 365 nm, second row). (b) Normalized absorption spectra of 3b, 4b, 3e, and 4e in chloroform solution. (c) Normalized absorption spectra of 3b, 3i, 4b, and 4i in chloroform solution. (d) Normalized emission spectra of 3b, 3h, 4b, and 4h in chloroform solution.

spectrum is characterized by two spectral features, a highenergy peak and a broad low-energy band (see Supporting Information, Table S1). The high-energy peak located at approximately 330−400 nm can be attributed to the π−π* transition in the molecule backbone. The low-energy band with major absorption peaks at 457−601 nm for 3a−3i and 465− 645 nm for 4a−4i are ascribed to the charge-transfer transition between electron-donating ethylene units and electron-accepting NDI units. For 3a−3i, the maximum absorption profile remains featureless, whereas in the case of 4a−4g, shoulder peaks appear at long wavelength (Figure 2b, compounds 3b, 3e versus 4b, 4e). It suggests that molecular aggregation maybe present in the solution of ArVNDIVAr. Interestingly, large bathochromic shifts are observed for the absorbance of the HONDIVAr π-systems by varying 4′-substituents in the phenyl group of aryl vinylenes. The stronger the electron-donating property of the 4′-substituent in aryl ethylene is, the longer wavelength the maximum absorption peak bathochromic shifts. When the 4′-substituent of aryl ethylene was changed from 12808

DOI: 10.1021/acs.joc.7b02140 J. Org. Chem. 2017, 82, 12806−12812

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The Journal of Organic Chemistry

129.03, 127.7, 126.9, 124.5, 123.8, 122.4, 121.2, 105.7, 44.8, 44.3, 38.0, 37.9, 30.9, 30.8, 28.8, 28.7, 24.2, 24.1, 23.3, 23.2, 14.2, 10.8, 10.7 ppm; ESI-HRMS (m/z) [M + H]+ calcd for C38H45N2O5 609.3323, found 609.3311. (E)-2,7-Bis(2-ethylhexyl)-4-hydroxy-9-(4-nitrostyryl)benzo[lmn][3,8]phenanthroline-1,3,6,8-(2H,7H)-tetraone (3b): Yellow solid, 56 mg, yield 86%; mp = 169−170 °C; IR (KBr, cm−1) 3357, 2959, 2927, 2857, 1728, 1642, 1458, 1340; 1H NMR (300 MHz, CDCl3) δ 12.84 (s, 1H), 8.95 (s, 1H), 8.79 (d, J = 16.3 Hz, 1H), 8.34−8.25 (m, 3H), 7.81 (d, J = 8.7 Hz, 2H), 7.36 (d, J = 16.3 Hz, 1H), 4.19−4.07 (m, 4H), 1.98−1.88 (m, 2H), 1.41−1.26 (m, 16H), 0.98−0.87 (m, 12H) ppm; 13C NMR (75 MHz, CDCl3) δ 168.7, 164.1, 163.9, 163.0, 162.3, 147.7, 143.2, 139.4, 133.0, 132.2, 131.7, 129.2, 128.0, 127.5, 125.1, 124.4, 124.1, 122.2, 105.6, 44.9, 44.3, 38.0, 37.9, 30.8, 30.7, 28.7, 28.6, 24.16, 24.12, 23.24, 23.16, 14.2, 10.79, 10.71 ppm; ESI-HRMS (m/z) [M − H]− calcd for C38H44N3O7 654.3174, found 654.3175. (E)-4-(2-(2,7-Bis(2-ethylhexyl)-9-hydroxy-1,3,6,8-tetraoxo1,2,3,6,7,8-hexahydrobenzo[lmn][3,8]phenanthrolin-4-yl)vinyl)benzonitrile (3c): Yellow solid, 47 mg, yield 74%; mp = 170−171 °C; IR (KBr, cm−1) 2958, 2926, 2856, 2225(νCN), 1729, 1698, 1642, 1457; 1H NMR (400 MHz, CDCl3) δ 12.82 (s, 1H), 8.94 (s, 1H), 8.74 (d, J = 16.3 Hz, 1H), 8.30 (d, J = 1.5 Hz, 1H), 7.73 (q, J = 8.4 Hz, 4H), 7.31 (d, J = 16.3 Hz, 1H), 4.18−4.06 (m, 4H), 1.99−1.87 (m, 2H), 1.41−1.25 (m, 16H), 0.96−0.87 (m, 12H) ppm; 13C NMR (101 MHz, CDCl3) δ 168.7, 164.0, 163.9, 163.0, 162.3, 141.3, 139.6, 133.5, 132.8, 132.1, 130.8, 129.2, 127.9, 127.4, 125.0, 124.1, 122.4, 122.0, 118.9, 112.0, 105.6, 44.9, 44.3, 38.0, 37.9, 30.8, 30.7, 28.7, 28.6, 24.2,24.1, 23.23, 23.16, 14.2, 10.79, 10.71 ppm; ESI-HRMS (m/z) [M + H]+ calcd for C39H44N3O5 634.3275, found 634.3268. (E)-2,7-Bis(2-ethylhexyl)-4-hydroxy-9-(4-methylstyryl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (3d): Red solid, 38 mg, yield 61%; mp = 159−160 °C; IR (KBr, cm−1) 2958, 2927, 2857, 1730, 1644, 1456; 1H NMR (400 MHz, CDCl3) δ 12.73 (s, 1H), 8.95 (s, 1H), 8.63 (d, J = 16.3 Hz, 1H), 8.24 (s, 1H), 7.54 (d, J = 7.7 Hz, 2H), 7.34 (d, J = 16.3 Hz, 1H), 7.22 (d, J = 7.7 Hz, 2H), 4.15− 4.05 (m, 4H), 2.40 (s, 3H), 1.96−1.88 (m, 2H), 1.40−1.27 (m, 16H), 0.99−0.86 (m, 12H) ppm; 13C NMR (101 MHz, CDCl3) δ 168.7, 163.8, 163.3, 163.0, 162.3, 140.8, 139.2, 136.2, 134.0, 132.0, 129.6, 129.0, 127.5, 126.6, 125.6, 124.3, 123.6, 122.3, 120.8, 105.5, 44.7, 44.1, 37.9, 37.8, 30.7, 30.6, 28.6, 28.5, 24.1, 24.0, 23.13, 23.05, 21.5, 14.1, 10.7, 10.6 ppm; ESI-HRMS (m/z) [M − H]− calcd for C39H45N2O5 621.3323, found 621.3318. (E)-2,7-Bis(2-ethylhexyl)-4-hydroxy-9-(2-(naphthalen-2-yl)vinyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (3e): Red solid, 50 mg, yield 76%; mp = 170−171 °C; IR (KBr, cm−1) 2958, 2927, 2857, 1729, 1698, 1644, 1605, 1457; 1H NMR (300 MHz, CDCl3) δ 12.69 (s, 1H), 8.95 (s, 1H), 8.74 (d, J = 16.3 Hz, 1H), 8.19 (s, 1H), 7.83 (s, 1H), 7.79−7.72 (m, 4H), 7.44 (ddd, J = 10.4, 7.0, 3.6 Hz, 3H), 4.16−4.01 (m, 4H), 1.98−1.86 (m, 2H), 1.43−1.28 (m, 16H), 0.98−0.87 (m, 12H) ppm; 13C NMR (75 MHz, CDCl3) δ 168.7, 163.9, 163.4, 163.0, 162.3, 140.5, 136.1, 134.3, 133.6, 133.5, 131.9, 128.9, 128.5, 128.4, 128.3, 127.8, 127.0, 126.7, 126.6, 124.3, 123.8, 123.7, 120.9, 105.5, 44.8, 44.2, 38.0, 37.9, 30.9, 30.8, 28.8, 28.6, 24.2, 24.1, 23.3, 23.2, 14.3, 10.8, 10.7 ppm; ESI-HRMS (m/z) [M + H]+ calcd for C42H47N2O5 659.3489, found 659.3481. (E)-2,7-Bis(2-ethylhexyl)-4-hydroxy-9-(4-methoxystyryl)-benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (3f): Red solid, 48 mg, yield 76%; mp = 158−159 °C; IR (KBr, cm−1) 3356, 2958, 2925, 2854, 1729, 1646, 1456; 1H NMR (400 MHz, CDCl3) δ 12.72 (s, 1H), 8.98 (s, 1H), 8.60 (d, J = 16.2 Hz, 1H), 8.26 (s, 1H), 7.61 (d, J = 8.3 Hz, 2H), 7.36 (d, J = 16.3 Hz, 1H), 6.95 (d, J = 8.2 Hz, 2H), 4.15− 4.08 (m, 4H), 3.87 (s, 3H), 1.98−1.88 (m, 2H), 1.40−1.28 (m, 16H), 0.96−0.87 (m, 12H) ppm; 13C NMR (101 MHz, CDCl3) δ 168.7, 163.8, 163.1, 162.9, 162.2, 160.5, 140.9, 135.9, 131.8, 129.5, 129.0, 128.9, 126.4, 124.3, 124.1, 123.5, 122.3, 120.3, 114.3, 105.5, 55.4, 44.7, 44.1, 37.9, 37.8, 30.7, 30.6, 28.6, 28.5, 24.1, 24.0, 23.1, 23.0, 14.1, 10.7, 10.6 ppm; ESI-HRMS (m/z) [M − H]− calcd for C39H45N2O6 637.3278, found 637.3272. (E)-2,7-Bis(2-ethylhexyl)-4-hydroxy-9-(2-(thiophen-2-yl)-vinyl)benzo[lmn][3,8]phenanthroline1,3,6,8(2H,7H)-tetraone (3g): Red

NO2 to NMe2, the maximum absorption peak 457 nm red shifts to 601 nm (Δλmax = 144 nm, compound 3b versus 3i) for HONDIVArs, and the peak 465 nm red shifts to 645 nm (Δλmax = 180 nm compound 4b versus 4i) for ArVNDIVArs (Figure 2c). Noticeably, the emission spectra show similar trends for the bathochromic shifts, and λem could be tuned from blue to near-infrared for HONDIVArs and ArVNDIVArs, in which big differences of bathochromic shifts, 229 nm (506 to 735 nm, compound 3b versus 3h) and 242 nm (513 to 755 nm, compound 4b versus 4h), are observed, respectively (Figure 2d). The optical energy gap of 4h measured from the onset of its absorption is 1.7 eV, combined with the LUMO of −3.56 eV obtained from the cyclic voltammetry curve, and the HOMO is calculated to be −5.26 eV. In conclusion, we have established a convenient method for the tunable synthesis of coplanar NDI-based conjugated molecules through Heck−Mizoroki reactions of the corresponding 2,6-dibromo-NDI with aryl ethylenes. The hydoxylated and mono-olefination or diolefination is controlled mainly by the catalyst and base used in the reaction system. Strong base facilitates the formation of hydroxylated and monoolefination products, HONDIVArs, whereas diolefination products, ArVNDIVArs, prefer weak base conditions. It is worth noting that the absorbance and emission of the HONDIVAr and ArVNDIVAr π-systems can be finely adjusted by changing the 4′-substituents of aryl ethylenes, and the spectra of ArVNDIVArs are tunable in a wider range than HONDIVArs.

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EXPERIMENTAL SECTION

General. Chemical reagents were purchased and used as received. All air- and water-sensitive reactions were performed under nitrogen atmosphere. NMR spectra were recorded on Bruker 300, 400, or 500 MHz NMR spectrometers. IR spectra were acquired on a Pekin-Elmer 782 IR spectrometer. Melting points were obtained on a Beijing Tech X-4 apparatus without correction. Mass spectra were recorded on a Bruker APEX-2 FT-ICRMS MALDI-TOF analyzer using MALDI mode. Absorption spectra were recorded on a Shimidazu UV-3600 UV−vis−NIR spectrophotometer. Cyclic voltammetry was performed using a BASI Epsilon workstation, and measurements were carried out in acetonitrile containing 0.1 M n-Bu4NPF6 as a supporting electrolyte. Carbon electrode was used as a working electrode and a platinum wire as a counter electrode; all potentials were recorded versus Ag/AgCl (saturated) as a reference electrode. The scan rate was 100 mV s−1. General Procedure for the Synthesis of HONDIVAr via 2,6Dibromonaphthalene Diimide with Aryl Ethylenes. A solution of 2,6-dibromonaphthalene diimide 1 (0.1 mmol), aryl ethylenes 2a− 2i (0.2 mmol), Pd(PPh3)4 (0.01 mmol), and K2CO3 (0.3 mmol) in 2 mL of DMF was stirred at 90 °C under nitrogen atmosphere. The reaction mixture was stirred until completion, which was monitored by TLC. Then solution was neutralized to pH 6−7 with NH4Cl(aq), diluted by ethyl acetate (10 mL), and washed with brine (10 mL). The aqueous layer was extracted with ethyl acetate, and the combined organic layers were dried over anhydrous sodium sulfate. After removal of sodium sulfate through filtration, the solution was concentrated under reduced pressure. The obtained mixture was purified by flash column chromatography over silica gel (gradient: petroleum ether/ dichloromethane = 4/1 to 1/2) to afford the desired products 3a−3i. (E)-2,7-Bis(2-ethylhexyl)-4-hydroxy-9-styrylbenzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (3a): Red solid, 51 mg, yield 84%; mp = 159−160 °C; IR (KBr, cm−1) 2958, 2927, 2857, 1730, 1644, 1456; 1H NMR (400 MHz, CDCl3) δ 12.76 (s, 1H), 8.97 (s, 1H), 8.67 (d, J = 16.3 Hz, 1H), 8.27 (s, 1H), 7.67 (d, J = 7.5 Hz, 2H), 7.43 (t, J = 7.4 Hz, 2H), 7.38 (d, J = 5.7 Hz, 1H), 7.35 (d, J = 2.9 Hz, 1H), 4.17−4.06 (m, 4H), 1.98−1.90 (m, 2H), 1.41−1.27 (m, 16H), 0.97−0.86 (m, 12H) ppm; 13C NMR (101 MHz, CDCl3) δ 168.8, 163.9, 163.6, 163.1, 162.4, 140.8, 136.8, 136.2, 132.3, 129.2, 129.09, 12809

DOI: 10.1021/acs.joc.7b02140 J. Org. Chem. 2017, 82, 12806−12812

Note

The Journal of Organic Chemistry solid, 55 mg, yield 90%; mp = 156−157 °C; IR (KBr, cm−1) 3357, 2958, 2924, 2853, 1728, 1644, 1456; 1H NMR (300 MHz, CDCl3) δ 12.70 (s, 1H), 8.88 (s, 1H), 8.51 (d, J = 16.1 Hz, 1H), 8.22 (s, 1H), 7.51 (d, J = 16.1 Hz, 1H), 7.34 (d, J = 5.1 Hz, 1H), 7.26 (d, J = 2.2 Hz, 1H), 7.07 (dd, J = 5.1, 3.6 Hz, 1H), 4.14−4.05 (m, 4H), 1.97−1.87 (m, 2H), 1.41−1.27 (m, 16H), 0.98−0.86 (m, 12H) ppm; 13C NMR (75 MHz, CDCl3) δ 168.8, 163.8, 163.4, 163.0, 162.3, 142.5, 140.2, 131.7, 129.1, 129.0, 128.6, 128.1, 127.0, 126.7, 125.9, 124.4, 123.7, 122.4, 120.7, 105.6, 44.8, 44.2, 38.0, 37.9, 30.8, 30.7, 28.7, 28.6, 24.1, 23.2, 23.2, 14.2, 10.8, 10.7 ppm; ESI-HRMS (m/z) [M + H]+ calcd for C36H43N2O5S 615.2887, found 615.2888. (E)-4-(4-(Diphenylamino)styryl)-2,7-bis(2-ethylhexyl)-9hydroxybenzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (3h): Green solid, 54 mg, yield 70%; mp = 235−236 °C; IR (KBr, cm−1) 3361, 2956, 2923, 2853, 1698, 1659, 1645, 1588, 1456; 1H NMR (400 MHz, CDCl3) δ 12.72 (s, 1H), 8.99 (s, 1H), 8.63 (d, J = 16.2 Hz, 1H), 8.27 (s, 1H), 7.54 (d, J = 8.4 Hz, 2H), 7.37 (d, J = 16.2 Hz, 1H), 7.30 (t, J = 7.7 Hz, 4H), 7.16 (d, J = 7.9 Hz, 4H), 7.11−7.07 (m, 4H), 4.12 (dd, J = 14.6, 7.4 Hz, 4H), 1.96−1.86 (m, 2H), 1.40− 1.26 (m, 16H), 0.95−0.87 (m, 12H)ppm; 13C NMR (101 MHz, CDCl3) δ 168.9, 164.0, 163.3, 163.2, 162.5, 148.9, 147.4, 141.2, 136.1, 132.1, 130.5, 129.6, 129.1, 128.8, 126.6, 125.2, 124.7, 124.3, 123.8, 122.7, 122.6, 120.5, 105.8, 44.8, 44.3, 38.1, 37.9, 30.9, 30.8, 28.8, 28.7, 24.2, 24.1, 23.3, 23.2, 14.2, 10.8, 10.7 ppm; ESI-HRMS (m/z) [M + H]+ calcd for C50H54N3O5 776.4058, found 776.4049. (E)-4-(4-(Dimethylamino)styryl)-2,7-bis(2-ethylhexyl)-9hydroxybenzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (3i): Green solid, 48 mg, yield 74%; mp = 146−147 °C; IR (KBr, cm−1) 3361, 2957, 2924, 2854, 1697, 1644, 1594, 1566, 1456; 1H NMR (300 MHz, CDCl3) δ 12.64 (s, 1H), 8.97 (s, 1H), 8.56 (d, J = 16.2 Hz, 1H), 8.20 (s, 1H), 7.48 (d, J = 8.8 Hz, 2H), 7.34 (d, J = 16.2 Hz, 1H), 6.67 (d, J = 8.8 Hz, 2H), 4.10 (dt, J = 11.1, 5.7 Hz, 4H), 3.03 (s, 6H), 1.97−1.88 (m, 2H), 1.42−1.26 (m, 16H), 0.97−0.88 (m, 12H) ppm; 13C NMR (75 MHz, CDCl3) δ 168.9, 164.0, 163.2, 162.8, 162.5,, 151.1, 141.7, 137.1, 131.9, 129.2, 128.9, 126.2, 125.0, 123.8, 123.5, 122.7, 121.6, 119.4, 112.2, 105.8, 44.7, 44.2, 40.4, 38.0, 37.9, 30.8, 28.8, 28.7, 24.1, 23.3, 23.2, 14.3, 10.8, 10.7 ppm; ESI-HRMS (m/ z) [M + H]+ calcd for C40H50N3O5 652.3745, found 652.3743. General Procedure for the Synthesis of ArVNDIVAr via 2,6Dibromonaphthalene Diimide with Aryl Ethylenes. A solution of 2,6-dibromonaphthalene diimide 1 (0.1 mmol), aryl eththylenes 2a−2i (0.2 mmol), Pd(PtBu3)2 (0.01 mmol), and Cy2NMe (0.3 mmol) in 2 mL of DMAc was stirred at 90 °C under nitrogen atmosphere. The reaction mixture was stirred until completion, which was monitored by TLC. Then solution was diluted by ethyl acetate (10 mL) and washed with brine (10 mL). The aqueous layer was extracted with ethyl acetate, and the combined organic layers were dried over anhydrous sodium sulfate. After removal of sodium sulfate through filtration, the solution was concentrated under reduced pressure. The obtained mixture was purified by flash column chromatography over silica gel (gradient: petroleum ether/dichloromethane = 2/1 to 1/4) to afford the desired products 4a−4i. 2,7-Bis(2-ethylhexyl)-4,9-di((E)-styryl)benzo[lmn][3,8]phenanthroline-1,3,6,8-(2H,7H)-tetraone (4a): Red solid, 57 mg, yield 82%; mp = 220−221 °C; IR (KBr, cm−1) 2958, 2926, 2856, 1729, 1697, 1443; 1H NMR (400 MHz, CDCl3) δ 8.98 (s, 2H), 8.75 (d, J = 16.3 Hz, 2H), 7.68 (d, J = 7.4 Hz, 4H), 7.50−7.40 (m, 6H), 7.37 (d, J = 7.2 Hz, 2H), 4.16−4.07 (m, 4H), 1.98−1.91 (m, 2H), 1.41−1.28 (m, 16H), 0.96−0.88 (m, 12H) ppm; 13C NMR (101 MHz, CDCl3) δ 164.1, 163.1, 142.5, 137.3, 136.8, 131.5, 129.3, 129.1, 127.9, 127.3, 126.9, 125.4, 120.5, 44.8, 38.0, 30.9, 28.7, 24.2, 23.3, 14.3, 10.8 ppm; ESI-HRMS (m/z) [M + H]+ calcd for C46H51N2O4 695.3843, found 695.3836. 2,7-Bis(2-ethylhexyl)-4,9-bis((E)-4-nitrostyryl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (4b): Yellow solid, 35 mg, yield 45%; mp = 236−237 °C; IR (KBr, cm−1) 2958, 2926, 2856, 1729, 1651, 1519, 1340; 1H NMR (300 MHz, CDCl3) δ 9.04 (s, 2H), 8.90 (d, J = 16.2 Hz, 2H), 8.31 (d, J = 8.9 Hz, 4H), 7.84 (d, J = 8.9 Hz, 4H), 7.49 (d, J = 16.1 Hz, 2H), 4.25−4.11 (m, 4H), 2.02−1.93 (m, 2H), 1.43−1.30 (m, 16H), 0.93 (dd, J = 11.0, 7.1 Hz, 12H) ppm; 13C

NMR (101 MHz, CDCl3) δ 163.9, 162.8, 147.8, 142.8, 141.8, 134.2, 131.7, 131.3, 128.1,127.5, 125.8, 124.3, 121.4, 44.8, 37.9, 30.7, 28.6, 24.1, 23.1, 14.1, 10.7 ppm; ESI-HRMS (m/z) [M + H]+ calcd for C46H49N4O8 785.3544, found 785.3535. 4,4′-((1E,1′E)-(2,7-Bis(2-ethylhexyl)-1,3,6,8-tetraoxo-1,2,3,6,7,8hexahydrobenzo[lmn][3,8]phenanthroline-4,9-diyl)bis(ethene-2,1diyl))dibenzonitrile (4c): Yellow solid, 45 mg, yield 61%; mp = 236− 237 °C; IR (KBr, cm−1) 2958, 2924, 2854, 2225(νCN), 1729, 1658, 1446; 1H NMR (400 MHz, CDCl3) δ 9.03 (s, 2H), 8.86 (d, J = 16.3 Hz, 2H), 7.79 (d, J = 8.2 Hz, 4H), 7.73 (d, J = 8.1 Hz, 4H), 7.44 (d, J = 16.3 Hz, 2H), 4.25−4.11 (m, 4H), 1.98−1.93 (m, 2H), 1.42−1.28 (m, 16H), 0.99−0.86 (m, 12H) ppm; 13C NMR (126 MHz, CDCl3) δ 163.9, 162.8, 141.9, 140.9, 134.8, 132.7, 131.8, 130.6, 130.6, 128.0, 127.5, 125.7, 121.3, 118.8, 112.2, 44.8, 37.9, 30.7, 28.6, 24.1, 23.1, 14.1, 10.7 ppm; ESI-HRMS (m/z) [M + H]+ calcd for C48H49N4O4 745.3748, found 745.3738. 2,7-Bis(2-ethylhexyl)-4,9-bis((E)-4-methylstyryl)benzo[lmn][3,8]phenanthroline-1,3,6,8-(2H,7H)-tetraone (4d): Red solid, 53 mg, yield 73%; mp = 213−214 °C; IR (KBr, cm−1) 2958, 2925, 1731, 1656, 1456; 1H NMR (300 MHz, CDCl3) δ 9.05 (s, 2H), 8.77 (d, J = 16.3 Hz, 2H), 7.60 (d, J = 8.1 Hz, 4H), 7.49 (d, J = 16.3 Hz, 2H), 7.23 (d, J = 8.1 Hz, 4H), 4.25−4.12 (m, 4H), 2.41 (s, 6H), 2.00−1.93 (m, 2H), 1.40−1.30 (m, 16H), 0.98−0.85 (m, 12H) ppm; 13C NMR (101 MHz, CDCl3) δ 164.0, 163.1, 142.4, 139.4, 137.2, 134.0, 131.3, 129.6, 127.7, 127.1, 125.7, 125.2, 120.1, 44.6, 37.9, 30.7, 28.6, 24.1, 23.1, 21.5, 14.1, 10.7 ppm; ESI-HRMS (m/z) [M + H]+ calcd for C48H55N2O4 723.4162, found 723.4156. 2,7-Bis(2-ethylhexyl)-4,9-bis((E)-2-naphthalen-2-yl)vinyl)benzo[lmn][3,8]phenanthroline-1,3,6,8-(2H,7H)-tetraone (4e): Red solid, 40 mg, yield 51%; mp = 235−236 °C; IR (KBr, cm−1) 2958, 2926, 2856, 1729, 1655, 1605, 1273, 1201; 1H NMR (300 MHz, CDCl3) δ 9.05 (s, 2H), 8.89 (d, J = 16.3 Hz, 2H), 7.97 (s, 2H), 7.90−7.80 (m, 8H), 7.62 (d, J = 16.3 Hz, 2H), 7.52−7.46 (m, 4H), 4.24−4.13 (m, 4H), 2.03−1.96 (m, 2H), 1.45−1.31 (m, 16H), 1.00−0.89 (m, 12H) ppm; 13C NMR (126 MHz, CDCl3) δ 164.1, 163.0, 142.3, 137.2, 134.2, 133.7, 133.5, 131.3, 128.8,128.6, 128.4, 127.8, 127.2, 127.0, 126.7, 126.5, 125.2, 123.9, 120.2, 44.6,37.9, 30.8, 28.6, 24.1, 23.2, 14.2, 10.7 ppm; ESI-HRMS (m/z) [M + H]+ calcd for C54H55N2O4 795.4162, found 795.4156. 2,7-Bis(2-ethylhexyl)-4,9-bis((E)-4-methoxystyryl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (4f): Red solid, 50 mg, yield 66%; mp = 238−239 °C; IR (KBr, cm−1) 2959, 2925, 2853, 1728, 1657, 1456; 1H NMR (300 MHz, CDCl3) δ 8.86 (s, 2H), 8.59 (d, J = 16.3 Hz, 2H), 7.57 (d, J = 8.4 Hz, 4H), 7.36 (d, J = 16.3 Hz, 2H), 6.92 (d, J = 8.3 Hz, 4H), 4.18−4.02 (m, 4H), 3.85 (s, 6H), 1.95− 1.88 (m, 2H), 1.40−1.28 (m, 16H), 0.97−0.87 (m, 12H) ppm; 13C NMR (75 MHz, CDCl3) δ 164.1, 163.1, 160.7, 142.3, 136.8, 131.0, 129.6, 129.4, 127.0, 125.0, 124.4, 119.6, 114.4, 55.5, 44.7, 38.0, 30.9, 28.7, 24.2, 23.3, 14.3, 10.8 ppm; ESI-HR MS (m/z) [M + H]+calcd for C48H55N2O6 755.4054, found 755.4046. 2,7-Bis(2-ethylhexyl)-4,9-bis((E)-2-(thiophen-2-yl)vinyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (4g): Red solid, 56 mg, yield 80%; mp = 232−233 °C; IR (KBr, cm−1) 2957, 2924, 2853, 1731, 1655, 1593; 1H NMR (300 MHz, CDCl3) δ 9.12 (s, 2H), 8.80 (d, J = 16.0 Hz, 2H), 7.81 (d, J = 16.1 Hz, 2H), 7.62−7.46 (m, 4H), 7.43 (s, 2H), 4.36−4.20 (m, 4H), 2.19−2.01 (m, 2H), 1.60−1.43 (m, 16H), 1.10 (dd, J = 14.0, 6.6 Hz, 12H) ppm; 13C NMR (75 MHz, CDCl3) δ 164.1, 163.2, 142.6, 141.9, 131.2, 130.2, 129.0, 128.3, 127.4, 126.0, 125.3, 120.1, 44.7, 38.0, 30.9, 28.7, 24.2, 23.3, 14.3, 10.8 ppm; ESI-HRMS (m/z) [M + H]+ calcd for C42H47N2O4S2 707.2972, found 707.2974. 4,9-Bis((E)-4-(diphenylamino)styryl)-2,7-bis(2-ethylhexyl)benzo[lmn][3,8]phenanthroline-1,3,6,8-(2H,7H)-tetraone (4h): Green solid, 83 mg, yield 81%; mp = 311−312 °C; IR (KBr, cm−1) 3355, 2956, 2923, 2853, 1654, 1587, 1568, 1507; 1H NMR (300 MHz, CDCl3) δ 9.03 (s, 2H), 8.72 (d, J = 16.3 Hz, 2H), 7.56 (d, J = 8.7 Hz, 4H), 7.47 (d, J = 16.2 Hz, 2H), 7.33−7.27 (m, 8H), 7.15 (d, J = 7.6 Hz, 8H), 7.19−7.0 (m, 8H), 4.20−4.08 (m, 4H), 1.99−1.90 (m, 2H), 1.42−1.27 (m, 16H), 0.99−0.86 (m, 12H) ppm; 13C NMR (101 MHz, CDCl3) δ 164.2, 163.2, 148.9, 147.2, 142.3, 136.8, 131.2, 130.4, 12810

DOI: 10.1021/acs.joc.7b02140 J. Org. Chem. 2017, 82, 12806−12812

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The Journal of Organic Chemistry

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129.4,128.8, 127.2, 125.2, 125.0, 124.5, 123.7, 122.5, 119.6, 44.6, 37.9, 30.8, 28.7, 24.1, 23.1, 14.1, 10.7 ppm; ESI-HRMS (m/z) [M + H]+ calcd for C70H69N4O4 1029.5313, found 1029.5320. 4,9-Bis((E)-4-(dimethylamino)styryl)-2,7-bis(2-ethylhexyl)benzo[lmn][3,8]phenanthroline-1,3,6,8-(2H,7H)-tetraone (4i): Green solid, 65 mg, yield 83%; mp = 243−244 °C; IR (KBr, cm−1) 2956, 2923, 2853, 1695, 1651, 1590, 1567; 1H NMR (400 MHz, CDCl3) δ 8.95 (s, 2H), 8.63 (d, J = 16.3 Hz, 2H), 7.51 (d, J = 7.4 Hz, 4H), 7.41 (d, J = 16.2 Hz, 2H), 6.67 (d, J = 7.8 Hz, 4H), 4.17−4.08 (m, 4H), 3.02 (s, 12H), 2.00−1.92 (m, 2H), 1.41−1.30 (m, 16H), 0.98−0.85 (m, 12H) ppm; 13C NMR (101 MHz, CDCl3) δ 164.3, 163.3, 151.0, 142.2, 137.5, 130.7, 129.3, 127.0, 125.1, 124.6, 121.7, 118.6, 112.0, 44.5, 40.2, 37.9, 30.8, 28.7, 24.1, 23.2, 14.2, 10.7 ppm; ESI-HRMS (m/z) [M + H]+ calcd for C50H61N4O4 781.4687, found 781.4675.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.joc.7b02140. Optical properties of products, 1H and 13C NMR, and computational details (PDF)

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. ORCID

Chunling Gu: 0000-0002-3799-3275 Liang Cheng: 0000-0001-7427-2939 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the National Program on Key Research Project and the National Natural Science Foundation of China. We also thank the Chinese Academy of Sciences for financial support. C.G., L.X., and H.F. received funding from the National Natural Science Foundation of China (Grant Nos. 21472195 and 21203212). Y.L., L.C., D.W., and L.L. received funding from the National Program on Key Research Project (Grant No. 2016YFA0602900) and the National Natural Science Foundation of China (Grant No. 21420102003).

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REFERENCES

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DOI: 10.1021/acs.joc.7b02140 J. Org. Chem. 2017, 82, 12806−12812

Note

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DOI: 10.1021/acs.joc.7b02140 J. Org. Chem. 2017, 82, 12806−12812