A Three-Step Sequence Strategy for Facile Construction of Donor-Acceptor Type Molecules: Triphenylamine- Substituted Acenes

Canadian Journal of Chemistry

A Three-step Sequence Strategy for Facile Construction of Donor-Acceptor Type Molecules: Triphenylamine- Substituted Acenes

Journal: Canadian Journal of Chemistry

Manuscript ID cjc-2019-0254.R1

Manuscript Type: Article

Date Submitted by the 21-Sep-2019 Author:

Complete List of Authors: Zhang, Chen; Wuhan University of Technology, chemical Engineering and Life Sciences Tang, Ming; Wuhan University of Technology, chemical Engineering and Life SciencesDraft Sun, Bing; Wuhan University of Technology, chemical Engineering and Life Sciences Wang, Weizhou; Wuhan University of Technology, chemical Engineering and Life Sciences Yi, Ying; Wuhan University of Technology, chemical Engineering and Life Sciences Zhang, Fang-Lin; Wuhan University of Technology, chemical Engineering and Life Sciences

Is the invited manuscript for consideration in a Special Not applicable (regular submission) Issue?:

Keyword: triphenylamine, anthracene, C–H activation, fluorescence

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A Three-step Sequence Strategy for Facile Construction of Donor-Acceptor Type Molecules: Triphenylamine-Substituted Acenes

Chen Zhang, Ming Tang, Bing Sun, Weizhou Wang, Ying Yi and Fang-Lin Zhang

Chen Zhang, Ming Tang, Bing Sun, Ying Yi and Fang-Lin Zhang. chemical Engineering and Life Sciences, Wuhan University of Technology, Wuhan 430070, Hubei, PR China. Weizhou Wang. College of Chemistry and Chemical Engineering, and Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang 471934, PR China. Corresponding authors: Weizhou Wang (e-mail: [email protected]), Ying Yi (e-mail: [email protected]) and Fang-Lin Zhang (e-mail: [email protected])

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Abstract: A new synthetic strategy was successfully developed for highly efficient construction of triphenylamine-substituted polycyclic aromatic hydrocarbons (PAHs), including anthracenes, tetraphenes, pentaphenes and trinaphthylene. These molecules exhibited special structural characteristics, including donor-acceptor-donor (D-A-D) and donor-acceptor (D-A). Diverse aryl iodides coupled well with chlorinated 2-methyl benzaldehydes via a transient ligand-directed C–H bond arylation strategy to furnish various PAH precursors. The subsequent palladium-catalyzed Suzuki cross-couplings with 4-(diphenylamino)phenylboronic acid produced corresponding triphenylamine derivatives. Further Brønsted acid-promoted cycloaromatization generated the triphenylamine-substituted PAHs readily. The photophysical properties was investigated by UV-visible absorption and fluorescence emission spectroscope together with density functional theory (DFT) calculations.

Key words: triphenylamine, anthracene, C–H activation, fluorescence.

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Introduction Due to their unique molecular structure and optical property, organic conjugated molecules bearing donor–acceptor (D-A) system are widely used as photoelectron materials in the area of organic solar cells, organic light-emitting diodes (OLEDs), sensors, data storage displays and organic crystal field-effect transistors (OFETs) etc1-6. The diverse combinations of various donor and acceptor moieties endow these systems easily tunable highest occupied molecular orbital (HOMO) energy levels and lowest unoccupied molecular orbital (LUMO) energy levels, adjustable optical bandgap, large π-conjugation length, intramolecular charge transfer and strong π-π stacking interactions5,7, which contribute to the readily tunable optical and electrical properties of the hole-transporting materials (HTMs). Triphenylamine (TPA) group proves to be a widely used donor unit for construction of opto- and electroactive organic small molecules and polymeric materials since it has good electron donating and hole-transporting property as well as special nonplanar propeller starburst molecular shape8-10. Polycyclic aromatic hydrocarbons (PAHs), such as anthracenes11, phenanthrenes12, pyrenes13 and tetracenes14, exhibit excellent fluorescence characteristics and have been introduced into the D- A system to improve the photoelectric properties like color purity and electroluminescence (EL) efficiency of materials15. Literature survey showed that a variety of D-A configuration molecules with TPA as donor moiety and PAHs as acceptor moieties have been prepared. For instance, in 2016, Putala group6 reported a series of D-A system molecules featuring TPA and analogues connecting to different positions of the aromatic ring cores by alkyne. In 2017, Hariharan etc.16 synthesized a set of twisting D-A molecules with TPA as donor, aromatic hydrocarbons include benzene (Ph), naphthalene (Nap), anthracene (An), phenanthrene (Phe) and pyrene (Py) as acceptor via the Suzuki-Miyaura cross-couplings with aryl (Ph, Nap, An, Phe and Py) boronic acids. The dual-core derivatives of TPA end-capped anthracence and pyrene were also constructed using two-step Suzuki couplings13,15. Furthermore, the TPA unit cooperated with PAHs were applied to build copolymer macromolecules through coupling interactions17. Most of them used anthracene as core and introduced TPA moiety into the C-9 and/or C-10 positions by Suzuki-Miyaura couplings starting from commercially available halogenated polyacenes18-26. However, other polycyclic segments are rarely utilized because of the expensive costs or exhausting synthetic processes of PAHs, especially with extensive fused aromatic rings14,27. To circumvent the above limitations, our previous work developed a highly efficient two-step strategy to readily construct PAHs28,29 (Scheme 1). The first step proceeded via a transient directing group enabled palladium-catalyzed ortho-C(sp3)–H arylation of benzaldehydes, while the second step involvedDraft a Brønsted acid-promoted cycloaromatization27,30. In this work, D- A-D and D-A arrays end-capped with one or more TPA as donor units were elaborately designed and facilely synthesized. The highly efficient cascade arylations and cycloaromatizations of

Our previous work: O I 1) Pd(OAc)2 via: transient DG O I N O I 2) TfOH Pd H OAc

This work: Donor Donor R R I O 1) Pd(OAc)2 transient DG I TPA4BA I 2) cross-coupling Cl 3) TfOH Donor R Donor: R = N N Scheme 1. Synthesis of TPA derivatives. benzaldehydes with halides provided a series of PAHs, including anthracene, tetraphene, pentaphene and trinaphthylene, which served as acceptor units. Particularly, the trinaphthylene molecule as a central core decorated with three TPA groups at 2, 8 and 14-positions formed a special nonplanar propeller star-shaped structure31. Result and Discussion Synthesis of donor-acceptor type molecules Based on our previous work, a new three steps synthetic route to prepare TPA derivatives with polyacene core was developed28,29. First, a transient directing group enabled palladium-catalyzed ortho-C(sp3)–H arylation of benzaldehyde 6 with iodobenzenes afforded the precursor 7. Subsequent Suzuki cross-couplings with 4-(diphenylamino)phenylboronic acid (TPA4BA) produced corresponding triphenylamine derivatives 8. Further cycloaromatization by treatment with trifluoromethanesulfonic acid (TfOH) generated TPA derivatives with D-A array. TPA derivatives combined with anthracene core were widely utilized as organic functional materials3,19. However, those previous anthracene derivatives mainly restricted on the highly reactive C-9 or C-10 position of anthracene32. Herein, we obtained new anthracene derivatives with TPA group on the C-2 or C-6 position (Scheme 2). These derivatives contain electron-donating group (methyl) and electron withdrawing group (chloride). Furthermore, the chloride substituent allowed readily derivatizations via cross-coupling reactions. Then, this new three-step sequence strategy were further extended to the synthesis of tetraphene derivatives. By using of 2- iodonaphthalene as coupling partner, D-A molecule 2a and the acceptor tetraphene was successfully synthesized (Scheme 3). The tetracene derivatives with methyl at C-9 position (2b) was also obtained in good yield.

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To further explore the substrate scope, 1,4-diiodobenzene was examined to construct TPA derivatives bearing a pentaphene segment (Scheme 4). The D-A-D molecule 3a with pentaphene core was constructed by using TfOH as cycloaromatization reagent. In addition, D-A-D molecules with TPA groups on C-1, C-12 and C-2, C-10 positions (3b & 3c) were also successfully incorporated.

Pd(OAc) O 2 O AgTFA I glycine X AcOH/H2O (v/v=9/1) X 1 R1 (70%-74%) R 5 6 7 1 O R

TPA4BA TfOH 2 cross-coupling R (54%-73%) 1 (56%-73%) R R2 8 1

N N

1a 1b Cl

1c Scheme 2. Synthesis of TPA derivatives with anthracene as acceptor unit.

O Pd(OAc)2 O AgTFA I glycine H (Br) H (Br) AcOH/H2O (v/v=9/1) Cl (Me) (72%-73%) Cl (Me) 5 6 7 Draft O (Me) R TPA4BA TfOH

cross-coupling H (R) (70%-77%) (68%) R (Me) H (R) 8 2

N N

2a 2b Scheme 3. Synthesis of TPA derivatives with tetraphene as acceptor unit.

Pd(OAc) O 2 AgTFA I (Me)Cl O glycine Cl(Me) I AcOH/H2O (v/v=9/1) (Me)Cl (52%-66%) O 5 6 7 R

R O TPA4BA O TfOH R cross-coupling R (80%-82%) (66%-85%)

8 3

N N

3a N

N 3c

3b Scheme 4. Synthesis of TPA derivatives with pentaphene as acceptor unit.

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Recently, star-shaped π-conjugated molecules have attracted intense interest because of their special properties for overcoming the quenching of luminescence and improving the light-harvesting ability33,34. Due to the limitations of synthetic strategys, the reports on the star-shaped molecules with trinaphthylene as the core are rare. Most synthetic routes used Kobayashi's silylaryl triflates as precursors to synthesize trinaphthylene derivatives under metal-catalyzed cyclotrimerization35- 36. However, the construction of precursors often requires cumbersome synthetic steps. Besides, in 2019, Xinliang Feng etc.37 constructed porous nanographene C78 with trinaphthylene core via Suzuki-Miyaura coupling and a subsequent on-surface assisted cyclodehydrogenation on Au(111) which used 2,3,6,7,10,11-hexabromotriphenylene and naphthalene-1-boronic acid pinacol ester as precursors. Based on our facile synthetic route, we assumed that 1,3,5-triiodobenzene could be appropriate substrate to access the star-shaped trinaphthylene derivatives employing readily available starting materials (Scheme 5). The soluble nonplanar propeller star-shaped molecule with terminal groups of three triphenylamines 4 was successfully obtained via cycloaromatization using TfOH.

Pd(OAc) O O 2 I I AgTFA Cl glycine O AcOH/H2O (v/v=9/1) I (74%) O Cl

5g 6c 7i Cl R R O R R TPA4BA TfOH O cross-coupling (76%) (73%) O

R R 8i 4

R= N Draft

R 4 Scheme 5. Synthesis of TPA derivatives with trinaphthylene as acceptor unit. Characterization of donor-acceptor type molecules To investigate their photophysical properties, UV-visible absorption and fluorescence emission spectra were recorded, and the pertinent photophysical data were summarized in Table 1. The UV Vis absorption spectra of compounds in dichloromethane solution were illustrated in Figure 1 and 2. The black line named “0” in Figure 1 was the absorption spectra of anthracene It’s observed that most of the compounds showed two obvious absorption bands from 280 nm to 400 nm. The bands appeared in the region of 280-320 nm were assigned to the π-π* local electron transitions of the TPA unit, the photoabsorption bands at 340-400 nm could be attributed to the intramolecular charge transfer (ICT) from TPA to acene moieties. And the shoulder peak of compounds 1a-1c and 4 observed at 400-450 nm might also originate from the ICT transition. In Figure 1, the photoabsorption of 2b around 400 nm was significantly low, which was different from the others' could be attributed to the different position of TPA compared with 2a and the electron-donating ability of the methyl substituent. Also, the lower photoabsorption Figure 1. Normalized absorption spectra of 1a-2b in dilute dichloromethane solution.

0.5 0 1a 1b 0.4 1c 2a 2b 

1 0.3 - M 1 - m c 

 0.2  



0.1

0.0 300 400 500 Wavelength (nm) of 3c around 400 nm probably because of the T-shaped structure, which has large dihedral angles and seriously hindered the charge-transfer between TPA and acene.

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Figure 2. Normalized absorption spectra of 3a-4 in dilute dichloromethane solution.

3a 0.8 3b 3c 4 0.6  1 - M 1 - m

c 0.4    



0.2

0.0 300 350 400 450 500 550 Wavelength (nm) Figure 3. Normalized fluorescence emission spectra of 1a-2b upon excitation at the absorption maximum in dilute dichloromethane solution (1×10-5 M).

1a 1.0 1b 1c 0.8 2a 2b ) . u . ( a

0.6 i t y s n t e

n 0.4 I Draft 0.2

0.0 400 450 500 550 600 650 Wavelength (nm) Figure 4. Normalized fluorescence emission spectra of 3a-4 upon excitation at the absorption maximum in dilute dichloromethane solution (1×10-5 M).

1.0 3a 3b 0.8 3c 4 ) . u . ( a

0.6 i t y s n t e

n 0.4 I

0.2

0.0 400 450 500 550 600 650 Wavelength (nm) The ICT process is well-known to exhibit a fluorosolvatochromism originated from its highly polarized excited state, namely the fluorescence emission peak is red-shifted along with an increase in the solvent polarity. To clarify ICT-based optical properties of the novel TPA-substituted PAHs, solvent polarity dependent fluorescence emission spectra of 1c (Figure 5) and 4 (Figure 6) were measured representatively. The solvent-polarity dependent photophysical studies of TPA derivatives showed significant bathochromic in the absorption maximum. The fluorescence emission spectra maximum demonstrates obviously solvatochromic shift over 108 nm from 433 nm in cyclohexane to 541 nm in acetonitrile for 1c and 86 nm from 424 nm in cyclohexane to 510 nm in acetonitrile for 4 with the increase of solvent polarity together with the gradually disappeared vibrational fine structures. These results indicate that the novel TPA-substituted PAHs exhibit a typical ICT property. Figure 5. Solvent polarity dependent normalized fluorescence emission spectra of 1c upon excitation at the absorption maximum

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Cyclohexane 1.0 Toluene Tetrahydrofuran 1,4-dioxane 0.8 Acetonitrile Methanol ) . u . ( a

0.6 i t y s n t e

n 0.4 I

0.2

0.0 400 450 500 550 600 650 wavelength (nm) Figure 6. Solvent polarity dependent normalized fluorescence emission spectra of 4 upon excitation at the absorption maximum

Cyclohexane Toluene 1.0 Tetrahydrofuran 1,4-dioxane 0.8 Acetonitrile Methanol ) . u . ( a

0.6 i t y s n t e

n 0.4 I 0.2 Draft 0.0 400 450 500 550 600 650 Wavelength (nm)

The fluorescence emission spectra of TPA substituted acenes in dichloromethane solution showed characteristic emission bands ranging from 453 nm to 506 nm (Figure 3 and 4). Compared to 1b and 1a, the emission spectra of 1c with chloride as substituent have red-shifted by 23 and 16 nm, respectively. This result may be ascribed to the increased electron-withdrawing ability of the substituent at C-6 position of anthracene, which led to better π-π* delocalization in the conjugated system. Compound 2a exhibited a comparable red-shifted about 15 nm to 2b, which probably because of the electron-donating ability of the methyl substituent. In the cases of bulky 3a, 3b and 3c with pentaphene core, their emission spectra showed obvious blue-shifted probably because of the conjugated structures were wrecked by increased number of twisted TPA unit and the relatively weak electron-withdrawing ability of acenes. Table 1. UV-visible absorption and fluorescence emission spectra data of the compounds

a b λabs /nm λem/nm λabs/nm λem /nm 1a 343 490 3a 343, 361, 477 1b 345 483 398 1c 348 506 3b 379 455, 478 2a 347 477 3c 363 453,472 2b 346 462 4 372 480 aAbsorption spectra were measured in dichloromethane. bFluorescence emission spectra were measured in dichloromethane (1×10-5 M) and excited at the absorption maximum. Density functional theory (DFT) calculations were carried out to investigate the electronic transitions of the compounds. Figure 7, Figure S1 and Figure S2 showed the calculated HOMOs and LUMOs orbital distributions of all these compounds. The HOMOs were mainly distributed on the TPA moieties and modestly on the acene moieties and the LUMOs were mostly located on the acene units. Considering the special orbital distribution including the partial overlap between the HOMO and LUMO at the PAH moieties, the electronic transition from the HOMO to the LUMO could be assigned to the ICT transition from the TPA donor terminals to the PAH acceptor cores, which was consistent with the conclusion of UV Vis absorption spectra. In Table 2, compound 1c exhibited the lowest calculated energy gap and compound 1b exhibited the highest energy gap compared with 1a and 1c, which had the same anthracene core showed that the electron-withdrawing substituent at C-6 position of anthracene could reduce the energy gap. Compounds 3a-3c showed an increased energy gap from 3.23 eV to 3.40

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8 eV could be attributed to the enhanced nonlinear structure of molecules, which could cause growing resistance to electronic transitions and lower the position of the longest-wavelength absorption peak (form 398nm for 3a to 363nm for 3c). Table 2. Calculated band gaps.

a Compd EHOMO(eV) ELUMO(eV) Eg(eV)

1a -4.87 -1.68 3.19 1b -4.84 -1.61 3.23 1c -4.96 -1.89 3.07 2a -4.90 -1.60 3.30 2b -4.89 -1.50 3.39 3a -4.85 -1.62 3.23 3b -4.88 -1.58 3.30 3c -4.81 -1.41 3.40 4 -4.90 -1.67 3.23 aCalculated at the B3LYP/6-31G(d) theory level for the TPA substituted acences.

Figure 7. HOMO and LUMO representations of compounds 1a-2b calculated at the B3LYP/6-31G(d) theory level.

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Conclusion A new three-step synthetic strategy for facile access to D-A system molecules was successfully developed. This sequence reaction combined transient ligand-directed ortho-C(sp3)–H bond activation and palladium-catalyzed Suzuki cross-coupling as well as Brønsted acid-promoted cycloaromatization together to achieve high efficiency. Through this newly-developed methodology, the PAH acceptors with three, four, five and seven fused aromatic rings were well constructed and suitable for further derivatizations. More interestingly, star-shaped trinaphthylene derivative was also obtained readily. The novel TPA- substituted PAHs exhibit typical ICT property and all synthesized compounds had 343-398 nm absorption bands and 462-506 nm emission bands in dilute dichloromethane solution. This synthetic route provides an opportunity for rapid construction of triphenylamine-substituted acenes. Experimental section Materials and instrumentation All other reagents were obtained from commercial sources and used without further purification unless otherwise noted. Solvents were obtained from Sigma-Aldrich, Alfa-Aesar, Oakwood, and Acros and used directly without further purification. 1 H NMR was recorded on Bruker instrument at 500MHz using CDCl3 or DMSO-d6 as solvents. Chemical shifts were reported in parts per million (ppm) relative to solvent (CDCl3: 7.27 ppm; DMSO-d6: 2.50 ppm). The coupling constants (J) are given in 13 Hertz unit (Hz). C NMR was recorded on Bruker instrument at 126 MHz using CDCl3 as solvents. Chemical shifts were reported in ppm referenced to the center line of a triplet at 77.2 ppm of CDCl3. UV-visible absorption spectra were determined on a Shimadzu UV1700 spectrophotometer. Fluorescent emission spectra were carried out on a Denovix DS-11FX luminescence spectrometer. High-resolution mass spectra (HRMS) were recorded on an Agilent Mass spectrometer using ESI- TOF or Bruker autoflex TOF (MALDI-TOF). Synthesis General procedure A (1) A reaction tube with magnetic stir bar was added substrate 5 (1.000 mmol), Pd(OAc)2 (22.4 mg, 0.100 mmol), AgTFA (552.2 mg, 2.500 mmol), glycine (60.0 mg, 0.800 mmol), substrate 6 and 10 mL premixed solution of AcOH/H2O = 9/1 (v/v) in air. The reaction mixture was stirred at room temperature for 10 minutes, then at 100 ℃ for 36 hours. Upon completion, the

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reaction mixture was cooled to room temperature, filtered through a silica gel plug, the mixture was dried over anhydrous Na2SO4 and concentrated in vacuo. Purification on silica gel (petroleum ether/ethyl acetate) afforded the desired product 7.

(2) A Schlenk flask with magnetic stir bar was added substrate 7 (0.400 mmol), PdCl2(PPh3)2 (14.0 mg, 0.020 mmol), K2CO3 (110.6 mg, 0.800 mmol), TPA4BA and 5 mL premixed solution of Toluene/Methanol/H2O = 15/5/4 (v/v/v) in air. The reaction vessel was then filled with nitrogen and the reaction mixture was stirred at room temperature for 24 hours. Upon completion, the reaction mixture was diluted with CH2Cl2, washed with H2O, dried over anhydrous Na2SO4 and concentrated in vacuo. Purification on silica gel (petroleum ether/CH2Cl2) afforded the desired product 8. (3) A reaction tube (10 mL) with magnetic stir bar was added substrate 8 (0.200 mmol), TfOH(1.5 mg, 5 mol%) and 5 mL DCM in air. The reaction mixture was stirred at room temperature for 5 hours. Upon completion, the reaction mixture was diluted with CH2Cl2, extracted with saturated NaHCO3 aqueous solution, dried over anhydrous Na2SO4 and concentrated in vacuo. Purification on silica gel (petroleum ether/CH2Cl2) afforded the desired product 1-4. General procedure B (1) See general procedure A(1).

(2) A Schlenk flask with magnetic stir bar was added substrate 7 (0.400 mmol), Pd(OAc)2 (18.0 mg, 0.030 mmol), 2- dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (17.3 mg, 0.080 mmol), K3PO4∙3H2O (639.2 mg, 2.400 mmol), TPA4BA and 5 mL THF in air. The reaction vessel was then filled with nitrogen and the reaction mixture was stirred at room temperature for 24 hours. Upon completion, the reaction mixture was diluted with CH2Cl2 , washed with H2O, dried over anhydrous Na2SO4 and concentrated in vacuo. Purification on silica gel (petroleum ether/CH2Cl2) afforded the desired product 8. (3) See general procedure A(3). 4.2.1. 2-(4-bromobenzyl)benzaldehyde (7a) By following the synthetic procedure A(1), 1-bromo-4-iodobenzene (282.9 mg, 1.000 mmol) and 2-methylbenzaldehyde 1 (180.8 mg, 1.500 mmol) afforded 7a (295.1 mg, 70%). Colorless liquid; H NMR (500 MHz, CDCl3) δ 10.21 (s, 1H), 7.87 (d, J = 7.6 Hz, 1H), 7.60 – 7.53 (m, 1H), 7.47 (t, J = 7.4 Hz, 1H), 7.41 (d, J = 8.3 Hz, 2H), 7.27 (d, J = 7.7 Hz, 1H), 7.05 (d, J = 8.3 Hz, 2H), 4.43 (s, 2H). Draft 4.2.2. 2-(4-chlorobenzyl)-4-methylbenzaldehyde (7b) By following the synthetic procedure A(1), 1-chloro-4-iodobenzene (238.5 mg, 1.000 mmol) and 2,4-dimethylbenzaldehyde 1 (201.3 mg, 1.500 mmol) afforded 7b (173.8 mg, 71% yield). Yellow liquid; H NMR (500 MHz, CDCl3) δ 10.15 (s, 1H), 7.76 (d, J = 7.8 Hz, 1H), 7.29 – 7.24 (m, 3H), 7.11 (d, J = 8.3 Hz, 2H), 7.08 (s, 1H), 4.40 (s, 2H), 2.42 (s, 3H). 13C NMR (126 MHz, CDCl3) δ 192.02, 144.97, 142.25, 138.95, 133.43, 132.41, 132.00, 131.69, 130.12, 128.58, 127.94, 37.45, 21.77. HRMS (ESI): + + m/z calculated for C15H13ClO [M+H] 246.0625, found 246.0627. 4.2.3. 2-(4-bromobenzyl)-4-chlorobenzaldehyde (7c) By following the synthetic procedure A(1), 1-bromo-4-iodobenzene (282.9 mg, 1.000 mmol) and 4-chloro-2- 1 methylbenzaldehyde (231.9 mg, 1.500 mmol) afforded 7c (229.1 mg, 74% yield). Orange liquid; H NMR (500 MHz, CDCl3) δ 10.16 (s, 1H), 7.81 (d, J = 8.2 Hz, 1H), 7.46 – 7.41 (m, 3H), 7.24 (d, J = 1.9 Hz, 1H), 7.04 (d, J = 8.4 Hz, 2H), 4.39 (s, 2H). 13 C NMR (101 MHz, CDCl3) δ 191.11, 144.02, 140.42, 138.32, 134.34, 132.24, 131.79, 131.60, 130.54, 127.57, 120.51, 37.29. + + HRMS (ESI): m/z calculated for C14H10BrClO [M+H] 309.9583, found 309.9583. 4.2.4. 4-chloro-2-(naphthalen-2-ylmethyl)benzaldehyde (7d) By following the synthetic procedure A(1), 2-iodonaphthalene (254.0 mg, 1.000 mmol) and 4-chloro-2-methylbenzaldehyde 1 (231.9 mg, 1.500 mmol) afforded 7d (202.1 mg, 72% yield). Brown liquid; H NMR (500 MHz, CDCl3) δ 10.27 (s, 1H), 7.84 (d, J = 8.4 Hz, 2H), 7.82 (d, J = 8.6 Hz, 1H), 7.80 – 7.76 (m, 1H), 7.58 (s, 1H), 7.51 – 7.47 (m, 2H), 7.43 (dd, J = 8.3, 1.8 Hz, 13 1H), 7.35 – 7.30 (m, 2H), 4.60 (s, 2H). C NMR (126 MHz, CDCl3) δ 190.95, 144.69, 140.38, 136.91, 133.64, 133.44, 132.47, 132.28, 131.65, 128.48, 127.68, 127.65, 127.44, 127.30, 127.16, 126.25, 125.75, 37.89. HRMS (ESI): m/z calculated for + + C18H13ClO [M+H] 282.0625, found 282.0626. 4.2.5. 2-((6-bromonaphthalen-2-yl)methyl)-4-methylbenzaldehyde (7e) By following the synthetic procedure A(1), 2-bromo-6-iodonaphthalene (333.0 mg, 1.000 mmol) and 2,4- 1 dimethylbenzaldehyde (201.3 mg, 1.500 mmol) afforded 7e (248.3 mg, 73% yield). Brown liquid; H NMR (500 MHz, CDCl3) δ 10.21 (s, 1H), 7.97 (s, 1H), 7.79 (d, J = 7.8 Hz, 1H), 7.68 (d, J = 8.5 Hz, 1H), 7.62 (d, J = 8.8 Hz, 1H), 7.52 (t, 2H), 7.37 (d, 13 J = 8.4 Hz, 1H), 7.27 (d, J = 7.8 Hz, 1H), 7.12 (s, 1H), 4.58 (s, 2H), 2.41 (s, 3H). C NMR (101 MHz, CDCl3) δ 192.12, 145.04, 142.36, 138.64, 133.16, 132.54, 131.99, 131.75, 129.64, 129.37, 129.30, 128.47, 127.98, 127.22, 127.00, 119.32, 38.17, + + 21.83. HRMS (ESI): m/z calculated for C19H15BrO [M+H] 340.0286, found 340.0285. 4.2.6. 2,2'-(1,4-phenylenebis(methylene))bis(4-chlorobenzaldehyde) (7f) By following the synthetic procedure A(1), 1,4-diiodobenzene (329.9 mg, 1.000 mmol) and 4-chloro-2-methylbenzaldehyde 1 (386.5 mg, 2.500 mmol) afforded 7f (253.0 mg, 66% yield). Yellow solid; m.p. 157-159 °C; H NMR (500 MHz, CDCl3) δ

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10.21 (s, 2H), 7.81 (d, J = 8.2 Hz, 2H), 7.41 (d, J = 8.2 Hz, 2H), 7.26 (s, 2H), 7.09 (s, 4H), 4.40 (s, 4H). HRMS (ESI): m/z + + calculated for C22H16Cl2O2 [M+H] 384.0498, found 384.0499. 4.2.7. 2-((6-bromonaphthalen-2-yl)methyl)-4-methylbenzaldehyde (7g) By following the synthetic procedure A(1), 1,3-diiodobenzene (329.9 mg, 1.000 mmol) and 4-chloro-2-methylbenzaldehyde 1 (386.5 mg, 2.500 mmol) afforded 7g (199.3 mg, 52% yield). Yellow solid; m.p. 86-88 °C; H NMR (500 MHz, CDCl3) δ 10.18 (s, 2H), 7.81 (d, J = 8.3 Hz, 2H), 7.41 (d, J = 8.1 Hz, 2H), 7.26 – 7.19 (m, 3H), 7.00 (d, J = 7.7 Hz, 2H), 6.96 (s, 1H), 4.40 (s, + + 4H). HRMS (ESI): m/z calculated for C22H16Cl2O2 [M+H] 384.0498, found 384.0499. 4.2.8. 2-((6-bromonaphthalen-2-yl)methyl)-4-methylbenzaldehyde (7h) By following the synthetic procedure A(1), 1,4-diiodobenzene (329.9 mg, 1.000 mmol) and 2-chloro-4-methylbenzaldehyde 1 (386.5 mg, 2.500 mmol) afforded 7h (213.9 mg, 52% yield). Yellow solid; m.p. 164-166 °C; H NMR (500 MHz, CDCl3) δ 10.57 (s, 2H), 7.18 (s, 2H), 7.06 (s, 4H), 6.95 (s, 2H), 4.33 (s, 4H), 2.35 (s, 6H). HRMS (ESI): m/z calculated for + + C24H20Cl2O2 [M+H] 412.0811, found 412.0814. 4.2.9. 2,2',2''-(benzene-1,3,5-triyltris(methylene))tris(4-chlorobenzaldehyde) (7i) By following the synthetic procedure A(1), 1,3,5-triiodobenzene (455.7 mg, 1.000 mmol) and 2-chloro-4,6- dimethylbenzaldehyde (674.4 mg, 4.000 mmol) afforded 7i (268 mg, 0.500 mmol, 50% yield). Yellow solid; m.p. 132-134 °C; 1 H NMR (500 MHz, CDCl3) δ 10.13 (s, 3H), 7.79 (d, J = 4.7 Hz, 3H), 7.41 (d, J = 4.4 Hz, 3H), 7.16 (s, 3H), 6.76 (s, 3H), 4.34 13 (s, 6H). C NMR (126 MHz, CDCl3) δ 190.97, 144.31, 140.34, 140.26, 133.72, 132.22, 131.45, 127.60, 127.41, 37.55. HRMS + + (ESI): m/z calculated for C30H21Cl3O3 [M+H] 536.0527, found 536.0526. 4.2.10. 2-((4'-(diphenylamino)-[1,1'-biphenyl]-4-yl)methyl)benzaldehyde (8a) By following the synthetic procedure A(2), 7a (110.1 mg, 0.40 mmol) and TPA4BA (173.5 mg, 0.60 mmol) afforded 8a 1 (248 mg, 73% yield). Brown solid; m.p. 154-156°C; H NMR (500 MHz, CDCl3) δ 10.31 (s, 1H), 7.91 (d, J = 7.6 Hz, 1H), 7.58 (td, J = 7.5, 0.8 Hz, 1H), 7.52 (d, J = 8.1 Hz, 2H), 7.46 (t, J = 7.3 Hz, 3H), 7.34 (d, J = 7.6 Hz, 1H), 7.30 (t, J = 6.7 Hz, 13 4H), 7.23 (d, J = 8.1 Hz, 2H), 7.16 (dd, J = 7.9, 5.7 Hz, 6H), 7.06 (t, J = 7.3 Hz, 2H), 4.52 (s, 2H). C NMR (126 MHz, CDCl3) δ 192.43, 192.37, 147.73, 147.12, 142.99, 138.92, Draft138.75, 134.82, 134.03, 133.95, 132.18, 131.71, 129.29, 129.20, 127.64, + + 127.06, 126.83, 124.44, 123.92, 122.93, 37.72. HRMS (ESI): m/z calculated for C32H25NO [M+H] 440.1970, found 440.1972. 4.2.11. 2-((4'-(diphenylamino)-[1,1'-biphenyl]-4-yl)methyl)-4-methylbenzaldehyde (8b) By following the synthetic procedure B(2), 7b (97.9 mg, 0.400 mmol) and TPA4BA (173.5 mg, 0.600 mmol) afforded 8b 1 (120.0 mg, 66% yield). Yellow solid; m.p. 161-163 °C; H NMR (500 MHz, CDCl3) δ 10.25 (s, 1H), 7.81 (d, J = 7.8 Hz, 1H), 7.51 (d, J = 8.1 Hz, 2H), 7.47 (d, J = 8.5 Hz, 2H), 7.29 (t, J = 7.8 Hz, 5H), 7.25 (s, 1H), 7.23 (d, J = 8.0 Hz, 2H), 7.16 (d, J = 13 4.9 Hz, 3H), 7.15 (d, J = 5.2 Hz, 3H), 7.06 (t, J = 7.3 Hz, 2H), 4.48 (s, 2H), 2.43 (s, 3H). C NMR (126 MHz, CDCl3) δ 192.00, 147.73, 147.09, 144.95, 142.95, 139.07, 138.64, 134.86, 132.51, 132.46, 131.78, 129.28, 129.16, 127.83, 127.62, 126.78, + + 124.42, 123.94, 122.91, 37.65, 21.83. HRMS (ESI): m/z calculated for C33H27NO [M+H] 454.2126, found 454.2126. 4.2.12. 4-chloro-2-((4'-(diphenylamino)-[1,1'-biphenyl]-4-yl)methyl)benzaldehyde (8c) By following the synthetic procedure A(2), 7c (123.8 mg, 0.400 mmol) and TPA4BA (173.5 mg, 0.600 mmol) afforded 8c (106.2 mg, 56% yield). Red solid; m.p. 172-174 °C; 1H NMR (500 MHz, DMSO) δ 10.28 (s, 1H), 7.89 (d, J = 8.1 Hz, 1H), 7.56 (d, J = 8.5 Hz, 6H), 7.32 (t, J = 7.8 Hz, 4H), 7.25 (d, J = 8.1 Hz, 2H), 7.10 – 7.06 (m, 2H), 7.04 (d, J = 7.9 Hz, 4H), 7.02 13 (d, J = 8.7 Hz, 1H), 4.48 (s, 2H). C NMR (126 MHz, CDCl3) δ 191.02, 147.69, 147.21, 144.83, 140.39, 139.04, 137.90, 134.59, 133.40, 132.36, 131.63, 129.30, 129.20, 127.65, 127.43, 126.98, 124.46, 123.89, 122.97, 37.43. HRMS (ESI): m/z + + calculated for C32H24ClNO [M+H] 474.1580, found 474.1583. 4.2.13. 4'-(diphenylamino)-3-(naphthalen-2-ylmethyl)-[1,1'-biphenyl]-4-carbaldehyde (8d) By following the synthetic procedure B(2), 7d (112.3 mg, 0.400 mmol) and TPA4BA (173.5 mg, 0.600 mmol) afforded 8d 1 (133.2 mg, 68% yield). Yellow solid; m.p. 181-183 °C; H NMR (500 MHz, CDCl3) δ 10.31 (s, 1H), 7.96 (d, J = 8.0 Hz, 1H), 7.79 (ddd, J = 16.7, 9.0, 6.6 Hz, 3H), 7.66 (d, J = 8.1 Hz, 1H), 7.61 (s, 1H), 7.55 (s, 1H), 7.51 (d, J = 8.6 Hz, 2H), 7.49 – 7.43 (m, 2H), 7.39 (d, J = 8.4 Hz, 1H), 7.30 (t, J = 7.8 Hz, 4H), 7.16 (d, J = 8.2 Hz, 4H), 7.14 (d, J = 10.9 Hz, 2H), 7.09 (t, J = 7.3 13 Hz, 2H), 4.69 (s, 2H). C NMR (126 MHz, CDCl3) δ 191.83, 148.43, 147.34, 145.95, 143.32, 137.89, 133.63, 132.94, 132.69, 132.35, 132.16, 129.65, 129.39, 128.21, 128.02, 127.63, 127.35, 127.14, 126.06, 125.51, 124.94, 124.88, 123.46, 123.10, 38.44. + + HRMS (ESI): m/z calculated for C36H27NO [M+H] 490.2126, found 490.2125. 4.2.14. 2-((6-(4-(diphenylamino)phenyl)naphthalen-2-yl)methyl)-4-methylbenzaldehyde (8e) By following the synthetic procedure A(2), 7e (112.3 mg, 0.400 mmol) and TPA4BA (173.5 mg, 0.600 mmol) afforded 8e 1 (137.0 mg, 68% yield). Yellow solid; m.p. 192-194 °C; H NMR (500 MHz, CDCl3) δ 10.26 (s, 1H), 8.00 (s, 1H), 7.82 (q, J = 8.0, 5.1 Hz, 3H), 7.73 (d, J = 8.5 Hz, 1H), 7.62 (d, J = 8.5 Hz, 2H), 7.58 (s, 1H), 7.36 (d, J = 8.3 Hz, 1H), 7.33 – 7.26 (m, 5H), 13 7.19 (t, J = 8.6 Hz, 6H), 7.15 (s, 1H), 7.07 (t, J = 7.3 Hz, 2H), 4.61 (s, 2H), 2.42 (s, 3H). C NMR (126 MHz, CDCl3) δ 192.03, 147.71, 147.27, 144.96, 142.84, 137.93, 137.69, 135.00, 132.63, 132.57, 132.47, 132.45, 131.83, 129.30, 128.37, 128.09,

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127.97, 127.86, 127.82, 126.87, 125.47, 124.79, 124.46, 123.99, 122.98, 38.16, 21.83. HRMS (ESI): m/z calculated for + + C37H29NO [M+H] 504.2283, found 504.2284. 4.2.15. 3,3''-(1,4-phenylenebis(methylene))bis(4'-(diphenylamino)-[1,1'-biphenyl]-4-carbaldehyde) (8f) By following the synthetic procedure B(2), 7f (153.3 mg, 0.400 mmol) and TPA4BA (164.0 mg, 1.00 mmol) afforded 8f 1 (229.1 mg, 75% yield). Brown solid; m.p. 204-206 °C; H NMR (500 MHz, CDCl3) δ 10.25 (s, 2H), 7.91 (d, J = 8.0 Hz, 2H), 7.62 (d, J = 8.0 Hz, 2H), 7.50 (d, J = 8.5 Hz, 4H), 7.49 (s, 2H), 7.32 (t, J = 7.7 Hz, 8H), 7.17 (d, J = 8.0 Hz, 8H), 7.15 (d, J = 13 8.6 Hz, 4H), 7.13 (s, 4H), 7.10 (t, J = 7.3 Hz, 4H), 4.48 (s, 4H). C NMR (126 MHz, CDCl3) δ 191.82, 148.40, 147.35, 145.89, 143.48, 138.34, 132.75, 132.69, 132.20, 129.64, 129.44, 128.97, 128.03, 124.88, 123.48, 123.14, 37.87. HRMS (ESI): m/z + + calculated for C58H44N2O2 [M+H] 801.3436, found 801.3435. 4.2.16. 3,3''-(1,3-phenylenebis(methylene))bis(4'-(diphenylamino)-[1,1'-biphenyl]-4-carbaldehyde) (8g) By following the synthetic procedure B(2), 7g (153.3 mg, 0.400 mmol) and TPA4BA (164.0 mg, 1.000 mmol) afforded 8g 1 (260.2 mg, 85% yield). Orange solid; m.p. 193-195 °C; H NMR (500 MHz, CDCl3) δ 10.22 (s, 2H), 7.89 (d, J = 8.0 Hz, 2H), 7.59 (d, J = 8.0 Hz, 2H), 7.45 (d, J = 8.6 Hz, 4H), 7.45 (s, 2H), 7.31 (t, J = 7.8 Hz, 8H), 7.21 (t, J = 7.5 Hz, 1H), 7.16 (d, J = 7.7 Hz, 8H), 7.12 (d, J = 8.6 Hz, 4H), 7.09 (t, J = 7.4 Hz, 4H), 7.04 (d, J = 3.8 Hz, 2H), 7.02 (s, 1H), 4.47 (s, 4H). 13C NMR (126 MHz, CDCl3) δ 191.76, 148.37, 147.34, 145.84, 143.33, 140.62, 132.75, 132.67, 132.19, 129.55, 129.42, 129.23, 128.82, + + 128.01, 126.76, 124.86, 123.46, 123.11, 38.19. HRMS (ESI): m/z calculated for C58H44N2O2 [M+H] 801.3436, found 801.3435. 4.2.17. 4'-(diphenylamino)-3-(4-((4'-(diphenylamino)-2-formyl-5-methyl-2,3-dihydro-[1,1'-biphenyl]-3- yl)methyl)benzyl)-5-methyl-[1,1'-biphenyl]-2-carbaldehyde) (8h) By following the synthetic procedure B(2), 7h (164.0 mg, 0.400 mmol) and TPA4BA (164.0 mg, 1.000 mmol) afforded 8h 1 (219.3 mg, 66% yield). Brown solid; m.p. 213-215 °C; H NMR (500 MHz, CDCl3) δ 10.02 (s, 2H), 7.32 (t, J = 7.8 Hz, 8H), 7.22 (d, J = 8.5 Hz, 4H), 7.19 (s, 4H), 7.17 (s, 10H), 7.14 (d, J = 8.4 Hz, 4H), 7.10 (t, J = 7.4 Hz, 4H), 7.06 (s, 2H), 4.43 (s, 13 4H), 2.41 (s, 6H). C NMR (126 MHz, CDCl3) δ 194.25, 147.77, 147.47, 147.31, 143.01, 142.58, 138.38, 132.41, 131.41, 130.94, 130.04, 129.75, 129.41, 129.09, 124.77, 123.35, 122.63, 38.44, 21.74. HRMS (ESI): m/z calculated for + + C60H48N2O2 [M+H] 829.3749, found 829.3747. Draft 4.2.18. 3,3'',3''''-(benzene-1,3,5-triyltris(methylene))tris(4'-(diphenylamino)-[1,1'-biphenyl]-4-carbaldehyde) (8i) By following the synthetic procedure B(2), 7i (214.3 mg, 0.400 mmol) and TPA4BA (262.4 mg, 1.600 mmol) afforded 8i 1 (339.1 mg, 73% yield). Brown solid; m.p. 155-157 °C; H NMR (500 MHz, CDCl3) δ 10.15 (s, 3H), 7.82 (d, J = 8.0 Hz, 3H), 7.52 (d, J = 8.0 Hz, 3H), 7.39 (d, J = 8.5 Hz, 7H), 7.37 (s, 4H), 7.30 (d, J = 7.6 Hz, 6H), 7.28 (d, J = 3.0 Hz, 6H), 7.15 (d, J = 13 7.8 Hz, 12H), 7.10 – 7.06 (m, 12H), 6.84 (s, 3H), 4.39 (s, 6H). C NMR (126 MHz, CDCl3) δ 191.64, 148.31, 147.35, 145.74, 143.18, 140.88, 132.69, 132.65, 132.14, 129.46, 129.40, 127.99, 127.21, 124.84, 124.77, 123.43, 123.10, 38.07. HRMS (ESI): + + m/z calculated for C84H63N3O3 [M+H] 1162.4903, found 1162.4904. 4.2.19. 4-(anthracen-2-yl)-N,N-diphenylaniline (1a) By following the synthetic procedure A(3), 8a (87.9 mg, 0.20 mmol) afforded 1a (63 mg, 0.15 mmol, 76% yield). Brown solid; m.p. 172-174 °C; 1H NMR (500 MHz, CDCl3) δ 8.48 (s, 1H), 8.45 (s, 1H), 8.21 (s, 1H), 8.09 (d, J = 8.8 Hz, 1H), 8.06 – 8.01 (m, 2H), 7.78 (d, J = 8.8 Hz, 1H), 7.70 (d, J = 8.5 Hz, 2H), 7.55 – 7.42 (m, 2H), 7.34 (t, J = 7.8 Hz, 4H), 7.25 (d, J = 8.5 13 Hz, 2H), 7.22 (d, J = 7.8 Hz, 4H), 7.10 (t, J = 7.3 Hz, 2H). C NMR (101 MHz, CDCl3) δ 147.67, 147.40, 137.21, 134.78, 132.09, 132.00, 131.70, 130.75, 129.34, 128.72, 128.24, 128.13, 127.97, 126.36, 126.00, 125.48, 125.30, 125.29, 124.74, + + 124.54, 123.93, 123.05. HRMS (ESI): m/z calculated for C32H23N [M+H] 422.1864, found 422.1865. 4.2.20. 4-(6-methylanthracen-2-yl)-N,N-diphenylaniline (1b) By following the synthetic procedure A(3), 8b (90.7 mg, 0.200 mmol) afforded 1b (48 mg, 54% yield). Brown solid; m.p. 1 191-193 °C; H NMR (500 MHz, CDCl3) δ 8.43 (s, 1H), 8.34 (s, 1H), 8.18 (s, 1H), 8.06 (d, J = 8.8 Hz, 1H), 7.95 (d, J = 8.7 Hz, 1H), 7.79 (s, 1H), 7.76 (dd, J = 8.8, 1.5 Hz, 2H), 7.70 (d, J = 8.6 Hz, 4H), 7.35 (d, J = 8.2 Hz, 1H), 7.33 (s, 1H), 7.25 (d, J 13 = 8.7 Hz, 2H), 7.23 (d, J = 7.7 Hz, 4H), 7.11 (t, J = 7.3 Hz, 2H), 2.59 (s, 3H). C NMR (126 MHz, CDCl3) δ 147.71, 147.31, 136.79, 134.95, 134.89, 132.03, 131.55, 130.94, 130.75, 129.34, 128.62, 128.38, 127.95, 126.44, 126.13, 125.18, 124.96, + + 124.82, 124.52, 123.99, 123.03, 22.03. HRMS (ESI): m/z calculated for C33H25N [M+H] 436.2021, found 436.2023. 4.2.21. 4-(6-chloroanthracen-2-yl)-N,N-diphenylaniline (1c) By following the synthetic procedure A(3), 8c (94.8 mg, 0.200 mmol) afforded 1c (59.3 mg, 65% yield). Brown solid; m.p. 178-180 °C; 1H NMR (500 MHz, CDCl3) δ 8.44 (s, 1H), 8.34 (s, 1H), 8.17 (s, 1H), 8.06 (d, J = 8.9 Hz, 1H), 8.00 (s, 1H), 7.96 (d, J = 9.0 Hz, 1H), 7.80 (dd, J = 8.8, 1.4 Hz, 1H), 7.68 (d, J = 8.6 Hz, 2H), 7.41 (dd, J = 9.0, 1.8 Hz, 1H), 7.32 (t, J = 7.8 Hz, 13 4H), 7.23 (d, J = 8.6 Hz, 2H), 7.20 (d, J = 7.7 Hz, 4H), 7.09 (t, J = 7.3 Hz, 2H). C NMR (126 MHz, CDCl3) δ 147.64, 147.56, 137.63, 134.47, 132.10, 131.79, 131.29, 130.99, 130.14, 129.80, 129.32, 128.57, 127.94, 126.70, 126.57, 126.41, 125.97, + + 125.14, 124.69, 124.60, 123.81, 123.11. HRMS (ESI): m/z calculated for C32H22ClN [M+H] 456.1474, found 456.1477. 4.2.22. N,N-diphenyl-4-(tetraphen-9-yl)aniline (2a)

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By following the synthetic procedure A(3), 8d (97.9 mg, 0.200 mmol) afforded 2a (66.1 mg, 70% yield). White solid; m.p. 1 239-241 °C; H NMR (500 MHz, CDCl3) δ 9.19 (s, 1H), 8.86 (d, J = 8.1 Hz, 1H), 8.42 (s, 1H), 8.24 (s, 1H), 8.20 (d, J = 8.7 Hz, 1H), 7.88 (d, J = 9.0 Hz, 1H), 7.86 – 7.84 (m, 1H), 7.83 (d, J = 9.1 Hz, 1H), 7.71 (t, J = 8.0 Hz, 3H), 7.67 (d, J = 9.3 Hz, 1H), 7.64 (s, 1H), 7.32 (t, J = 7.9 Hz, 4H), 7.24 (d, J = 8.5 Hz, 2H), 7.21 (d, J = 7.7 Hz, 4H), 7.09 (t, J = 7.3 Hz, 2H). 13C NMR (126 MHz, CDCl3) δ 147.71, 147.31, 136.79, 134.95, 134.89, 132.03, 131.55, 130.94, 130.75, 129.34, 128.62, 128.38, 127.95, + + 126.44, 126.13, 125.18, 124.96, 124.82, 124.52, 123.99, 123.03, 22.03. HRMS (ESI): m/z calculated for C36H25N [M+H] 472.2021, found 472.2022. 4.2.23. 4-(9-methyltetraphen-3-yl)-N,N-diphenylaniline (2b) By following the synthetic procedure A(3), 8e (100.7 mg, 0.200 mmol) afforded 2b (75.2 mg, 77% yield). Yellow solid; 1 m.p. 247-249 °C; H NMR (500 MHz, CDCl3) δ 9.14 (s, 1H), 8.86 (d, J = 8.5 Hz, 1H), 8.29 (s, 1H), 8.06 (d, J = 8.6 Hz, 1H), 8.04 (s, 1H), 7.92 (d, J = 8.3 Hz, 1H), 7.82 (d, J = 8.9 Hz, 2H), 7.74 – 7.63 (m, 3H), 7.43 (d, J = 8.5 Hz, 1H), 7.32 (t, J = 7.8 13 Hz, 4H), 7.23 (d, J = 8.4 Hz, 2H), 7.20 (d, J = 7.9 Hz, 3H), 7.08 (t, J = 7.3 Hz, 2H), 2.62 (s, 3H). C NMR (126 MHz, CDCl3) δ 147.70, 147.41, 139.02, 135.47, 135.27, 134.64, 132.26, 130.76, 130.58, 129.44, 129.31, 128.45, 128.22, 128.14, 127.93, 127.76, 127.11, 126.28, 126.08, 125.96, 125.46, 124.51, 123.98, 123.37, 123.02, 121.21, 21.96. HRMS (ESI): m/z calculated + + for C37H27N [M+H] 486.2177, found 486.2177. 4.2.24. 4-(6-chloroanthracen-2-yl)-N,N-diphenylaniline (3a) By following the synthetic procedure A(3), 8f (160.2 mg, 0.200 mmol) afforded 3a (122.2 mg, 80% yield). Brown solid; 1 m.p. 232-234 °C; H NMR (500 MHz, CDCl3) δ 9.25 (s, 2H), 8.30 (s, 2H), 8.21 (t, J = 4.1 Hz, 4H), 7.86 (d, J = 8.9 Hz, 2H), 7.71 (d, J = 8.5 Hz, 4H), 7.68 (s, 2H), 7.33 (t, J = 7.8 Hz, 8H), 7.24 (d, J = 8.5 Hz, 4H), 7.21 (d, J = 7.8 Hz, 8H), 7.09 (t, J = 13 7.3 Hz, 4H). C NMR (126 MHz, CDCl3) δ 147.66, 147.42, 137.98, 134.74, 132.64, 131.18, 131.03, 129.35, 129.02, 128.90, + + 128.04, 127.64, 127.00, 125.53, 124.56, 124.52, 123.91, 123.07, 121.62. HRMS (ESI): m/z calculated for C58H40N2 [M+H] 765.3225, found 765.3227. 4.2.25. 4,4'-(pentaphene-2,10-diyl)bis(N,N-diphenylaniline) (3b) By following the synthetic procedure A(3), 8g (160.2 mg, 0.200 mmol) afforded 3b (125.0 mg, 82% yield). Brown solid; 1 Draft m.p. 201-203 °C; H NMR (500 MHz, CDCl3) δ 9.31 (d, J = 12.1 Hz, 2H), 8.37 (s, 1H), 8.31 (d, J = 13.6 Hz, 2H), 8.24 (d, J = 8.5 Hz, 1H), 8.23 (s, 1H), 8.11 (d, J = 8.7 Hz, 1H), 7.88 (d, J = 8.3 Hz, 1H), 7.86 (d, J = 7.3 Hz, 1H), 7.76 – 7.68 (m, 6H), 7.36 13 – 7.31 (m, 8H), 7.26 (t, 4H), 7.21 (t, 8H), 7.12 – 7.07 (m, 4H). C NMR (126 MHz, CDCl3) δ 147.68, 147.45, 137.91, 134.80, 131.17, 129.55, 129.33, 128.91, 128.23, 128.04, 126.98, 126.61, 125.54, 125.21, 124.57, 123.92, 123.06, 122.03, 121.71. + + HRMS (ESI): m/z calculated for C58H40N2 [M+H] 765.3225, found 765.3227. 4.2.26. 4,4'-(3,10-dimethylpentaphene-1,12-diyl)bis(N,N-diphenylaniline) (3c) By following the synthetic procedure A(3), 8h (166.2 mg, 0.200 mmol) afforded 3c (130.0 mg, 82% yield). Brown solid; 1 m.p. 218-220 °C; H NMR (500 MHz, CDCl3) δ 9.25 (s, 2H), 8.23 (s, 2H), 7.79 (s, 2H), 7.65 (s, 2H), 7.50 (d, J = 8.2 Hz, 4H), 13 7.38 (s, 2H), 7.18 – 7.13 (m, 12H), 7.03 – 6.98 (m, 12H), 2.62 (s, 6H). C NMR (126 MHz, CDCl3) δ 147.60, 147.08, 139.89, 135.14, 134.90, 133.15, 130.82, 130.51, 130.09, 129.24, 129.01, 128.50, 127.41, 126.36, 125.92, 124.50, 123.43, 122.76, + + 120.24, 21.84. HRMS (ESI): m/z calculated for C60H44N2 [M+H] 793.3538, found 793.3539. 4.2.27. 4,4',4''-(trinaphthylene-2,8,14-triyl)tris(N,N-diphenylaniline) (4) By following the synthetic procedure A(3), 8i (166.2 mg, 0.200 mmol) afforded 4 (168.2 mg, 76% yield). Brown solid; m.p. 1 164-166 °C; H NMR (500 MHz, CDCl3) δ 8.82 (s, 3H), 8.79 (s, 3H), 8.11 (s, 3H), 7.96 (d, J = 8.5 Hz, 3H), 7.76 (d, J = 8.5 Hz, 3H), 7.69 (d, J = 8.4 Hz, 6H), 7.33 (t, J = 7.8 Hz, 12H), 7.25 (d, J = 8.5 Hz, 6H), 7.22 (d, J = 7.7 Hz, 12H), 7.10 (t, J = 7.3 13 Hz, 6H). C NMR (126 MHz, CDCl3) δ 147.69, 147.39, 137.96, 134.70, 132.93, 131.54, 129.37, 129.11, 128.51, 127.93, + + 125.52, 124.78, 124.60, 123.87, 123.08, 122.40, 122.04. HRMS (ESI): m/z calculated for C84H57N3 [M+H] 1108.4586, found 1108.4587. Acknowledgments We are grateful to the financial support from the Fundamental Research Funds for the Central Universities (WUT: 2017IVA114, 2018IVB045). References and notes

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Scheme 1. Synthesis of TPA derivatives. Scheme 2. Synthesis of TPA derivatives with anthracene as acceptor unit. Scheme 3. Synthesis of TPA derivatives with tetraphene as acceptor unit.

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Scheme 4. Synthesis of TPA derivatives with pentaphene as acceptor unit. Scheme 5. Synthesis of TPA derivatives with trinaphthylene as acceptor unit.

Figure 1. Normalized absorption spectra of 1a-2b in dilute dichloromethane solution. Figure 2. Normalized absorption spectra of 3a-4 in dilute dichloromethane solution. Figure 3. Normalized fluorescence emission spectra of 1a-2b upon excitation at the absorption maximum in dilute dichloromethane solution (1×10-5 M). Figure 4. Normalized fluorescence emission spectra of 3a-4 upon excitation at the absorption maximum in dilute dichloromethane solution (1×10-5 M). Figure 5. Solvent polarity dependent normalized fluorescence emission spectra of 1c upon excitation at the absorption maximum Figure 6. Solvent polarity dependent normalized fluorescence emission spectra of 4 upon excitation at the absorption maximum Figure 7. HOMO and LUMO representations of compounds 1a-2b calculated at the B3LYP/6-31G(d) theory level.

Table 1. UV-visible absorption and fluorescence emission spectra data of the compounds Table 2. Calculated band gaps.

Draft

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