perylene and Constraint on Emission Color Tuning

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Electron Push–Pull Effects in 3,9-Bis(p-(R)diphenylamino)perylene and Constraint on Emission Color Tuning Mina Ahn, Min-Ji Kim, and Kyung-Ryang Wee J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b01849 • Publication Date (Web): 28 Aug 2019 Downloaded from pubs.acs.org on August 30, 2019

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The Journal of Organic Chemistry

Electron Push–Pull Effects in 3,9-Bis(p-(R)-diphenylamino)perylene and Constraint on Emission Color Tuning

Mina Ahn, Min-Ji Kim, and Kyung-Ryang Wee* Department of Chemistry and Institute of Basic Science, Daegu University, Gyeongsan 38453, Republic of Korea.

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The Journal of Organic Chemistry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Abstract A series of perylene-based donor–acceptor–donor (D–A–D) compounds, 3,9-Bis(p-(R)diphenylamino)perylene (R: CN (2a), F (2b), H (2c), Me (2d), and OMe (2e)), were synthesized using 3,9-dibromoperylene with p-(R)-diphenylamine, and the intramolecular charge transfer (ICT) on the D–A–D system with regards to the electron push–pull substituents effect was investigated. By introducing various p-(R)-diphenylamine derivatives with electron-donating or electron-withdrawing R groups, the energy band gaps of the D–A– D compounds were systematically controlled, and the emission colors were efficiently tuned from green to red. As expected, the steady state emission spectra of all D–A–D compounds were observed, as well as the emission color being controlled, depending on the Hammett substituent constants (𝜎𝑝). In the Lippert-Mataga plots, the different charge transfer character was observed depending on the electron push–pull substitution, which showed gradually increased ICT characters from the electron-withdrawing to donating substitution. However, exceptionally, the strong electron withdrawing group of CN substituted 2a did not correlate with the other R group compounds. From the experimental data and DFT calculations, we assume that there is a constraint on emission color tuning to make higher energy of blue emission in the D–A–D molecular system, due to the reverse charge transfer property caused by the strong electron withdrawing group.

Keywords: Perylene, Diphenylamine, Donor-Acceptor, Electron Push-Pull, Intramolecular Charge Transfer, Band-gap Control, Emission Color Tuning


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Introduction Polycyclic aromatic hydrocarbons (PAHs) based materials play an important role in emerging technologies concerning molecular electronics, optoelectronics, energy conversion devices, and diverse forms of nano-technology.1 For example, Anthracene and Tetracene derivatives have been used as emitting materials to produce efficient and stable emission for full color organic electroluminescence devices (OLEDs) or organic light-emitting field-effect transistor (OLEFET), which demonstrated good chromaticity and luminescence efficiency with high device stability.2-3 To achieve multi-functional optoelectronic properties, many researchers are trying to develop various types of PAHs based materials. Among the various PAHs, Perylene has been regarded as an appealing light-emitting dopant molecule in OLEDs application, due to its good optical and electronic properties. Perylene in dilute solution exhibits excellent fluorescence quantum yields as high as 0.94,4 and shows an intense blue emission.5-6 In addition, the planar geometry enables molecular aggregation, which causes the generation of self-quenching, broad emission band, and bathochromic shift.7 In particular, perylene has mainly focused on the study of the perylene diimides (PDIs), which shows the different electronic and optical properties by introducing various substituents for the baypositions at the (1, 6, 7, and 12)-positions of the conjugated perylene core.8-10 The PDIs have been utilized in various applications, such as organic field-effect transistors (OFETs),11-15 light-harvesting arrays,16-17 and organic photovoltaic cells (OPVs).18-26 Furthermore, PAHs containing the donor–acceptor (D–A) system have been intensively investigated and applied to diverse research areas, due to their unique photophysical and electrochemical properties. In particular, PAHs-based dipolar organic molecules containing D–A units have been well known in many organic optoelectronic device applications.27-30 In the PAHs-based dipolar organic molecules, the donor or acceptor units influence the regulating molecular orbital partitioning, energy band gap, emission color, and charge transfer efficiency.27 Basically, these properties can be modulated either by increasing the donor and acceptor strength, or altering the π-conjugated linker between the donor and acceptor unit.31 Also, PAHs containing D–A molecular systems show intramolecular charge transfer (ICT) properties, and the ICT can be controlled by changing the donor or acceptor units.32 For example, pyrene is of interest to regioselective functionalization considering the substitution of symmetry or asymmetry about the main active site at the (1, 3, 6, and 8)positions and the K-regions at the (4, 5, 9, and 10)-positions with regards to the donor and



acceptor system.27,33 Specifically, Wang et al. reported the emission color of pyrene-based chromophores is controlled by simple functional R group (R= F, H, Me, tBu, OMe) modification at the para position of the diphenylamine (DPA) donor.34-35 Not only for the pyrene based D-A molecule, various PAHs based D–A molecules that showed controllable ICT properties have also been reported by many researchers.36-39 Likewise, donor or acceptor substituted perylenes are particularly important in terms of the controllable ICT property, which is enhanced by introducing electron-donating or electron-withdrawing groups on the centrosymmetric perylene core.34,40 The amount of charge transferred from the donor to acceptor depends on the substitution of the donor, and can be roughly described by the electron-donating or -withdrawing ability of the substituent.41 The ICT effects on perylene based D–A systems through donor modulation have been reported in the previous literature. Zagranyarski et al. reported that the optical and electronic properties of the (1, 6, 7, 12)tetrachloroperylene compounds are tuned depending on substitution of the electron-donating or -withdrawing groups at the four peri-positions, which are the (3, 4, 9, 10)-positions of the perylene core.42 Although various Perylene-based D–A materials were reported, systematic and fine control by electron push–pulled substitutions on the Perylene based D–A molecule is still to be reported. In addition, the ICT properties with emission color tuning range in the Perylene based D–A molecule also lack substantial information. In this study, we designed and synthesized a series of perylene D–A–D molecules consisting of two DPA donor units linked directly to perylene at the (3, 9)-positions as an acceptor unit. This excluded the effect on the π-conjugated linker, and facilitated stronger ICT effects between the donor and acceptor units. By introducing various DPA (p-(R)diphenylamine) derivatives with electron-donating or -withdrawing R groups, the energy band gap of the D–A–D compound was systematically controlled, and the emission colors were efficiently tuned from green to red. Different charge transfer character was observed depending on the electron push–pull substitution, which showed gradually increased ICT characters from the electron-withdrawing to donating substitution. In particular, the CNsubstituted compound emission was originated by reverse ICT character from arylamine to CN unit. This result indicates that there is a constraint on emission color tuning to make higher energy of blue emission in the D–A–D molecular system, due to the reverse charge transfer property caused by the strong electron withdrawing group.


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Results and discussion Synthesis Scheme 1. Synthesis of 3,9-bis(N,N-bis(4′-(R)-phenyl)amino)perylene. R Br I

CuI LiNH 2 R K3 PO4 24h , 130 oC DMF

R

H N

R N

Br N R

1

Buchwald-Hartwig coupling

R

2 R

2a : R=CN 2b : R=F 2c : R=H 2d : R=Me 2e : R=OMe

(60%) (78%) (79%) (83%) (81%)

Scheme 1 shows the synthetic procedures for a series of perylene-based D–A–D compounds, 3,9-Bis(p-(R)-diphenylamino)perylene (R: CN (2a), F (2b), H (2c), Me (2d), and OMe (2e)). For the first step, the donor units of the various electron-donating or withdrawing group substituted diphenylamines at the para-positions, p-(R)-diphenylamine (R: CN (1a), F (1b), H (1c), Me (1d), and OMe (1e)), were prepared according to the previously reported procedures. Then, the Perylene based D–A–D compounds were successfully synthesized by modified Buchwald-Hartwig cross-coupling reaction using 3,9-dibromoperylene with 2 molar ratios of p-(R)-diphenylamines (1). Specifically, 3,9-bis(p-(R)-diphenylamino)perylene (2) was prepared in the presence of 5 mol.% Pd2(dba)3 with Xantphos as a catalyst and excess amounts of NaOtBu base as an orange or red solid in toluene solvent with a yield of 60–81 %. All of the compounds were purified by silica gel column chromatograph using hexane/dichloromethane mixture eluents, and further purified by recrystallizations for high purity. The molecular structure of all compounds was characterized by 1H- and

13C{1H}-

NMR, elemental analysis, and mass spectrometry. The experimental section and the Supporting Information (SI) provide the detailed synthetic procedures and characterization data.



Figure 1. UV-vis absorption (top) and emission (bottom) spectra of compounds 2 in CH2Cl2 solution.


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Table 1. Photophysical properties of 2a-2e 𝑑 𝑑 7 ―1 𝑘rad × 107𝑠𝑘―1 nr × 10 𝑠 𝑘rad/𝑘nr

𝜆𝑚𝑎𝑥abs

𝜆𝑚𝑎𝑥PL

Stokes

(nm)

(nm)

Shift

Φ𝑐𝑓

τF

Compd

sol𝑎/film𝑏

sol𝑎/film𝑏

(cm-1)

sol𝑎/film𝑏

(ns)

2a

451/463

525/629

3,125

0.91/0.57

3.538

25.7

2.54

10.1

2b

491/499

558/578

2,445

0.64/0.31

4.265

15.0

8.44

1.78

2c

491/508

561/608

2,541

0.65/0.32

4.715

13.8

7.42

1.86

2d

503/513

582/605

2,698

0.61/0.30

6.246

9.77

6.24

1.57

2e

514/541

624/566

3,430

0.37/0.27

7.800

4.74

8.08

0.59

a

Measured in CH2Cl2 at room temperature (RT). b Measured in thin neat films. c Relative to 9,10-diphenylantracene or rhodamine B as standards in CH2Cl2 at RT. d Values of 𝑘rad and 𝑘nr were calculated according to the equations, 𝑘rad = Φ𝑓 /𝜏F and 𝑘nr = (1/𝜏F) ― 𝑘rad.

Photophysical Properties As shown in Fig. 1 and Fig S4-S6, the steady state UV-visible absorption and fluorescence spectra were measured both in solution and film state, and Table 1 summarizes the spectral parameters. Fig. 1 (top), and Fig. S4 of the SI show that the absorption spectra of 2a–2e were different from pure perylene unit, but the 2a showed similar absorption spectrum to perylene in the range (400–525) nm, which is red-shifted within 15 nm for the 𝑆0→𝑆1 band of perylene with less vibrational structures. In the nonpolar solvent, these properties were clearly explained, showing the broader structured absorption peak than perylene at around (400–500) nm, as shown in Fig. S5 of the SI. In addition, the 2a showed distinctive structureless single peaks in the range (250–350) nm, which were not observed in the other compounds, and the peak shape was similar to that of the pure perylene compound. The 2b– 2e compounds showed structured and relatively intense absorption bands in the range (240−310) nm, which can be attributed to the π−π* transitions of each substituent and perylene core, and showed broad, relatively weak absorption bands in the range (450−600) nm, which can be attributed to the charge transfer absorption in the ground state. From the steady state absorption spectral comparison between 2a and 2b–2e, the 2a showed a unique origin, due to the remaining perylene character. We also carefully compared the molar absorption coefficient for the 2a–2e compounds with each substituent and perylene core, to understand the substituent effects in the D–A–D compounds. It was found that the lowenergy band is relatively more affected than the high-energy band by the para substituents of the N,N-diphenylamine according to the molar absorption coefficient. In particular, the



compounds 2a−2e have a high-energy band that corresponds to a molar absorption coefficient at around (32,047–57,135) cm−1 M−1, and a low-energy band that corresponds to a molar absorption coefficient ranging (23,791 to 44,422) cm−1 M−1. Exceptionally, the CNsubstituted 2a has the stronger molar absorption coefficient in both the high- and low-energy bands than those of the other compounds. To understand the inter-molecular interactions in the steady state absorption properties, the absorption spectra in the thin film were also recorded (Fig. S6), and all the compounds were found to exhibit a broader red shift trend in comparison to their corresponding absorption spectra in solution, which implies that the perylene based D–A–D molecules may aggregate in a head to-tail arrangement to form a Jaggregate.

Figure 2. Plots of the absorption maximum and radiative decay rate constants (𝑘𝑟) versus Hammett substituent constants (𝜎𝑝).

As shown in Fig. 1 (bottom), the emission maxima of the 2a–2e ranged from (525 to 624) nm in CH2Cl2 solutions, and the emission profiles covered from green to red. In addition, we measured the solvent-dependent emission spectra for each D–A–D compound to determine the origin of emission. Fig. S10 of the SI show that all compounds are red-shifted with increasing solvent polarity from cyclohexane to CH3CN, which indicates the presence of charge transfer state in the excited state. The compounds 2b–2e show a strong ICT property in accordance with increasing the electron-donating power of the substituents, while the compound 2a diverges from this tendency. This result implies that partial charge transfer is finely controlled in this perylene based D–A–D system with substituent effects, but the trend


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is not completely consistent with the substituent effects. Table 1 shows that going from compound 2a to 2e, the fluorescence quantum yields, in general, decrease while the lifetimes increase with increasing the electron-donating power of the substituents, showing the energy gap law behavior. Both the above-mentioned values were mainly explained by the radiative and nonradiative decay rate constants. All the emission decay profiles were well fitted by the single exponential functions, suggesting the radiative decay from a single specific excited state.43 Using the relationship between the Φ𝑓 and τF values, the radiative and nonradiative decay rate constants were calculated. Following the energy gap law, the 𝑘𝑟 value gradually decreases, while the 𝑘𝑛𝑟 value rapidly increases with increasing the electron-donating power. However, as shown in Table 1, and Fig. S8 of the SI, there was a general trend in the 𝑘𝑟 value, but not in the 𝑘𝑛𝑟 value, showing that the 𝑘𝑟 value changes according to the 𝜎𝑝 value with good linear correlation. This means that the 𝑘𝑟 value is controlled by the electron effect of the substituents, and as a result, the 𝑘𝑟 value plays a key role in controlling the emission color. In particular, among the perylene series, the CN substituted 2a compound was well fitted to the correlation between the 𝑘𝑟 value and the 𝜎𝑝 value, as well as the absorption maximum and the 𝜎𝑝 value, as shown in Fig. 2. Based on these results, the CN compound seems to show the same trend as the other compounds, but the distinctive effect of the CN compound was identified, which will be further discussed in a later section.

Figure 3. Relative slope comparison of the Lippert–Mataga plots for the 2a–2e.



The intramolecular charge transfer (ICT) process was further evaluated by the relationship between the Stokes shifts in various solvents, and the Lippert-Mataga equation. Therefore, the sensitivity of the solvent polarity can be analyzed in terms of the difference between the dipole moments in the ground and excited states. The Stokes shift between the maximum absorption and emission wavelengths, in wavenumbers (Δν), is expressed using Eq. (1): 𝑣𝑎 ― 𝑣𝑓 =

( ) ( 2

ℎ𝑐𝑎30 =

×

( ) 2

ℎ𝑐𝑎30

)

𝜀―1 𝑛―1 ― × (𝜇𝑒 ― 𝜇𝑔)2 2𝜀 + 1 2𝑛 + 1 × (∆𝜇)2∆𝑓

(1)

where, μe − μg (Δμ) is the difference between the dipole moments of the excited and ground states, c is the speed of light, h is Planck’s constant, and a0 is the radius of the Onsager cavity around the fluorophore. The dielectric constant (ε) (ε: 2.02; cyclohexane, 2.38; toluene, 7.6; THF, 9.1; CH2Cl2, 37.5; CH3CN) and the refractive index (n) of the solvents are included in the term Δf, known as orientation polarizability. The Onsager radii, which were obtained by DFT calculations, were considered to be half of the average size of (19.8, 19.1, 18.6, 20.7, and 20.0) Å for 2a–2e, respectively. Fig. 3 shows the Stokes shift for the ICT process in various solvents changed linearly with Δf. Using the slope values in Eq. (1), the values of dipole moment change (Δμ) for 2a–2e were estimated to be (19.8, 15.2, 14.3, 20.3, and 21.7) D, respectively. Table S3 of the SI shows the values of the ground state dipole moment (𝜇𝑔) for energy minimized structures obtained by the DFT method close to zero due to the symmetry of compounds. Using the values of the ground state dipole moment (𝜇𝑔) and dipole moment change (Δμ), the excited state dipole moments (𝜇𝑒) were calculated to be (20.6, 15.2, 14.3, 20.3, and 22.0) D for 2a–2e. This result explains that the excited state dipole moments for 2a–2e are considerably larger than the ground state dipole moments, qualitatively showing the small charge transfer gap in the ground state and the large charge transfer gap in the excited state, as measured in the UV–Vis and emission spectroscopy. As anticipated, the trend in the excited state dipole moments was consistent with the trend in the slope of the Lippert-Mataga plots in the order 2c < 2b < 2d < 2a < 2e, which is consistent with the red-shifting interval on increasing the solvent polarity from cyclohexane to CH3CN. In short, except for 2a, according to increasing the electron-donating power of the substituents, the excited state dipole moments increase. From these results, we assumed that


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the emission of the CN substituted 2a, which has similar molecular structure to the other compounds, results from the different chromophore region.

Figure 4. CV curves of 2a–2e in CH2Cl2 solution containing 0.1 M TBAP as electrolyte, at a scan rate of 0.1 Vs−1.

Electrochemical Properties As shown in Fig 4, the electrochemical properties of 2a–2e were also investigated by cyclic voltammetry (CV), which was performed by using a three-electrode cell system; a glassy carbon electrode was used as the working electrode, while a platinum wire and SCE were used as the counter and reference electrodes, respectively. All compounds showed reversible oxidation peaks, and the first oxidation onset potential is located at (0.62, 0.64, 0.61, 0.52, and 0.44) V for 2a–2e, respectively. These peaks can be ascribed to the diphenylamine perylene unit in its oxidized form. Once a unit electron is taken out from the triarylamine to generate the oxidized form, the molecules are stabilized by the π-conjugation effect. This means that the stronger the electron-donating group of the substituents, the better the π-conjugation effect, which affects the values of the first oxidation onset potential.



Figure 5. Comparison of the experimental and calculated energy levels of HOMO–LUMO.

As shown in Fig. 5, the experimental and the calculated HOMO-LUMO energy levels for the D–A–D perylene series were compared. The experimental HOMO energy levels were estimated from the first oxidation onset potential, indicating approximately (−5.44 ± 0.2) eV. Because no cathodic reduction processes were measured, using the optical band gaps calculated from the edge of the absorption spectra, the experimental LUMO energy levels were estimated from the optical band gaps and the HOMO energy levels. In common with the HOMO energy levels, most of the LUMO energy levels show similar values, indicating approximately (-3.12 ± 0.13) eV. The calculated HOMO energy levels were in the range (5.63 ± 1.24) eV, and were higher than the experimental ones, except for 2a. The calculated LUMO energy levels were in the range (-2.84 ± 1.01) eV, and all compounds were higher than the experimental ones. The experimental and calculated values of the HOMO–LUMO energy level indicated that the OMe substitution is the most efficient electron donor group in this D–A–D perylene series. However, the most efficient electron acceptor group was not exactly matched with the experimental and calculated values in this system. The experimental value showed that the F (2b) is the best electron acceptor, while the calculated value showed the CN (2a) is the best electron acceptor. The calculated HOMO and LUMO energy levels increased with increasing electron-donating power in the order 2e > 2d > 2c > 2b > 2a,


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whereas the experimental ones were less sensitive to electronic variations of the substituents. The effect of the HOMO and LUMO levels on the substituent is also explained as a function of the Hammett substituent constants (σp), both experimentally and computationally. Fig. S8 of the SI shows that except for 2a, the experimental HOMO and LUMO energy levels of 2b– 2e show good linear correlation with the σp values, showing the HOMO slope is larger than that of the LUMO. However, compound 2a deviates from the tendency of the HOMO and LUMO energy levels of the 2b–2e. In the case of the calculated HOMO and LUMO energy levels of all compounds, the same as mentioned above applies to the experimental results of compounds 2b–2e. On the basis of the correlation of the HOMO/LUMO energy level and the Hammett substituent constants (σp), it can be seen that except for the 2a, the substituent effect impacts on the HOMO level control with the tuning of the band gap. Table 2 also summarizes the optical and calculated energy band gaps (𝐸𝑔) for 2a–2e. As the electronwithdrawing power of the para-substituent of the diphenylamino moiety increases, both of the energy band gaps are gradually expanded, showing that the calculated energy gaps are larger than the optical gaps. These results demonstrate that the band gap of the donor and acceptor substituted molecules can be significantly reduced, when compared to the pure perylene molecule. Therefore, whatever powerful electron-withdrawing group and electrondonating group are appended, the emission color is capable of the region from green to red only, and it is difficult to tune higher energy of the blue emission region. We suggest that only with the effect of the substituents, the emission color of the similar molecular structures is finely controlled by tuning the band gap. Table 2. Energy band gap properties of 2a-2e HOMO𝑎

LUMO𝑏

𝐸𝑔opt

HOMO𝑐

LUMO𝑐

𝐸𝑔

Compounds

(eV)

(eV)

(eV)

(eV)

(eV)

(eV)

2a

-5.42

-2.99

2.43

-5.63

-2.84

2.79

2b

-5.44

-3.12

2.32

-4.84

-2.17

2.67

2c

-5.41

-3.10

2.31

-4.68

-2.00

2.68

2d

-5.32

-3.07

2.25

-4.55

-1.92

2.63

2e

-5.24

-3.06

2.18

-4.39

-1.83

2.56

a

ox 𝐸HOMO (eV) = ― 𝑒(𝐸onset + 4.8). b 𝐸LUMO (eV) = ―𝑒(𝐸HOMO + 𝐸gopt). c Obtained by DFT calculation.



Page 14 of 27

DFT Calculations Fig. 6 shows the HOMO and LUMO orbitals of perylene based D–A–D compounds (2a– 2e), which were obtained by the Gaussian 16 and visualized Chem3D and GaussView program. The geometries were optimized by the DFT method using the B3LYP correlation function, employing the 6-31G (d,p) level in the vacuum state. The HOMOs for 2a–2e are distributed on the entire molecule, delocalized in the most perylene moiety with N atom and a little phenyl moiety. Given the HOMO orbital distribution of phenyl moiety, except for 2a, 2b–2e compounds were affected by the substituent effect, and it was demonstrated by the tendency of the calculated HOMO energy level, as shown in Fig. 5. The H-1 orbitals of 2a– 2e were largely populated on the diphenylamino moiety containing the para substituents. In contrast, the LUMO for 2a–2e was mainly distributed on the perylene core. Similarly, the L+1 orbitals of 2b–2e were distributed on the perylene cores with slight contribution to the phenyl moieties as the substituent’s electron-withdrawing power is increased. In contrast, the L+1 orbital of 2a was populated on the diphenylamino moiety containing the para substituents but not N atom, as well as perylene core. Due to the strong electron-withdrawing power of CN unit, the L+1 orbital distribution of 2a compound was completely transferred to the diphenylamino moiety from the perylene core. However, as shown in Table S4 of the SI, the relatively small energy level difference of the L+1 and LUMO of 2a allows both acceptor properties to be considered. 2a

2b

2c

2d

2e

L+1

LUMO

HOMO

H-1 Figure 6. Frontier orbital distributions (HOMO-1, HOMO, LUMO, LUMO+1) of 2a–2e calculated by DFT with B3LYP function and 6-31G (d,p) basis.


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Fig. S12 and Table S6 of the SI show the time-dependent DFT (TD-DFT) with the same functional and basis set confirms the origin of the π–π* transitions and the ICT transitions of 2a–2e with the spectral shift showing. The TD-DFT calculations exhibited three distinct absorption bands that are not perfectively matched with the experimental data, due to the strong spectral shift in the ICT transition. In particular, it can be seen that among the perylene series, the compound 2a has strong spectral shift in both π–π* and ICT transitions, and the most similar absorption spectrum shape to the TD-DFT calculation. Considering the transition assignment of the spectra band, the ICT bands consist of the major transition from the HOMO to the LUMO, and the minor transition from the H-1 to the LUMO. The former corresponded to transition from the perylene moiety with nitrogen atom as an electron donor to the perylene core as an electron acceptor, while the latter corresponded to transition from the diphenylamino moiety including substituents as an electron donor to the perylene core as an electron acceptor. Compound 2a has the structured absorption peak at about 380 nm, which shows the larger contribution to the transition from HOMO to L+1 than from H-2 to LUMO, and its transition corresponded to the perylene moiety with nitrogen atom as an electron donor to diphenylamino moiety, without N atom as an electron acceptor. However, compound 2b–2e compounds showed a greater contribution in the transition from H-2 to LUMO than from HOMO to L+1. It can be suggested that compound 2a has a unique transition origin distinct from the 2b–2e; the sole nitrogen atom acts like an electron donor due to the strong electronegativity and lone pair, and as a result, the transition of the 2a can occur within the diphenylamine region. As a result, unlike the other compounds, the ICT of 2a occurs not only in the opposite direction, but also in the same direction, as shown in the other compounds. Therefore, we assume that the 2a shows the additional reverse ICT property, as well as the ICT property that generally appears in the 2b–2e, and there is a limit to the emission control, due to the inversion of the region to allow ICT to occur.



Conclusion A series of perylene-based donor-acceptor-donor (D–A–D) compounds, 3,9-Bis(p-(R)diphenylamino)perylene (2a–2e), were designed and synthesized using a Buchwald-Hartwig coupling reaction, and their photophysical and electrochemical properties were investigated both experimentally and computationally. Based on the UV-Vis spectroscopy and theoretical calculation, donor-acceptor substituted molecules showed the ICT character accompanied by a significant decrease of the optical energy gap, compared with the pure donor and acceptor unit. Moreover, the ICT process was controlled from the simple substituent effect, and the emission color was adjusted from green to red. A good linear correlation between the photophysical properties and the Hammett substituent constants (σp) indicates that all compounds follow the general trend. However, exceptionally, the CN (2a) compound has proven to have unique properties that are different from the other compounds on the basis of the UV–Vis absorption spectrum measured in the Lippert-Mataga plot and the DFT/TD-DFT calculation. In particular, the DFT calculation showed that with regards to the emission control, the CN compound reached breaking point, due to the reverse ICT. As a result, we assumed that there is constraint on emission color tuning to make the higher energy of blue emission in the D–A–D molecular system, due to the reverse charge transfer property caused by the strong electron withdrawing group.


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Experimental Section General Based on standard Schlenk techniques, all of the synthesis experimental procedures were performed under a dry argon condition. All of the reagents and solvents were obtained from Sigma-Aldrich, Duksan and Chemical Oriental Chemical Industries, and used without purification. Deuterated solvent for NMR experiments was obtained from Merck or Cambridge Isotope Lab. Inc. All reactions were monitored with thin layer chromatography (TLC) using commercial TLC plates (Merck Co.). Silica gel column chromatography was performed on silica gel 60 G (230–400 mesh ASTM, Merck Co.). The synthesized compounds were characterized by 1H-NMR or 13C-NMR, and elemental analysis. The 1H and proton-decoupled

13C

spectra were recorded on a Bruker500 spectrometer operating at 500

and 125 MHz, respectively, and all proton and carbon chemical shifts were measured relative to internal residual chloroform (99.5 % CDCl3) from the lock solvent. The elemental analyses (C, H, N, O) were performed using Thermo Fisher Scientific Flash 2000 series analyzer. The 3,9-dibromoperylene44,

N,N-bis(4′-cyanophenyl)amino45

(1a)

and

N,N-bis(4′-

fluorophenyl)amino46 (1b), diphenylamine46 (1c), N,N-bis(4′-methylphenyl)amino46 (1d), and N,N-bis(4′-methoxyphenyl)amino46 (1e) were prepared based on the previously published method. The UV/Vis absorption spectra were recorded with photodiode array spectrophotometry by Agilent (HP8453), and the fluorescence emission measurements were carried out using Jasco spectrofluorometry (FP-6300) with a wavelength resolution of ~1 nm. Fluorescence lifetimes were measured by PicoQuant FluoTime 200 that takes advantage of the time-correlated single photon counting method. A pulsed diode laser operated at 20 MHz repetition rate was used as the excitation source. The FWHM of a laser pulse was typically 45 ps, and the instrument response function was ~190 ps when the Hamamatzu photomultiplier tube (H5783-01) was used. The emission quantum yields (ΦPL) were calculated using William’s comparative method for samples of five different concentrations of (1 – 10) μM, using 9,10-diphenylanthracene (ФPL = 0.95) as a reference standard. A CH Instruments 701D potentiostat was used for electrochemical measurements, and cyclic voltammetry (CV) was performed in an electrolytic solution prepared using 1 mM of electroactive compounds and 0.1 M tetrabutyl ammonium hexafluorophosphate (NBu4PF6) at RT under argon atmosphere. A three-electrode configuration, glassy carbon, platinum wire, and SCE, were used as working, counter, and reference electrodes, respectively. Thermal properties were determined



by thermogravimetric analysis (TGA) in the temperature range of 0−600 °C under a N2 atmosphere by heating at a rate of 10 °C/min.

Synthesis of 3,9-Bis(p-(R)-diphenylamino)perylene (2) A mixture of 3,9-dibromoperylene (0.6 g, 1.47 mmol), p-(R)-diphenylamine (3.82 mmol, R: CN (1a), F (1b), H (1c), Me (1d), and OMe (1e)), sodium tert-butoxide (1.02 g, 10.6 mmol), Xantphos (0.04 g, 5 mol.%), Pd2(dba)3 (0.07 g, 5 mol.%) in toluene/1,2dimethoxyethane (2:1, 40 mL) was refluxed under argon at 110 °C for overnight. After cooling to RT, deionized water (50 mL) was poured, and organic layer was separated using a separating funnel. The water layer was washed using methylene chloride (×3) for the extracted remained organic residue. After combined all of the organic solvents, the organic layer was dried over anhydrous MgSO4, and then filtered off. The solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography using CH2Cl2/hexane mixture eluent. Finally, 3,9-Bis(p-(R)-diphenylamino)perylene compounds were further purified by using hexane hot filter washing. 3,9-bis(N,N-bis(4′-cyanophenyl)amino)perylene (2a): Rf 0.15 (CH2Cl2/hexane = 1:1). Red powder (0.6 g, Yield: 60 %). mp 274 °C. IR νmax (ZnSe) 2211, 1602, 1577, 1523, 1509, 1382, 1322, 1170, 819, 806, 798, 754 cm-1. 1H-NMR (500 MHz, CDCl3, ppm) δ 8.19–8.16 (m, 2H), 8.15–8.13 (m, 2H), 7.69–7.67 (m, 2H), 7.45 (d, J = 7.5 Hz, 8H), 7.36 (t, J = 8.0 Hz, 2H), 7.26 (d, J = 8.0 Hz, 2H), 7.09 (d, J = 9.0 Hz, 8H).

13C{1H}

(125 MHz, CDCl3, ppm) δ 150.0,

133.7, 130.6, 128.8, 128.6, 128.5, 128.1, 126.8, 126.7, 122.4, 121.5, 121.0, 120.6, 118.9, 105.6. Anal. Calcd for C48H26N6: C, 83.95; H, 3.82; N, 12.24. Found: C, 83.74; H, 3.81; N, 12.45. 3,9-bis(N,N-bis(4′-fluorophenyl)amino)perylene (2b): Rf 0.40 (CH2Cl2/hexane = 1:3). Red powder (0.75 g, Yield: 78 %). mp 150 °C. IR νmax (ZnSe) 1496, 1388, 1267, 1213, 1153, 823, 809, 792, 761 cm-1. 1H-NMR (500 MHz, CDCl3, ppm) δ 8.10–8.08 (m, 2H), 8.05–8.01 (m, 2H), 7.70–7.68 (m, 2H), 7.29 (td, J = 8.5, 3.5 Hz, 2H), 7.15 (dd, J = 8.0, 2.0 Hz, 2H), 6.93– 6.89 (m, 8H), 6.86–6.81 (m, 8H).

13C{1H}

(125 MHz, CDCl3, ppm) δ 159.2, 157.3, 144.7,

143.3, 131.8, 131.6, 130.1, 129.2, 129.0, 127.1, 124.1, 123.5, 120.9, 116.1. Anal. Calcd for C44H26F4N2: C, 80.23; H, 3.98; N, 4.25. Found: C, 80.14; H, 3.81; N, 4.36. 3,9-bis(N,N-diphenylamino)perylene (2c): Rf 0.38 (CH2Cl2/hexane = 1:3). Orange powder (0.68 g, Yield: 79 %). mp 329 °C. IR νmax (ZnSe) 1583, 1488, 1388, 1324, 1290, 1267, 808,


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744, 692 cm-1. 1H-NMR (500 MHz, CDCl3, ppm) δ 8.10–8.08 (m, 2H), 8.07–8.04 (m, 2H), 7.74–7.71 (m, 2H), 7.28 (td, J = 8.5, 1.5 Hz, 2H), 7.23 (d, J = 8.0 Hz, 2H), 7.15 (t, J = 7.5 Hz, 8H), 7.01 (d, J = 7.5 Hz, 8H), 6.89 (td, J = 7.5, 1.0 Hz, 4H).

13C{1H}

(125 MHz, CDCl3,

ppm) δ 148.2, 143.2, 132.2, 130.1, 129.2, 127.8, 127.0, 124.3, 124.0, 122.0, 121.9, 121.0, 120.8, 117.8. Anal. Calcd for C44H30N2: C, 90.07; H, 5.15; N, 4.77. Found: C, 90.01; H, 5.00; N, 4.99. 3,9-bis(N,N-bis(4′-methylphenyl)amino)perylene (2d): Rf

0.33 (CH2Cl2/hexane = 1:4).

Red powder (0.78 g, Yield: 83 %). mp 257 °C. IR νmax (ZnSe) 2917, 2854, 1606, 1583, 1504, 1454, 1388, 1315, 1290, 1265, 806, 759, 711 cm-1. 1H-NMR (500 MHz, CDCl3, ppm) δ 8.05– 8.04 (m, 2H), 8.02–8.01 (m, 2H), 7.72 (s, 2H), 7.26 (td, J = 8.0, 3.5 Hz, 2H), 7.18–7.17 (m, 2H), 6.94 (d, J = 8.5 Hz, 8H), 6.88 (d, J = 8.5 Hz, 8H), 2.21 (s, 12H).

13C{1H}

(125 MHz,

CDCl3, ppm) δ 146.2, 131.7, 131.2, 130.1, 129.8, 128.9, 128.8, 127.2, 126.8, 124.4, 124.1, 122.1, 120.9, 120.3, 20.7. Anal. Calcd for C48H38N2: C, 89.68; H, 5.96; N, 4.36. Found: C, 89.41; H, 5.88; N, 4.71. 3,9-bis(N,N-bis(4′-methoxyphenyl)amino)perylene (2e): Rf 0.15 (CH2Cl2/hexane = 1:1). Red powder (0.84 g, Yield: 81 %). mp 130 °C. IR νmax (ZnSe) 2927, 2852, 1583, 1502, 1454, 1390, 1238, 1178, 1033, 825, 808 cm-1. 1H-NMR (500 MHz, CDCl3, ppm) δ 8.05–8.00 (m, 2H), 7.99–7.94 (m, 2H), 7.74–7.70 (m, 2H), 7.26–7.21 (m, 2H), 7.10 (dd, J = 8.0, 3.0 Hz, 2H), 6.88 (d, J = 9.0 Hz, 8H), 6.68 (d, J = 8.5 Hz, 8H), 3.68 (s, 12H).

13C{1H}

(125 MHz,

CDCl3, ppm) δ 154.8, 144.4, 142.6, 131.8, 131.6, 130.1, 128.3, 126.6, 126.5, 126.4, 124.5, 123.6, 120.5, 114.6, 55.5. Anal. Calcd for C48H38N2O4: C, 81.56; H, 5.42; N, 3.96; O, 9.05. Found: C, 82.00; H, 5.39; N, 3.77; O, 8.84.

Density functional theory calculations Density functional theory (DFT) calculations were performed by using Gaussian’16 software package. Full geometry optimizations in their ground state were performed using the B3LYP functional and the 6-31G (d,p) basis set for all atoms. The excitation energies and oscillator strengths for the lowest 100 singlet–singlet transitions at the optimized geometry in the ground state were obtained in time-dependent DFT (TD-DFT) calculations using the same basis set and functional as for the ground state. All Isodensity plots of the frontier orbitals were visualized by Chem3D Ultra and GaussView software. More detail DFT/TD-DFT calculation results for 9-bis(p-(R)-diphenylamino)perylenes were described in SI.




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ASSOCIATED CONTENT Supporting Information 1H

and

13C{1H}

NMR spectra of all of the D–A–D perylene compounds, TGA data,

Emission lifetime profile, Absorption and emission spectra in various solvents and solid state, Hammett plots, Lippert-Mataga plots, DFT/TD-DFT calculation results. This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author * [email protected] Notes The authors declare no competing financial interest.

ACKNOWLEDGMENTS This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF), funded by the Ministry of Education (NRF2017R1C1B1010736).



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TOC:


perylene and Constraint on Emission Color Tuning

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