Synthesis and Properties of Triphenylamine-containing Asymmetrical Perylene Diimides†

doi:10.7503/cjcu20150549

Abstract

Abstract:

Two asymmetrical perylene diimides with triphenylamine structure, N-(2-ethylhexyl)-N'-(4-triphenylamine)-3, 4, 9, 10-perylene diimide(PDI-ATPA) and 4, 4', 4''-tri[N-(2-ethylhexyl)-3, 4, 9, 10-perylene diimide]-triphenylamine(PDI-TATPA), were designed and synthesized, using branched alkyl chain substituted asymmetrical perylene monoanhydride monoimide(AsPDA-Ⅰ) as the electron-accepting species and different functional triphenylamines, 4-aminotriphenylamine(ATPA) and 4, 4', 4''-triaminotriphenylamine(TATPA), as the electron-donating moieties, respectively. The chemical structures were characterized by proton nuclear magnetic resonance(¹H NMR), Infrared(IR) spectra and elemental analysis. The optical properties and aggregation behavior in solution were investigated by UV-Vis absorption and fluorescence emission spectra. Besides, molecular simulations were carried out to elucidate the molecular orbitals, energy levels and dipole moments of two asymmetrical perylene diimides. The results demonstrated that introducing the triphenylamine structure at the imide nitrogen of perylene diimide not only broadens the photo absorption region of perylene diimide but also has no effect on the absorption properties of the perylene core because of nodes in the highes occupied molecular orbital(HOMO) and lowest unoccupied molecular orbital(LUMO) at the imide nitrogen. Photoinduced electron transfer(PET) process take place from the eletron-donating moieties-ATPA and TATPA to the electron-accepting unit-perylene core, which has been confirmed by molecular simulations and lead to the fluorescence quenching. PDI-TATPA showed a star-shaped structure with highly regularity, which has been proven by the simulation data of dipole moment and has caused the self-assembly behavior easily occur in solution. Due to the self-assembly behavior, there are some differences between the UV-Vis spectra of PDI-ATPA and that of PDI-TATPA.

Key words: Triphenylamine, Perylene diimide, Asymmetrical, Self-assembly

CLC Number:

O621.1

TrendMD:

KONG Lushi, TIAN Guofeng, LI Feng, QI Shengli, WU Dezhen. Synthesis and Properties of Triphenylamine-containing Asymmetrical Perylene Diimides^†[J]. Chem. J. Chinese Universities, 2015, 36(12): 2409.

Figures/Tables 8

Table 1 Elemental analysis, UV-Vis, and IR data of PDI-ATPA and PDI-TATPA

Compd.		Elemental analysis(%, calcd.)					UV-Vis(CHCl₃), λ_max/nm	IR(KBr), $ν ˙$ /cm^-1
Compd.		C		H		N	UV-Vis(CHCl₃), λ_max/nm	IR(KBr), $ν ˙$ /cm^-1
PDI-ATPA	80.62(80.52)		5.41(5.27)		5.63(5.73)		304, 460, 491, 527	2958, 2925, 2856, 1700, 1660, 1591, 1497, 1340, 750
PDI-TATPA	78.12(78.38)		5.15(5.02)		5.64(5.74)		310, 464, 493, 530	2954, 2925, 2858, 1697, 1656, 1589, 1502, 1340, 744

Table 1 Elemental analysis, UV-Vis, and IR data of PDI-ATPA and PDI-TATPA

Compd.		Elemental analysis(%, calcd.)					UV-Vis(CHCl₃), λ_max/nm	IR(KBr), $ν ˙$ /cm^-1
Compd.		C		H		N	UV-Vis(CHCl₃), λ_max/nm	IR(KBr), $ν ˙$ /cm^-1
PDI-ATPA	80.62(80.52)		5.41(5.27)		5.63(5.73)		304, 460, 491, 527	2958, 2925, 2856, 1700, 1660, 1591, 1497, 1340, 750
PDI-TATPA	78.12(78.38)		5.15(5.02)		5.64(5.74)		310, 464, 493, 530	2954, 2925, 2858, 1697, 1656, 1589, 1502, 1340, 744

Table 2 1H NMR data of PDI-ATPA and PDI-TATPA

Compd.	¹H NMR(400 MHz, CDCl₃), δ
PDI-ATPA	8.71—8.59(m, 8H, PhH), 7.30(t, 4H, J=7.8 Hz, PhH), 7.21(d, 8H, J=7.4 Hz, PhH), 7.07(t, 2H, J=7.2 Hz, PhH), 4.16(t, 2H, J=8.0 Hz, CH₂), 1.97(s, 1H, CH), 1.42—1.32(m, 8H, CH₂), 0.89(t, 6H, J=7.4 Hz, CH₃)
PDI-TATPA	8.41—8.13(m, 24H, PhH), 7.41—7.34(m, 12H, PhH), 4.15(t, 6H,J=8.6 Hz, CH₂), 1.92(s, 3H, CH), 1.42—1.33(m, 24H, CH₂), 0.91(t, 18H, J=7.2 Hz, CH₃)

Scheme 1 Synthetic routes of PDI-ATPA and PDI-TATPA

Fig.1 Normalized UV-Vis absorption spectra of AsPDA-Ⅰ(a), PDI-ATPA(b) and PDI-TATPA(c) in CHCl3 c(CHCl3)=1×10-5 mol/L.

Table 3 Optical data of AsPDA-Ⅰ, PDI-ATPA and PDI-TATPA

Compd.	λ_{abs. max}/nm	λ_{em. max}/nm	ε_max/(cm^-1·L·mol^-1)	λ_edge/nm	$E g a$ /eV	△λ/nm	φ^b
AsPDA-Ⅰ	522	535	164200	555	2.23	13	0.99
PDI-ATPA	527	537	109000	587	2.11	10	0.02
PDI-TATPA	530	539	122000	612	2.03	9	0.01

Table 3 Optical data of AsPDA-Ⅰ, PDI-ATPA and PDI-TATPA

Compd.	λ_{abs. max}/nm	λ_{em. max}/nm	ε_max/(cm^-1·L·mol^-1)	λ_edge/nm	$E g a$ /eV	△λ/nm	φ^b
AsPDA-Ⅰ	522	535	164200	555	2.23	13	0.99
PDI-ATPA	527	537	109000	587	2.11	10	0.02
PDI-TATPA	530	539	122000	612	2.03	9	0.01

Fig.2 Normalized UV-Vis absorption(a) and flourescence emission spectra(b) of AsPDA-Ⅰ(A), PDI-ATPA(B) and PDI-TATPA(C) in CHCl3 c(CHCl3)=1×10-5 mol/L, λexcit.=485 nm.

Fig.3 UV-Vis absorption spectra of PDI-ATPA(A) and PDI-TATPA(B) in CHCl3 with different concentrations c/(mol·L-1): a. 1×10-6; b. 5×10-6; c. 1×10-5; d. 2×10-5.

Table 4 Molecular simulation results of AsPDA- I, PDI-ATPA and PDI-TATPA

Compd.	Energy gap/eV	Diploe moment
AsPDA-Ⅰ	2.79	4.1594
PDI-ATPA	1.92	0.7271
PDI-TATPA	2.06	0.4360

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