Synthesis and Third-order Nonlinear Optical Properties of Indiumphthalocyanine-functionalized Four-arm Star Polymethylmethacrylate†

doi:10.7503/cjcu20130689

Abstract

Abstract:

Using tetra-kis(2-chloropropionamido) indium(Ⅲ) phthalocyanine chloride [InClPc(NHCOCHClCH₃)₄] as initiator, a novel four-arm star polymethylmethacrylate(PMMA-InClPc) with an indium chloride phthalocyanine core was synthesized by atom transfer radical polymerization(ATRP) method. PMMA-InClPc structure was characterized by Fourier transform infrared(FTIR) spectroscopy, ultraviolet-visible(UV-Vis) spectroscopy and hydrogen nuclear magnetic resonance spectroscopy(¹H NMR) techniques. The molecular weight and molecular weight distribution of polymer sample were measured by gel permeation chromatograph(GPC). Polymerization reaction kinetics of the synthesized polymer was also studied by GPC. The results show that polymerization process follows a first-order reaction kinetics. The third order nonlinear optical properties were measured by the Z-scan technique at 532 nm using a frequency-doubled Q-switching Nd∶YAG laser pulse with pulse width of 21 ps. When the molecular weight of polymer is 2902, the third-order nonlinear polarizability χ⁽³⁾ reaches the maximum value, which is 7.216×10^-10 esu by calculation. These results display that the synthesized PMMA-InClPc polymer has potential nonlinear optical applications.

Key words: Indium phthalocyanine chloride, Atom transfer radical polymerization, Third-order nonlinear polarizability, Z-scan

CLC Number:

O631

TrendMD:

SHEN Liyuan, WU Yanying, LIU Dajun, HE Xingquan. Synthesis and Third-order Nonlinear Optical Properties of Indiumphthalocyanine-functionalized Four-arm Star Polymethylmethacrylate^†[J]. Chem. J. Chinese Universities, 2014, 35(2): 409.

Figures/Tables 9

Scheme 1 Synthetic routes of PMMA-InClPc

Table 1 Data of UV-Vis spectrum of the indiumphtha-locyanine chloride derivatives

Sample	λ(B band)/nm	λ(Q band)/nm
InClPc(NO₂)₄	360	671, 744
InClPc(NH₂)₄	350	653, 710
InClPc(NHCOCHClCH₃)₄	364	626, 696
PMMA-InClPc	347	687

Fig.1 UV-Vis spectra of the indiumphthalocyanine chloride derivatives(0.1 mg/mL) in DMFa. InClPc(NO2)4; b. InClPc(NH2)4; c. InClPc(NHCOCHClCH3)4; d. PMMA-InClPc(NH2)4.

Fig.2 GPC traces of different reaction time of PMMA-InClPc obtained through ATRPReaction time, t/h: a. 1; b. 3; c. 6; d. 9; e. 11; f. 12.

Fig.3 Plots of ln([M0]/[Mt])(a) and conversion(b) versus time

Table 2 Data obtained from GPC traces of PMMA-InClPc

t/h	Conv.(%)	M_n	M_w/M_n
1	21.2	4657	1.22
3	24.9	17017	1.24
6	33.1	37294	1.31
9	37.9	54180	1.33
11	42.3	66231	1.35
12	43.3	75672	1.36

Fig.4 Closed aperture Z-scan curve of samples 1(A), 2(B) and 3(C)

Fig.5 Open aperture Z-scan curve of samples 1(A), 2(B) and 3(C)

Table 3 Nonlinear optical properties of PMMA-InClPc evaluated from Z-scans

Number	M_n	10¹¹β/(m·W^-1)	10¹⁷γ/(m²·W^-1)	10¹⁰χ⁽³⁾/esu	t/h
1	2015	420	7	4.132	0.5
2	2902	640	21	7.216	1
3	6253	330	11	3.845	2
4	9394				3

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