CN101381317B

CN101381317B - Third-order nonlinear optical material tetrabutyl ammonium fullerene and synthetic method thereof

Info

Publication number: CN101381317B
Application number: CN2008102244931A
Authority: CN
Inventors: 周云山; 王萱; 张立娟
Original assignee: Beijing University of Chemical Technology
Current assignee: Beijing University of Chemical Technology
Priority date: 2008-10-17
Filing date: 2008-10-17
Publication date: 2011-01-12
Anticipated expiration: 2028-10-17
Also published as: CN101381317A

Abstract

The invention provides a third-order nonlinear optical material, namely a tetrabutyl ammonium fullerene ball and a synthesizing method thereof, which belongs to the field of functional materials. The prior inorganic and organic nonlinear optical materials have the problems of easy deliquescence, poor thermal stability, complicated preparation and the like respectively. The molecular formula of the tetrabutyl ammonium fullerene ball provided by the invention is (NH4)18[(C16H36N)4]24[Mo132O372(H2O)72(CH3COO)30].ca.7NH4CH3COO.ca.173H2O. In the method, after {Mo132} and tetrabutyl ammonium bromide are dissolved in water respectively according to the mass ratio of 1 to 42, and are adjusted by acetic acid respectively until the pH value is between 3.5 and 4.5, the {Mo132} and the tetrabutyl ammonium bromide are mixed to obtain the tetrabutyl ammonium fullerene ball. The third-order nonlinear optical material has the advantages of uneasy deliquescence, high thermal stability, larger nonlinear absorption and non-linear refraction coefficient, self-defocusing property and simple preparation.

Description

A kind of third order non-linear optical material TBuA fullerene ball and synthetic method thereof

Technical field

The invention belongs to field of functional materials, be specifically related to a kind of hybrid inorganic-organic third order non-linear optical material and synthetic method thereof.

Background technology

Nonlinear optical material has important use and is worth at aspects such as optical Information Processing, all-optical switch, photometry calculation, optical communications.Third order non-linear optical material is to realize all-optical switch, photometry calculation and the complex conjugate basis of phase place, the efficient of the full optical device of the high bit rate data processing of series and parallel, the performance of used third-order non-linear material when depending on the optical signal coupling.Mineral crystal is the nonlinear optical material that is studied the earliest, and has been applied in the development of device, but the inorganic nonlinear optical material time of response is long, and preparation technology is difficulty, can select kind single, easily drawbacks limit such as deliquescence its application.In recent years, the third-order nonlinear optical character of organic compound material becomes the focus of research, and the material of reporting in the document has poly-sulphur benzene, ferrocene deriv etc. to grip organic polymer, soccerballene, semi-conductor and cluster compound etc. altogether.Organic molecule, superpolymer nonlinear optical material are big because of having nonlinear optical coefficients, transparent wavelength range is wide, and intrinsic is short switching time, the optical damage threshold height, advantage such as good processability and receive scientific research person's concern, but shortcomings such as poor heat stability, synthetic complexity but had.

Summary of the invention

The objective of the invention is to solve the problems of the prior art, a kind of deliquescence, synthetic method is simple, thermostability is high hybrid inorganic-organic third order non-linear optical material and synthetic method thereof of being difficult for is provided.

The molecular formula that hybrid inorganic-organic third order non-linear optical material TBuA richness provided by the present invention is reined in rare ball is

(NH ₄) ₁₈[(C ₁₆H ₃₆N) ₄N] ₂₄[Mo ₁₃₂O ₃₇₂(H ₂O) ₇₂(CH ₃COO) ₃₀]·ca.7NH ₄CH ₃COO·ca.173H ₂O。

TBuA richness provided by the present invention is reined in the synthetic method of rare ball, may further comprise the steps: with the amount of substance ratio is 1:42's

(NH ₄) ₄₂[Mo ₁₃₂O ₃₇₂(CH ₃COO) ₃₀(H ₂O) ₇₂] ca.300H ₂Oca.10CH ₃COONH ₄(code name is { Mo ₁₃₂) and Tetrabutyl amonium bromide respectively soluble in water, and after transferring pH to be 3.5～4.5 with acetate respectively,, stir the two mixing, obtain precipitation, filter, washing, natural air drying promptly obtains hybrid inorganic-organic third order non-linear optical material TBuA fullerene ball.

With existing third-order non-linear material compared, hybrid inorganic-organic third order non-linear optical material provided by the present invention (TBuA fullerene ball) has bigger non-linear absorption and nonlinear refraction coefficient, and highly stable at normal temperatures, synthetic method is simple, raw material is easy to get, the productive rate height.

Description of drawings

Fig. 1, concentration are 1 * 10 ^-5The DMF solution Z-scanning perforate curve of the TBuA fullerene ball of M.

Fig. 2, concentration are 1 * 10 ^-5The DMF solution Z-scanning closed pore curve of the TBuA fullerene ball of M.

Wherein solid line is the theoretical curve after the match, and the black round dot is an actual measured value.

The invention will be further described below in conjunction with the drawings and specific embodiments.

Embodiment

Employed Tetrabutyl amonium bromide and acetate are the commercial goods among the following embodiment.

(NH ₄) ₄₂[Mo ₁₃₂O ₃₇₂(CH ₃COO) ₃₀(H ₂O) ₇₂] ca.300H ₂Oca.10CH ₃COONH ₄({ Mo ₁₃₂) for to press literature method synthetic (Angew.Chem.Int.Ed.Eng1.37,3359-3363 (1998)), concrete steps are: with (NH ₄) ₆Mo ₇O ₂₄4H ₂O (5.6g, 4.5mmol) and CH ₃COONH ₄(12.5g 162.2mmol) is dissolved in the 250ml water, adds N ₂H ₄H ₂SO ₄(0.8g 6.1mmol) stirs 10min, after solution becomes blue-greenish colour, adds the CH of 50% (volume fraction) ₃COOH (83mL), solution becomes is green, leaves standstill in the 500ml Erlenmeyer flask 4 days, filters the alcohol flushing with 90%.

Embodiment

1) 0.234g Tetrabutyl amonium bromide (0.726mmol) is dissolved in the 20ml water, transfers pH=4 with acetate;

2) with 0.5g{Mo ₁₃₂(0.0173mmol) be dissolved in 20ml water, transfer pH=4 with acetate;

3) with step 1) and 2) in the solution that obtains mix, stir 20min, obtain precipitation, suction filtration, the water flushing, natural air drying obtains the TBuA fullerene ball, measures its molecular formula through infrared spectra, UV spectrum, ultimate analysis and thermogravimetric analysis and is (NH ₄) ₁₈[(C ₁₆H ₃₆N) ₄N] ₂₄[Mo ₁₃₂O ₃₇₂(H ₂O) ₇₂(CH ₃COO) ₃₀] ca.7NH ₄CH ₃COOca.173H ₂O.

It is 1 * 10 that the TBuA fullerene ball for preparing in the foregoing description is mixed with concentration ^-5Behind the DMF solution of the TBuA fullerene ball of M, measure its third order non-linear optical property.The third-order non-linear refractive index n ₂(m ²W ^-1), uptake factor β (mW ^-1), the real part Rex of polarizability ⁽³⁾With imaginary part Imx ⁽³⁾It is the main performance index of material.Adopt the Z-scan method on the NL303 of EKSPLA company type nanosecond Nd:YAG laser apparatus, to test.Record sample and present self-defocusing character, its data such as table 1.

Test condition: sample pool thickness L=1mm, incident wavelength λ=532nm, laser energy E ₀=20.28 μ J, focal length of lens 20cm, the linear transmittance S=0.25 of aperture, waist radius ω ₀=30 μ m, pulse width τ=5ns, light velocity c=3 * 10 ⁸M/s.

The performance perameter of the TBuA fullerene ball that table 1 the present invention is prepared

Claims

1. a third order non-linear optical material TBuA fullerene ball is characterized in that the molecular formula of described TBuA fullerene ball is

2. the synthetic method of the described a kind of third order non-linear optical material TBuA fullerene ball of claim 1 is characterized in that, may further comprise the steps: (the NH that with the amount of substance ratio is 1: 42 ₄) ₄₂[Mo ₁₃₂O ₃₇₂(CH ₃COO) ₃₀(H ₂O) ₇₂] ca.300H ₂Oca.10CH ₃COONH ₄Soluble in water respectively with Tetrabutyl amonium bromide, and after transferring pH=3.5～4.5 with acetate respectively, with the two mixing, stir, filter, washing, natural air drying obtains third order non-linear optical material TBuA fullerene ball.