RU860456C - 1,4-phenylenedi-2',2''-pyridyl derivatives as electrochrome substances and electrochrome compound on their base - Google Patents

Abstract

1. Derivatives of 1, phenylenedi, 2, 2-pyridyl of the general formula wherein a). R CHj, R, “2 X С104; b) R R, t-C H ,, R2 CftHj, X c) R CH ,, R, CHjCgH, i CgHs, X BF, as electrochromic substances. 2. An electrochromic composition containing a dipyridyl derivative, tert-butylferrocene, polymethylmethacrylate and y-butyrolactone, characterized in that, in order to increase the uniformity of the electron-driven absorption in the visible range of the optical spectrum and expand it in the near infrared region, it contains the derivative 1 as a dipyridyl derivative , A-phenylenedi-2,2-pyridyl having the general formula 2X 1 R CgHg, where Sche R, tert-C4H ,, ON O R2. CfiHj, X ClO R CHs, R,, R CgHj, X BF4. 4: with the following ratio of ingredients, wt.%: Derivative 1, -phenylenedi-2, 2-pyridyl - 0.8-3.0, tert-butylferrocene - 3.0-6.0, polymethylmethacrylate - 0.5- 2.0, y-butyrolactone - the rest.

Description

The invention relates to new organic compounds, namely Derivatives 1, -phenylenedi-2 Z-nhridyl, of the general formula

Ri

1

n, (1)

I .2x;

R

l

R, R.

R C1C,

X 6) R is STC, R, t-C4.Nd,

Rg GgHs, X B) R CH

R,

35

 RU, X BF ,, as electrochromic substances and electrochromic compositions based on them, which are used 5, mainly 5 to create a device with variable light transmission. changing when an electric field is applied, for example, filters of variable optical density for solar or laser radiation, stabilizers of various types of radiation, alphanumeric display devices, etc.

Electrochromic compositions are known, including the quaternary dipyridyl salt as an electrochromic substance.

Known compounds form highly reversible electrochromic redox systems, but electrochromic compositions based on them provide light modulation only in certain parts of the visible range of the optical spectrum.

Of the known organic electrochromic compounds, the closest to them is composition 5, including the Quaternary Hyi-D salt, dipyridyl; tert-but, 1lferroi. en ,; f-butyrolactone (solvent) and gulimetipmethacrylate (substance, increased viscosity of rouiee)

O / S, however, the absorption spectrum of the electro-reduced form of a given composition of states J is predominant from two bands at different intensities. od: -i3 at the border of the near UV and visible range J, and the second - in the visible range or at its border with the infrared region of Tbio and does not cover the entire wavelength diagonal zone.

Thus, the previously known quaternary dipyridyl salts and compositions based on them do not provide uniformity of electronically attenuated absorption over the entire visible range of the spectrum (by the type of neutral filter).

The aim of the invention is to provide new compounds with electrochromic properties, and an electrochronous composition based on them with increased uniformity of electron-driven absorption in the entire visible spectrum and the expansion of this absorption 5 near infrared region

This goal is achieved by the new derivatives 1 J4- (Enilandi-2, z pyridyl of formula I and the fact that the electrochromic composition containing the dipyridyl derivative, tert-butylferrocene polymethylmethacrylate and β-butyrolactone, as the dipyridyl derivative, contains the derivative 1, -phenylenedi 2, 2-pyridyl formula I at the following D ratio of ingredients, wt.: derivative 1, A-phenylene-di2, 2-pyridyl - 0.8-3.0, tert-butylferrocene - 3.0-6.0, polymethylmethacrylate - 0.5- 2,0, butyrolactone the rest.

Derivatives of 1, -phenylenedi-2, 2 pyridyl are obtained by reacting diethylbenzene with the corresponding ketone 8 glacial acetic acid in the presence of perchloric acid or boron trifluoride etherate at a temperature of 117 ° C for 10 min. The resulting dipyridyl salt is treated with an aqueous solution of methylamine at the boil for 1 hour.

1,4-phenylenedi-2, (1-methyl-, 6-diphenyl) pyridyl dihydrochlorate.

A mixture of 1.2 g (0.01 M) of diethinylbenzene, 2 g of benzalacetophenone (0.02 N) and 2 ml of HC104 (0.02 M) in 5 ml of glacial acetic acid is heated at 117 s for 10 minutes.

The mixture was cooled, diluted with ether and 3.8 g of dipyrilyl salt was filtered off. A solution of dipirilium salt in 50 ml of glacial acetic acid with 1 J of 5 ml of a 25 ° aqueous solution of methylamine is boiled for T h. It is cooled, diluted with ether and 2.58 g (b5.78) of the product are filtered off with t mp, (isopropyl alcohol + 4-HC104) Calculated, I: C 65.9, H 4.44, C1 9.18, N 3.66. S4gNz40vS12Ng. Found,%: C 65.3, H 4.55, C1 8.62, N 3.9. IR spectroscopy data: 1100, 1620

Diperchlorate 1, -phenylenedi-2, 2 (1 methyl-h phenyl-6-tertbutyl) pyridyl,

Obtained similarly from diethinylbenzene and benzalpinacoline, mp. 256 C (isopropyl alcohol + HC104). Yield 73.22, Calculated,%: C 62.83, H 5.75, C1 9.79, N 3.86. C Cl Found,% i C 63.01, H 5.89, C1 9.63, N 3.6. IR spectroscopy data: 1100, 1620, G; EXAMPLE 2 8 and, a LX-solution of polymethylmethacrylate in y-6-butyrolactone dissolves 1, A-phenylenedi-2, (1-methyl-4, 6-yenyl) -pyridyl dihydrochlorate (2% concentration) and a mixture of (mono-DI, tri-) tert-butylferrocene (concentration) and the resulting solution are filled into an electrochromic device, as in Example 1. A voltage of 1.4 V is applied to the electrodes. Optical densities determined from the absorption spectrum of the electron-driven state at X 400, 500 , 600 and 700 nm turned out to be equal to 0.97, 0.77, 0.97, 0.82, respectively, and the values at a 400, 600, 700 nm, respectively, 1.5, 1.5 and 1.25 (cm . sample 2 of table 1). Upon stress relieving, the composition returns to its original unpainted state. The application of a controlled constant voltage value and its removal accompanies with a controlled reproduction of the spectra of the absorption of the composition in the initial and electron-driven states. EXAMPLE 3 .. In a 0.5% solution of polymethylmethacrylate in jf-butyrolactone, 1,4-phenylenedi-2, (1-methyl-4, 6-diphenyl) -pyridyl dihydrochlorate (concentration) was dissolved and a mixture of (mono-DI, tri-} tert-butyl ferrocene (concentration) and the resulting solution are filled into an electrochromic device, as in Example 1. For example, 1.5 V is applied to the electrodes. From the absorption spectra in the initial and electron-driven states, a is determined at 400, 600 and 700 nm, which turned out to be 1.78, 1.68 and 1.25, respectively (see, sample 3 of table 1). When the voltage is removed, the composition returns to its original unpainted state. The application of a controlled constant voltage value and its removal is accompanied by a controlled reproduction of the absorption spectra of the composition in the initial and electron-driven states. EXAMPLE 4. In a 1% solution of polymethylmethacrylate a-butyrolactone, 1,4-phenyleidi-2, (1 methyl-4-phenyl-b-tert-butyl) -pyridyl dihydrochlorate (concentrations) and a mixture of ( mono-, di, tri-) tert-butylferrocenes (concentration) and the resulting solution are filled into the electrochromic device, as in Example 1. When the voltage is applied to the electrodes 1.4 V, the unpainted composition acquires a neutral color. From the absorption spectra in the initial and electron-driven states, the value of a is determined at A at 400, 600, 700 nm, which turned out to be 1, 1, and 1.95, respectively (see sample 4 of table 1). Upon stress relieving, the composition returns to its original unpainted state. The application of a controlled constant voltage value and its removal is accompanied by a controlled reproduction of the absorption spectra of the composition in the initial and electron-driven states. Example 5. 1,4-phenylenedi-2,2 (1-methyl-4-phenyl-6- (4-methylphenyl) pyridyl (1%) ditetrafluoroborate in polymethyl methacrylate in y-butyrolactone is dissolved. -th concentration) a mixture of (mono-, DI-, tri-) tert-butylferrocenes (concentration) and the resulting solution fill the electrochromic device, as in Example 1. When a voltage of 1.4 V is applied to the electrodes, the composition acquires a nearly neutral color. The absorption spectra in the initial and electron-driven states determine the value of a at ~ 400, 600, 700 nm, which turned out to be equal to, respectively 1, 1.05, 1.7 (see sample 5 of Table 1.) When the voltage is removed, the composition returns to its initial state. The application of a controlled constant voltage value and its removal is accompanied by a controlled reproduction of the absorption spectra of the composition in the initial and electroinduced state. Example 6. In a 2% solution of polymethylmethacrylate in y-butyrolactone, a mixture of 1,4-phenylenedi-2, (1-methyl-4-phenyl-6-tertbutyl) pyridyl dihydrochlorate is dissolved and 1,4-phenylenedi-2, (} -methyl-4,6-diphenyl) -pyridyl dihydrochlorate (respectively 0, and 1.2% concentration x) and the mixture (myiot, DI-, tri-) of tert-butylferrocene (concentration) and the resulting solution are filled; electrochromic device, as in example 1. At electro5 Diethrafluoroborate 1, 4-pheny and 2, (1-methyl- -phenyl-b - {- methylphenyl) pyridyl. Obtained similarly from diethinylbenzene, t-methylbenzalacetophenone and boron trifluoride etherate. T, pl. 2S C, Yield / 1.1 (isopropyl alcohol + HC104). Calculated,%: C 68.75 And k,) k, F 19.79, N 3.64., Found,%: C 68.66, H 4.87, F 19, + 7 N 3.55. IR spectroscopy data: 1080, 1b15. The procedure for determining the uniformity of the electron-driven absorption of electrochromic compositions in the visible spectrum and expanding this absorption in the near infrared region is as follows. Electrochromic compositions are tested in a device consisting of two glass plates coated with CPZO3 layers with dopants on the inner sides. The glass plates are superposed one on the other with a shift in one of the directions, which makes it possible to attach the contacts to the conductive coatings. A teflon frame is placed between the glasses. The space bounded by the Teflon frame and two glass plates is filled with an electrochromic composition. In the initial and electron-driven states, the absorption spectra of the device are recorded in the wavelength range of 350-750 nm. The absorbance spectra determine the increase in optical density at 400 500, 600, and 700 nm, and then a conditional value a is calculated - the ratio of the increase in the value of the optical density of the electron-driven state at the selected wavelength and L 500 nm. With perfect uniformity of electron-driven absorption, the value of a 1 at all wavelengths. The experimental values of the electrochromic compositions are shown in Table 1. I The expansion of the electron-driven absorption in the near IR region in the range 750-1200 nm is determined by comparing the spectra of the electron-driven absorption of the prototype and the inventive composition at voltages exceeding the threshold by 0.25 B. Voltage & the case of the prototype is 0.6 V; according to the invention, the composition is 1.15 V. Example (prototype) about 6 g). i P,:) asthzog) e; ; .m (-g njiMeTriKpi-ij- .rj r.-i R. - butyrolact Oi;: /. IBOut 1 .1-dimethyl-4.4 dipyridide 11g: and 1liperchlorate (.U) NOA concentration;; -; mixture (mono-, di-, tri-) tert-butyl-rorocene (6th concentration) and the resulting solution are filled into an electrochromic device with electrodes from 0.02 cm apart from each other. A voltage of 0 is applied to the electrodes , 75 V. The spectra in the initial and electron-driven states are used to determine the value of a at b 00, 600 and 700 nm, which turned out to be 23, 7, 1.5, respectively (see prototype of Table 1). B) The above composition (a) The electrochromic device is filled with In Oj electrodes located 0.02 cm apart from each other. In the wavelength range 700-1200 nm, the absorption spectra of the device are measured in the initial state and at a voltage of 0.85 V. The experimental data of the values of optical densities for the initial and electron-driven states are given in Table. 2. An increase in the external voltage at the electrodes has practically no effect on the absorption in the wavelength region of more than 750 nm, EXAMPLE 1. In a solution of polymethylmethacrylate in y-butyrolactone, 1-phenyleidi-2, (1-methyl-4,6-diphenyl) -pyridyl dihydrochlorate (058% concentration) and a mixture of (mono-5 DI-, tri-) are dissolved tert-butylferrocene (6% concentration) and obtained. solutions fill an electrochromic device, as in the example (prototype). When 1.3 V is applied to the electrodes, the unpainted composition becomes neutral in color. From the absorption spectra in the initial and electron-driven states, the value a is determined at l 400, 600, 700 nm, which turned out to be 1.5, 1.07, respectively (see sample 1 of table 1). Upon stress relieving, the composition returns to its original unpainted state. The imposition of a controlled value of a constant voltage and its removal is accompanied by a controlled reproduction of the spectra of the absorbed composition in the initial and electrical induced states

the voltage 1.5 V is applied from the absorption spectra in the initial and electron-driven states and at 400, 600, 700 nm, which turned out to be 1.23, 1.35, respectively (see sample 6 of the table 1). Upon stress relieving, the composition returns to its original state. The application of a controlled constant voltage value and its removal is accompanied by a controlled reproduction of the absorption spectra of the composition in the initial and electron-induced states. Example 7. In 0, a solution of polymethylmethacrylate in y-butyrolactone was dissolved a mixture of 1, α-phenylenedi-2, (1-methyl-α-phenyl-b-tert-butyl) -pyripyl and diererchlorate 1, phenylenedi-2, (-methyl-, 6-diphenyl) -pyridyl - both at a 1% concentration, as well as a mixture of (mono-, ditri-) tert-butylferrocenes in concentration and the resulting solution is filled into an electrochromic device with electrodes from each other at a distance of 0.02 cm. In the wavelength range of 700-1200 nm from

the absorption spectra of the device are measured in the initial state and at voltage 1, V. The experimental data on the optical densities for both states, shown in Table 2, show that the long-wavelength limit of the electron-driven absorption is at L 1150. An increase in the voltage value leads to an increase in absorption in the near-infrared region, and a voltage cut-off returns the composition to its original state.

Example 8

An electrochromic composition, as in Example 7, with an optical density value in the electro-driven state.

puppies in the infrared region of the composition according to the invention up to 1150 nm. The composition according to the invention exhibits light stability under irradiation conditions. The combination of the above properties makes it possible to create universal filters of variable optical density with electric control.

Table 1, which is close to unity, is irradiated for 6 hours with the light of the wavelength range of 380-3000 nm and an intensity of 200 mW / cm2. After the irradiation is completed and the voltage is turned off, the electrochromic composition goes into an unpainted state with the initial absorption spectrum. As can be seen from a comparison of the known composition and the composition according to the invention, the introduction of the synthesized compounds allows one to obtain an electrochromic composition with increased uniformity of electronically absorbed absorption in the entire visible range of the spectrum as a neutral filter with a coefficient of not higher than I. Comparison with the known electrochromic composition having a long-wavelength absorption limit of 750 nm shows an expansion of electron-driven absorption

the value of the applied voltage to the electrochromic device, expressed in volts;

sample thickness, cm;

the ratio of the increase in the optical densities of the composition in the electron-driven state at the selected wavelength (, nm) and ~ 500 nm.

where D is the optical density

L is the wavelength, nm;

U, B -Replacement of broken voltage to devices

d-sample length, see

t g 6 l and c