JPH03148290A - Dithiolene-type organic metal complex, its production, thin film and production thereof - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (M is Ni, Pt or Pd; R<1> to R<4> are alkyl or H; at least one of R<1> to R<4> is >=3C alkyl). EXAMPLE:Bis(4,4'-di-tert-butyl-dithiobenzyl)nickel. USE:A thin film can be produced by Langmuir Blodgett process and the film is useful as a recording layer of an optical recording medium. PREPARATION:The objective compound can be produced by reacting phosphorus sulfide to a benzoin compound of formula II containing 50-100mol% of alkyl- substituted benzoin having >=3C alkyl and reacting the product with a halide of a metal such as Ni, Pd or Pt or with a potassium halide.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a conventional dithiolene-type organometallic complex and a method for producing the same, as well as a thin film containing the complex and a method for producing the same.

[Conventional technology]

Conventionally, dithiolene type organometallic complex derivatives include bis(dithiobenzyl)nickel and bis(4-dimethylamino-dithiobenzyl)nickel.

Bis(4-diethylamino-dithiobenzyl)nickel, bis(4-dimethoxy-dithiobenzyl)nickel,
Bis(1,2-dithioferrate)nickel-tetra-n-butylammonium, bis(4-methyl-1,2
-dithioferrate)nickel-tetra-n-butylammonium, bis(3,4,5,6-tetramethyl-
1,2-dithioferto)nickel-tetra-n-butylammonium, bis(3,4,5,6-tetrachloro-1,2-dithiopherto)nickel-tetra-n
- Butylammonium and the like are known, and because they have absorption in the oscillation wavelength region of semiconductor lasers, they are used as organic recording materials for optical disks (Japanese Patent Application Laid-open No. 195336/1983, etc.). Also, this complex is
- Because it acts as a stacked oxygen quencher, it is used as an additive to improve the light resistance of recording materials with poor stability such as cyanine dyes (Japanese Patent Application Laid-Open No. 59-18
5694, etc.). When using these complexes in organic recording materials for optical disks, in order to increase recording sensitivity,
It is desirable to make the recording layer as thin as possible.

[Problem to be solved by the invention]

Methods for obtaining organic thin films include spin coating and vacuum evaporation of solution and polymer dispersion films, but with either method, it is difficult to obtain a homogeneous film, and it is difficult to obtain a film without defects such as pinholes. In order to obtain this, a certain degree of film thickness is required, which is not preferable. Therefore, the Langmuir-Prodgett method (hereinafter referred to as It is preferable to use the LB method (abbreviated as LB method).

However, it has been found that organic thin films cannot be produced by the LB method using the conventionally known dithiolene type organometallic complex derivatives described above.

The present invention provides a dithiolene-type organometallic complex that can be formed into a film by the LB method, a method for producing the same, and a thin film containing the compound.

[Means to solve the problem]

The dithiolene type organometallic complex according to the present invention is as follows.

General formula (1) (wherein, M represents Ni, Pt or Pd, RlR"
, R' and R4 represent an alkyl group or a hydrogen atom, at least one of which is an alkyl group having 3 or more carbon atoms, and may be the same or different.

Since the dithiolene type organometallic complex is a hydrophobic insoluble compound, it generally tends to cause aggregation and does not form a monomolecular film on the water surface, but as represented by the above general formula (1), R1, R2, At least one of R3 and R4 is a bulky alkyl group having 3 or more carbon atoms, particularly a branched alkyl group. In this respect, the general formula (1
), it is particularly preferred that R1, R2, R3 and R4 are all bulky alkyl groups having 3 or more carbon atoms, particularly branched alkyl groups.

Specific examples of the dithiolene type organometallic complex of the present invention include:
Bis(4,4'-di-tert-butyl-dithiobenzyl)nickel, bis(4-tert-butyl-dithiobenzyl)nickel, bis(4,4'-di-isopropyl-dithiobenzyl)nickel, bis(4-tert-butyl-dithiobenzyl)nickel isopropyl-dithiobenzyl)nickel, bis(4,4'-di-isobutyl-dithiobenzyl)nickel, bis(4-
isobutyl-dithiobenzyl)nickel, bis(4,4
'-di-isopentyl-dithiobenzyl)nickel, bis(4-inpentyl-dithiobenzyl)nickel, bis(4,4'-di-neopentyl-dithiobenzyl)
Nickel, bis(4-neopentyl-dithiobenzyl)
There are nickel, etc., and there are similar ones for platinum and palladium.

The dithiolene-type organometallic complex can be produced by reacting a benzoin compound with phosphorus sulfide and then reacting a metal halide of nickel, palladium, or platinum or a potassium metal halide. The benzoin compound used includes 50 to 100 mol% of alkyl-substituted benzoin having an alkyl group having 3 or more carbon atoms.

The above benzoin compound has the general formula (n) (however,
In the formula, Rs and R1 are hydrogen or a substituent such as an alkyl group having 3 or more carbon atoms, which may be the same or different. It can be obtained by condensing benzoin.

Examples of benzaldehyde compounds include benzaldehyde,
There are p-methylbenzaldehyde, p-ethylbenzaldehyde, p-dimethylaminobenzaldehyde, p-diethylaminobenzaldehyde, etc. As benzaldehyde having an alkyl group having 3 or more carbon atoms, p-t
ert-butylbenzaldehyde, p-isopropylbenzaldehyde, p-isobutylbenzaldehyde, p
-Isopentylbenzaldehyde, etc.

The dithiolene type organometallic complex is described in the Journal of
The American Chemical Society (Jouna)
of the American Chemica
Volume 87, pages 3583-3592 (
Schrau (1965)
It can be manufactured according to the method of Zer et al. That is, the benzoin compound represented by the general formula (II) is added in an excess amount (in particular, about 1.5 times the mole of the compound).
, s.

and optionally with (NH4)2S09 in an organic solvent such as dioxane to produce a thiophosphoric acid ester corresponding to the above compound.
A dithiolene type organometallic complex can be obtained by adding /2 mol of metal halide or potassium metal halide and refluxing.

Here, as the benzoin compound represented by the above general formula (n), an alkyl-substituted benzoin having an alkyl group having 3 or more carbon atoms (R5 or R
(at least one of s is an alkyl group having 3 or more carbon atoms) is used in an amount of 50 to 100 mol%. In particular, as this alkyl-substituted benzoin, in general formula (II), R
It is preferable that 5 and Rs are an alkyl group having 3 or more carbon atoms. Examples of the metal halide compounds include nickel chloride (NiC 2) and palladium chloride (Pd(I22)).
.

There are metal chlorides such as platinum chloride (ptcQ), and the potassium metal halides include potassium chloroplatinate (KtPtCQ4), potassium nickelate chloride (KgNICQ4), and potassium chloride. Examples include potassium metal chlorides such as potassium palladate (K2P d CL), and such metal halides or potassium metal halides may be hydrates.

The dithiolene type organometallic complex obtained in this way is
After the reaction, a precipitate is produced, which can be purified by washing with acetone or the like and recrystallizing it from ethyl acetate or the like.

Thin films of dithiolene-type organometallic complexes are produced using a monolayer deposition method in which a dithiolene-type organometallic complex is developed on a subphase and transferred onto a substrate while controlling the surface pressure. It can be obtained by transferring it to. In addition to the vertical dipping method, transfer to the substrate in the monolayer deposition method is possible.
This can also be done by a horizontal attachment method or the like. The LB method is well known as one of the monolayer accumulation methods.

In the present invention, substrates on which thin films such as LB films are formed include inorganic glasses such as quartz glass and silicate glass, and those on which metal is vapor-deposited, or those on which metal oxides are sputtered. is used, but its surface may be either hydrophilic or hydrophobic.

When forming a thin film of a dithiolene-type organometallic complex by the LB method, an amphiphilic film-forming substance having a long-chain alkyl group having about 10 to 24 carbon atoms may be added. Examples of film-forming substances include fatty acids such as stearic acid, aliphatic alcohols such as stearyl alcohol, and fatty acid etheals such as methyl stearate. The mixing ratio of the dithiolene type organometallic complex and the film-forming substance is the former/
The latter is preferably about 171 to 1/20 (molar ratio), and in order to suppress a decrease in optical density due to dilution, it is desirable that the proportion of the film-forming substance be as small as possible.

〔Example〕

Example 1 The present invention will be explained in more detail with reference to Examples below.

40g of 4-tert-butylbenzaldehyde and KCN
7. Using Og, N,N-dimethylformamide 2
By using 40ml as a solvent and reacting at 90°C for 3 hours, 4,4'-di-tert-butylbenzoin 7
．． 0 g was obtained. The obtained 4,4'-G-tert
-5.0 g of butylbenzoin to 55.1 g of P2S
, (NH4)i S 043 , 1 g in dioxane for 2 hours. After cooling and filtering, add N1Cn to the filtrate.
A solution of 5.5 g of .6H,0, dissolved in 60 mg of water was added, and the mixture was refluxed for 2 hours. After washing the generated precipitate with acetone,
Bis(4,4'-di-tert-butyl-dithiobenzyl)nickel (hereinafter abbreviated as N1(TBSB)i), which is a dark green needle-like crystal, is obtained by recrystallization from ethyl acetate.
2.1 g was obtained.

The thermal decomposition temperature of this is about 340 DEG C., and the 'H-NMR spectrum and IR spectrum (KBr method) are shown in FIGS. 1 and 2, respectively.

1H-NMR spectra were performed by dissolving the sample in deuterated chloroform and using trimethylsilane as a reference substance. In FIG. 1, the peak at 1.3 ppm is based on the hydrogen of the methyl group, and the peak around 7.3 ppm is based on the hydrogen of the benzene ring. In Figure 2, the absorption of 2950aa''1 is based on the C-H bond of the methyl group, and 1350c11-' 1140(
! The absorptions at 11-' and 880an''1 are characteristic of nickel dithiolene complexes.

Next, a thin film was produced using N1 (TBSB) obtained above using an HBM type LB film production apparatus manufactured by Kyowa Interface Science Co., Ltd.

That is, when the chloroform solution (concentration 0.1 mmoQ/Q) of Nx(TBSB)z obtained above was developed on pure water at a water temperature of 15°C and compressed at a compression speed of 20 aJ/win, the resultant solution shown in Figure 3 was obtained. A surface pressure-molecular occupied area curve (hereinafter abbreviated as FA curve) was obtained.

Next, when the hydrophobically treated glass substrate was moved up and down at a rate of 10 m/win under a constant surface pressure of 20 mN/m, the N x (T B S B ) 2 monolayer on the water surface became a Langmuir-Prodgett film (Y could be accumulated on the glass substrate as a film). The absorption spectrum of the obtained film is shown in FIG.

Comparative Example 1 Bis(dithiobenzyl)nickel, bis(4-dimethylamino-dithiobenzyl)nickel, bis(4-diethylamino-dithiobenzyl)nickel and bis(4,4
'-dimethoxy-dithiobenzyl) nickel was developed on the water surface under the same conditions as in Example 1, and the F-A curve was measured. was not formed.

〔Effect of the invention〕

The dithiolene type organometallic complex derivatives according to claims 1 to 3 or obtained according to claim 4 are novel.

A thin film of molecular order can be obtained from this compound by the LB method. This thin film is useful as a recording layer of an optical recording medium.

[Brief explanation of the drawing]

Figure 1 shows the 'H-NMR spectrum of N1 (TBSB), Figure 2 shows the IR spectrum of N1 (TBSI3)2, and Figure 3 shows the F-NMR spectrum of N1 (TBSB)2. The diagram showing the A curve and Figure 4 are Ni (TBSB)
2 Absorption Spectrum of Langmiure Projet Film The one shown in the same figure (d) is an improvement on this point, in which the high step part (in this example, the north pole) of the magnetic pole face facing the yoke 13 is formed in a sawtooth shape. This is what I did. In this way, it is possible to make the positive rising pulse large and the negative falling pulse small when pressing a key, and to make the positive rising pulse small and the negative falling pulse large when dekeying, making it possible to recover the key. By setting a threshold level higher than the positive rising pulse of time, it is possible to easily extract only the pulse that occurs when a key is pressed. Next, a second embodiment of the present invention will be explained with reference to FIGS. 7 and 8. In this embodiment, the full-stroke sensing means photoelectrically generates pulses as the key itself, which is the operator, moves. In this embodiment, a support frame 21a is provided protruding from the lower surface of the key 21, and a pattern plate 22 on which an opaque horizontal stripe pattern 22a is formed on a transparent film at a fine pitch by printing or the like is attached to the support frame 21a. is held along the longitudinal direction to constitute an optical change inducing means. On the other hand, for the frame 2 and the printed circuit board 23. The support frame 21a and the pattern [22 can be inserted into the H
Letter-shaped slits 2d and 25a are provided corresponding to each key, respectively, and a transmission type photosensor 24 is provided on both sides of the printed circuit board 23 with the slit 23a in between, with a light emitting part 24a and a light receiving part 24b facing each other. are arranged to constitute optical change detection means. Now, by pressing the key, the pattern board 22 is moved to the photo sensor 24.
When passing between the light emitting part 24a and the light receiving part 24b, the received light beam is intermittently blocked by the opaque horizontal striped pattern 22a, and a current flows to the light receiving part 24b each time the transparent part passes. Therefore, it is also possible to generate a large number of pulses corresponding to the amount of key movement operation in a non-contact manner during the entire key press operation. Next, a third embodiment of the present invention will be described with reference to FIGS. 9 to 12. In this embodiment as well, pulses are generated photoelectrically by movement of the key itself. In this embodiment, a hollow hanging portion 31a serving as an upper limit stopper and a lower limit stopper is provided on the lower surface of the 1l 151, and the wall surface 151b is formed into a cylindrical surface centered on the fulcrum axis C in the rotation direction of the key 31. As shown in FIG. 11, a pattern plate 32 having a black and white horizontal striped pattern is pasted thereon, or a horizontal striped pattern is directly applied to the rear wall surface 31b of the hanging portion 31a with jet ink to form a patterned surface 32a. . In this way, an optical change inducing means is constituted. On the other hand, a reflective photosensor 34 is disposed on the printed circuit board 33 for each key, facing the pattern surface 32, thereby configuring an optical change detecting means. As shown in FIGS. 12(A) to 12(C), this reflective photosensor 34 includes a light emitting element (LEp) 34a. A light emitting section 54A consisting of a condensing lens 34b, E54Q and a reflecting surface 34d, a light receiving element (photodiode or phototransistor) 34g, and light receiving lenses 34f, 34g.
and a light receiving section 34B consisting of a reflective surface 34h. Note that since the light emitting section 34A and the light receiving section 34B are constructed in the same way, FIG. The light emitted from the light emitting element 34a is transmitted through the condensing lens 34.
It becomes a parallel beam of light due to b, and after changing its direction at right angles on the reflecting surface 34d, it passes through the condensing lens 34c and the repatterned surface 32b.
The reflected light from the pattern surface 32b becomes a parallel beam of light by the light receiving lens ES4g, changes direction at right angles by the reflecting surface 34h, and then is reflected by the light receiving lens 34f onto the light receiving element 5.
The light is received on 4e. Therefore, when the pattern surface 32b swings downward about the fulcrum C by pressing a key, the light receiving section 34B intermittently receives the light emitted from the first light emitting section 34A and photoelectrically converts it, and according to the change in the amount of light received. generates a large number of electrical pulse signals. Note that the concave groove E51c provided in the hanging portion 31b is an escape groove in which the photosensor 34 is inserted and the key 1 is moved rearward when the key 31 is attached to and detached from the frame 2. Next, we will explain an example in which this invention is applied to an electronic keyboard instrument, such as an electronic piano, which can provide the same touch feeling as a keyboard instrument equipped with a hammer like a piano. . 13 to 24 show a fourth embodiment of the present invention. In this embodiment, the full-stroke sensing means senses the movement of an interlocking member that is moved by a greater amount than the movement of the key in conjunction with a key depression operation, and magnetically generates a pulse. First, this keyboard device will be briefly explained using FIGS. 13 and 14. The key 41 has a cylindrical inner surface concave surface 41a at its base end, and this concave surface 41a slidably contacts a cylindrical pin 43 fixed to the rear end of the slit 42a of the frame 42. A cylindrical pin 44 is fixed to the front end of the slit 42a, and the base end of an interlocking member (hereinafter referred to as a "hammer" for convenience) 45 made of a crank-shaped mass (for example, iron) is fixed to the front end of the slit 42a. The formed concave surface 45a having a cylindrical inner surface is slidably in contact with the rear end stepped portion 45'b, and the proximal end is connected to a pin 43.
The free end of the plate spring 46 fixed to the hammer 45 is engaged.
is biased in the clockwise direction as shown in FIG. 14, and the key 41 is also biased in the clockwise direction near the base end of the leaf spring 46, giving each of them a return habit. The hammer 45 has a recess 41b provided at the lower side of the key 41.
An engagement pressing portion 45c that engages with the key 41 is provided, and when the key 41 is rocked downward when the key is pressed, the hammer 45 is also rocked in the same direction against the biasing force of the leaf spring 46. At this time, since there is a large difference in the distance between the engagement pressing part 45Q of the hammer 45 and the pin 43, 44 which is the respective fulcrum (that is, the distance between the engagement pressing part 45c and the fulcrum 44 of the hammer 45 is larger than that of the hammer 45). (the distance is short), the stroke of the hammer 45 can be expanded several times by a slight stroke of the key 41, and a touch feeling similar to that of a piano can be obtained. In order to apply the present invention to a keyboard device having the above structure, it is convenient to use the hammer 45 whose movement is expanded. Therefore, as shown in FIG. 15, the lower side surface of the hammer 45 is subdivided into a fan shape with the pin 44 as the center.
A magnet pattern 45d in which ti and south poles are alternately magnetized is provided, and a resin frame 47 molded by injection molding as shown in FIG. 16 is fixed on the lower surface of the frame 42.
The magnet pattern 45d of the hammer 45 is inserted through each of the narrow gaps 47a of the frame 47 while maintaining a slight gap from both side walls. When molding the frame body 47, a first
A flexible substrate 48 having a plurality of conductive patterns 48a (for example, one octave of the hammer 45) as shown in FIG. 7 was bent and inserted so that the conductive patterns 48a were in the state shown in FIG. Then inject the resin. Conductive patterns 48a, as shown in FIG. The conductive patterns on both side walls 47b and 47d are shifted by one pitch of the magnet pattern 45d provided on the hammer 45. Here, to briefly explain the manufacturing method of the hammer 45, the hammer 45 is divided into three parts, a tip part 45e, a middle part 45f, and a base part 45g, as shown in FIG. For example, a notch 45h as shown in the middle part 45f shown in FIG. Outsert the resin layer 45i. Tip portion 45. Similarly, the base 45g is also outserted with resin on the ridgeline portion, and assembled into one piece as shown in FIG. 19.

Claims (1)

[Claims] 1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, M represents Ni, Pt or Pd, R^1, R
^2, R^3 and R^4 represent an alkyl group or a hydrogen atom, at least one of which is an alkyl group having 3 or more carbon atoms, and each may be the same or different. Organometallic complexes. 2. In the general formula (I) according to claim 1, R^1, R^
2. The dithiolene type organometallic complex according to claim 1, wherein R^3 and R^4 are branched alkyl groups having 3 or more carbon atoms. 3. The dithiolene type organometallic complex according to claim 2, wherein the branched alkyl group having 3 or more carbon atoms is a tert-butyl group. 4. After reacting a benzoin compound containing 50 to 100 mol% of an alkyl-substituted benzoin having an alkyl having 3 or more carbon atoms and phosphorus sulfide, reacting a metal halide of nickel, palladium or platinum or potassium metal halide. A method for producing a dithiolene type organometallic complex according to claim 1, characterized in that: 5. A thin film comprising the dithiolene type organometallic complex according to any one of claims 1 to 3. 6. The method for producing a thin film according to claim 5, characterized in that it is produced by a monolayer deposition method.