JP2010260951A - Method for controlling circularly-polarized light emission and circularly-polarized light emitting material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide: a method for controlling the direction of circularly-polarized light emission by selecting a functional group and pH of the circularly-polarized light emitting material; a method for controlling the direction of the circularly-polarized light emission by altering pH of the circularly-polarized light emitting material; a method for controlling the intensity of the circularly-polarized light emission by altering pH or temperature of the polymerized circularly-polarized light emitting material; and a new circularly-polarized light emitting material usable in the method. <P>SOLUTION: The method for making left-handed circularly-polarized light luminescent includes adjusting pH of a solution containing a composite of a predetermined aromatic hydrocarbon derivative included in a cyclodextrin to 12 or lower, or adjusting pH of the solution to ≥14. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for controlling circularly polarized light emission and a circularly polarized light emitting material, specifically, a method for controlling the emission direction of circularly polarized light by selecting the functional group and pH of the circularly polarized light emitting material, and the pH of the circularly polarized light emitting material. A method for controlling the emission direction of circularly polarized light by changing the pH, a method for controlling the intensity of circularly polarized light by changing the pH or temperature of the polymerized circularly polarized light emitting material, and a novel that can be used in the above method The present invention relates to a circularly polarized light emitting material.

  Circularly polarized light emission is the difference in emission intensity between right and left circularly polarized light emitted from optically active molecules. Circularly polarized luminescence has been developed as one of the most sensitive techniques for determining protein conformation in solution by examining the chiral environment in which fluorescent probes are present. Most studied are lanthanides and actinide complexes. For example, the invention described in Non-Patent Document 1 can be given as an example in which circularly polarized light is developed in a system using a lanthanide complex. This system has a very high quantum yield, and it is evaluated that circularly polarized light emission of several lanthanide cations can be expressed in the visible region with one kind of ligand. Circularly polarized light emission is also used to observe the chirality of the excited state, as the CD spectrum observes the chirality of the ground state.

  On the other hand, in recent years, examples using a circularly polarized light emitting material as a light emitting material have come out, and an attempt to construct an essential circularly polarized light source has been made. For example, circularly polarized light emission using a conjugated polymer is expected to be advantageous in terms of a stable thin film forming ability, a sensor that utilizes a change in conjugate length, and control of the emission wavelength. As this type of circularly polarized light-emitting material, a material that imparts a helical structure to a conjugated polymer by introducing a chiral substituent into the side chain of the conjugated polymer and exhibits the function of circularly polarized light emission is known. (For example, Patent Documents 1 and 2).

  In addition, an invention is disclosed in which a polysaccharide / conjugated polymer complex obtained by using a natural polysaccharide having a helical structure and conjugating it to a conjugated polymer non-covalently is used as a circularly polarized light-emitting material. (For example, patent document 3).

  Furthermore, it has been reported that excimer emission from pyrene encapsulated in gammacyclodextrin, which is a cyclic sugar compound, shows a left circularly polarized emission signal (Non-Patent Document 2).

  If the polarized light emitted from the circularly polarized light-emitting material can be freely controlled, it is considered useful in various fields such as various light-emitting devices, sensors, liquid crystal display devices, organic polarizing plates, and multi-element memory devices. . As a method for controlling the emission direction of circularly polarized light, a method of chemically modifying gamma cyclodextrin is known (Non-patent Document 3).

JP 2004-107542 A (published April 8, 2004) JP 2004-109707 A (published on April 8, 2004) JP 2008-303306 A (released on December 18, 2008)

A. Satrijo, S. C. J. Maskers, T. M. Swager, J. Am. Chem. Soc., 128, 9030 (2006). K. Kano et al, J. Am. Chem. Soc., 107, 6117 (1985). K. Kano et al, J. Am. Chem. Soc., 110, 204 (1988).

  However, Patent Documents 1 to 3 and Non-Patent Documents 1 and 2 only describe that the disclosed materials can emit circularly polarized light, and create right circularly polarized light and left circularly polarized light as desired. It cannot be divided. Further, in Non-Patent Document 3, the 6-position of gamma cyclodextrin has been successfully modified to reverse the direction of emission of circularly polarized light, but chemical modification of cyclodextrin, which is a cyclic sugar compound, is very difficult. There is a problem that.

  The present invention has been made in view of the above-described problems, and its purpose is to control the light emission direction of circularly polarized light by selecting the functional group and pH of the circularly polarized light emitting material, and to control the pH of the circularly polarized light emitting material. A method for controlling the emission direction of circularly polarized light by changing, a method for controlling the intensity of circularly polarized light by changing the pH or temperature of the polymerized circularly polarized light emitting material, and a novel circle that can be used in the above method It is to provide a polarized light-emitting material.

  In view of the above problems, the inventor selects the functional group of the aromatic hydrocarbon derivative to be included in the cyclodextrin according to the regularity, and adjusts the pH of the solution containing the complex of the cyclodextrin and the aromatic hydrocarbon derivative. It has been found that the light emission direction of circularly polarized light emitted from the composite can be specified by adjusting. Further, the present inventors have found that the light emission direction of circularly polarized light emitted from the composite can be freely changed to a desired direction only by adjusting the pH of the solution containing the composite.

  That is, the method according to the present invention is a method of emitting left circularly polarized light from a complex formed by inclusion of an aromatic hydrocarbon derivative in cyclodextrin, wherein the aromatic hydrocarbon derivative of the following (a) is The pH of the solution containing the complex formed by inclusion in dextrin is adjusted to 12 or less, or the solution containing the complex formed by inclusion of the aromatic hydrocarbon derivative (b) below in cyclodextrin It is characterized in that left circularly polarized light is emitted by adjusting the pH to 14 or more.

  (A) a functional group having a skeletal structure composed of two or more and five or less six-membered rings, wherein one of the six-membered rings has an oxygen atom or hydrogen atom capable of hydrogen bonding with a hydroxyl group of cyclodextrin Of the oxygen atoms or hydrogen atoms, the oxygen atom or hydrogen atom located closest to the carbon atom of the six-membered ring to which the functional group is bonded is bonded to the functional group. An aromatic hydrocarbon derivative located at an odd number when the carbon atom of the six-membered ring is zero.

  (B) a functional group having a skeletal structure composed of 2 or more and 5 or less 6-membered rings, wherein one of the 6-membered rings has an oxygen atom or hydrogen atom capable of hydrogen bonding with a hydroxyl group of cyclodextrin Of the oxygen atoms or hydrogen atoms, the oxygen atom or hydrogen atom located closest to the carbon atom of the six-membered ring to which the functional group is bonded is bonded to the functional group. An aromatic hydrocarbon derivative located at an even number when the carbon atom of the six-membered ring is zero.

  Further, the method according to the present invention is a method of emitting right circularly polarized light from a complex formed by inclusion of an aromatic hydrocarbon derivative in cyclodextrin, wherein the aromatic hydrocarbon derivative of the following (a) is cyclodextrin: The pH of the solution containing the complex formed by inclusion in the solution is adjusted to 14 or more, or the pH of the solution containing the complex formed by inclusion of the aromatic hydrocarbon derivative (b) below in cyclodextrin Is adjusted to 12 or less to emit right circularly polarized light.

  (A) a functional group having a skeletal structure composed of two or more and five or less six-membered rings, wherein one of the six-membered rings has an oxygen atom or hydrogen atom capable of hydrogen bonding with a hydroxyl group of cyclodextrin Of the oxygen atoms or hydrogen atoms, the oxygen atom or hydrogen atom located closest to the carbon atom of the six-membered ring to which the functional group is bonded is bonded to the functional group. An aromatic hydrocarbon derivative located at an odd number when the carbon atom of the six-membered ring is zero.

  (B) a functional group having a skeletal structure composed of 2 or more and 5 or less 6-membered rings, wherein one of the 6-membered rings has an oxygen atom or hydrogen atom capable of hydrogen bonding with a hydroxyl group of cyclodextrin Of the oxygen atoms or hydrogen atoms, the oxygen atom or hydrogen atom located closest to the carbon atom of the six-membered ring to which the functional group is bonded is bonded to the functional group. An aromatic hydrocarbon derivative located at an even number when the carbon atom of the six-membered ring is zero.

  The inventor sets the pH of the solution containing the complex in which the aromatic hydrocarbon derivative shown in (a) is included in cyclodextrin to 12 or less, or the aromatic hydrocarbon shown in (b) above. It has been found that left circularly polarized light can be obtained by setting the pH of a solution containing a complex including a derivative in cyclodextrin to 14 or more.

  In addition, the present inventor may set the pH of the solution containing the complex in which the aromatic hydrocarbon derivative shown in (a) above is included in cyclodextrin to 14 or more, or the aromatic carbonization of the following (b) It has been found that right circularly polarized light can be obtained by setting the pH of a solution containing a complex in which a hydrogen derivative is included in cyclodextrin to 12 or less.

  That is, the emission direction of the circularly polarized light emitted from the composite is determined by the position of the oxygen atom or hydrogen atom that can be hydrogen-bonded to the hydroxyl group of the cyclodextrin, which the functional group introduced into the aromatic hydrocarbon derivative has, and the composite It was found that it depends on the pH of the solution in which the body is dissolved, and that the emission direction of circularly polarized light can be controlled by the selection of the functional group and pH. Therefore, according to the above configuration, it is possible to reliably determine the light emission direction of the circularly polarized light in a desired direction.

  The aromatic hydrocarbon derivative is preferably a pyrene derivative having one carboxyl group, carboxylic acid group, sulfonic acid group or aminoalkyl group.

  The method of reversing the light emission direction of circularly polarized light according to the present invention is a method for controlling the light emission direction of circularly polarized light emitted from a complex formed by inclusion of an aromatic hydrocarbon derivative (c) below in cyclodextrin. Then, the light emitting direction of circularly polarized light is reversed by adjusting the pH of the solution containing the complex to a value of 12 or less or a value of 14 or more.

  (C) having a skeletal structure composed of two or more and five or less six-membered rings, and one of the six-membered rings is a functional group having an oxygen atom or hydrogen atom capable of hydrogen bonding with a hydroxyl group of cyclodextrin One aromatic hydrocarbon derivative.

  The present inventor has found that the pH of the solution containing the complex affects the emission direction of circularly polarized light. When the pH of the solution is 12 or less, the light emission direction of circularly polarized light is a certain direction due to the structure of the functional group of the aromatic hydrocarbon derivative, but the pH of the solution is increased to more than 12. As a result, it has been found that a point where the emission direction of circularly polarized light is reversed appears when the pH is in the range of more than 12 and less than 14.

  For example, if right circularly polarized light is obtained when the pH of the solution is 12 or lower, adjusting the pH to 14 or higher can change circularly polarized light to left circularly polarized light. If left circularly polarized light is obtained in the case of 14 or more, the circularly polarized light can be changed to right circularly polarized light by adjusting the pH to 12 or lower. For example, when the pH of the solution is more than 12 and less than 14, adjusting the pH to 12 or less or 14 or more can reverse the light emission direction of circularly polarized light.

  According to the said structure, the light emission direction of circularly polarized light can be freely controlled only by simple operation of changing the pH of the solution containing the said composite_body | complex. Therefore, it can be suitably used in fields such as a high-brightness liquid crystal display, a three-dimensional display, a storage material, and optical communication, which are expected to benefit from switching of circularly polarized light emission.

  The aromatic hydrocarbon derivative is preferably a pyrene derivative having one carboxyl group, carboxylic acid group, sulfonic acid group or aminoalkyl group.

  The method of controlling the intensity of the circularly polarized light according to the present invention is shown by circularly polarized light having a wavelength of 430 nm or more and 490 nm or less generated from the following polymer (d) by adjusting the pH of the solution containing the following polymer (d) to 7. The absolute value of the emission spectrum intensity is increased from the absolute value of the above-mentioned intensity when the pH of the solution containing the following polymer (d) is 14, and the pH of the solution containing the following polymer (d) is adjusted to 14. The absolute value of the emission spectrum intensity of circularly polarized light having a wavelength of 430 nm or more and 490 nm or less generated from the following polymer (d) is calculated from the absolute value of the intensity when the pH of the solution containing the following polymer (d) is 7. It is also characterized by decreasing.

  (D) A polymer in which a complex formed by inclusion of 1-pyrenebutyric acid in cyclodextrin is bonded via a polymer having a hydroxyl group or an amino group.

  In addition, the method of controlling the intensity of circularly polarized light according to the present invention is a circularly polarized light having a wavelength of 450 nm or more and 550 nm or less that is generated from the following polymer (e) by adjusting the pH of the solution containing the following polymer (e) to 7. The absolute value of the emission spectrum intensity indicated by is increased from the absolute value of the intensity when the pH of the solution containing the following polymer (e) is 14, and the pH of the solution containing the following polymer (e) is adjusted to 14. Thus, the absolute value of the emission spectrum intensity exhibited by circularly polarized light having a wavelength of 450 nm or more and 550 nm or less generated from the following polymer (e) is the absolute value of the above intensity when the pH of the solution containing the following polymer (d) is 7. It is characterized by being reduced from the value.

  (E) A polymer in which a complex formed by inclusion of 1-pyrenesulfonic acid in cyclodextrin is bonded via a polymer having a hydroxyl group or an amino group.

  In the method for controlling the intensity of the circularly polarized light according to the present invention, the temperature of the solution containing the following polymer (f) is increased from 5 ° C. to 65 ° C., and the wavelength of 450 nm to 600 nm is generated from the following polymer (f). The intensity of the fluorescence spectrum exhibited by circularly polarized light is reduced in a temperature-dependent manner, and the temperature of the solution containing the following polymer (f) is reduced from 65 ° C. to 5 ° C., resulting in the wavelength of 450 nm to 600 nm. It is characterized in that the intensity of the fluorescence spectrum shown by the following circularly polarized light is increased in a temperature-dependent manner.

  (F) a polymer obtained by bonding a complex formed by inclusion of an aromatic hydrocarbon derivative in cyclodextrin via a polymer having a hydroxyl group or an amino group, wherein the aromatic hydrocarbon derivative is It has a skeletal structure composed of 2 or more and 5 or less six-membered rings, and one of the six-membered rings is one functional group having an oxygen atom or hydrogen atom capable of hydrogen bonding with a hydroxyl group of cyclodextrin Have.

  In the method for controlling the intensity of circularly polarized light according to the present invention, the aromatic hydrocarbon derivative is preferably a pyrene derivative having one carboxyl group, carboxylic acid group, sulfonic acid group or aminoalkyl group.

  When the polymer (d), (e), or (f) is used instead of the complex formed by including the aromatic hydrocarbon derivative of (c) in cyclodextrin, the present inventor uses the polymer (d ), (E) or (f) by changing the pH or temperature of the solution, the intensity of circularly polarized light having a predetermined wavelength generated from the polymer (d), (e) or (f) is greatly changed. I found it.

  A complex formed by including an aromatic hydrocarbon derivative in cyclodextrin can be bound to either a lipophilic polymer or a hydrophilic polymer. Since the polymer (d), (e) or (f) has a structure in which a plurality of the composites are bonded via a lipophilic or hydrophilic polymer, it can be formed into a film or gel. Is possible.

  Therefore, according to the above configuration, it is possible to adjust the intensity of circularly polarized light by applying it to an application that is easier to use when the circularly polarized light emitting material is in the form of a film or gel, for example, an organic polarizing plate, a liquid crystal display device, etc. it can.

  The circularly polarized light-emitting material according to the present invention includes a cyclodextrin containing pyrene or naphthalene having a carboxyl group, a carboxylic acid group having 2, 3, 5, 6 or 10 carbon atoms, a sulfonic acid group, or an aminoalkyl group. It is characterized by contact.

  According to the said structure, since the light emission direction of circularly polarized light can be specified with the structure of a functional group, it can be used, for example as a test body of the method concerning this invention.

  The circularly polarized light-emitting material according to the present invention is a cyclodextrin containing pyrene or naphthalene having a carboxyl group, a carboxylic acid group having 2, 3, 5, 6 or 10 carbon atoms, a sulfonic acid group, or an aminoalkyl group. A plurality of circularly polarized light-emitting materials formed by inclusion in a polymer may be bonded via a polymer having a hydroxyl group or an amino group.

  In such a circularly polarized light-emitting material, changing pH or temperature causes deprotonation of a polymer having a hydroxyl group or an amino group, or changes in the inclusion direction of an aromatic hydrocarbon. It is possible to control the intensity of circularly polarized light by changing the angle. Further, it can be formed into a film or gel. Therefore, it is used for applications that are easier to use when the circularly polarized light-emitting material is in the form of a film or gel, such as an organic polarizing plate, a liquid crystal display device, etc., and used for controlling the intensity of circularly polarized light by the method according to the present invention. be able to.

  A method of emitting left circularly polarized light from a complex formed by inclusion of an aromatic hydrocarbon derivative according to the present invention in cyclodextrin is a composite formed by inclusion of the aromatic hydrocarbon derivative (a) in cyclodextrin. By adjusting the pH of the solution containing the body to 12 or lower, or by adjusting the pH of the solution containing the complex formed by inclusion of the aromatic hydrocarbon derivative of (b) in cyclodextrin to 14 or more This is a method of emitting left circularly polarized light.

  The method of emitting right circularly polarized light from a complex formed by inclusion of an aromatic hydrocarbon derivative according to the present invention in cyclodextrin includes the inclusion of the aromatic hydrocarbon derivative in (a) in cyclodextrin. The pH of the solution containing the complex is adjusted to 14 or higher, or the pH of the solution containing the complex formed by including the aromatic hydrocarbon derivative of (b) in cyclodextrin is adjusted to 12 or lower. This is a method for emitting right circularly polarized light.

  Therefore, since the light emission direction of circularly polarized light can be determined reliably, the light emission direction of circularly polarized light can be easily controlled.

  In addition, the method for reversing the emission direction of circularly polarized light emitted from the complex formed by inclusion of the aromatic hydrocarbon derivative of (c) in cyclodextrin according to the present invention is the method of resolving the solution containing the complex. In this method, the emission direction of circularly polarized light is reversed by adjusting the pH to a value of 12 or less or a value of 14 or more. Therefore, there is an effect that the light emission direction of circularly polarized light can be freely controlled by only a simple operation of changing the pH of the solution containing the complex.

CPL and PL from a complex in which 1-pyrenecarboxylic acid is included in cyclodextrin are shown for the case where the pH of the solution containing the complex is 7 and the case of 14. The CPL and PL from the complex in which 1-pyrenesulfonic acid is included in cyclodextrin are shown for the case where the pH of the solution containing the complex is 7 and the case of 14. CPL and PL from a complex in which 1-pyrenemethylamine hydrochloride is included in cyclodextrin are shown for the case where the pH of the solution containing the complex is 7 and the case of 14. FIG. CPL and PL from a complex in which 1-pyrenebutyric acid is included in cyclodextrin are shown for the case where the pH of the solution containing the complex is 7 and the case of 14. The relationship between pH and g _CPL when the pH of a solution containing a complex of an aromatic hydrocarbon derivative and cyclodextrin is changed is shown for the case where 1-pyrenesulfonic acid is used. The relationship between pH and g _CPL when the pH of a solution containing a complex of an aromatic hydrocarbon derivative and cyclodextrin is changed is shown for the case where 1-pyrenemethylamine hydrochloride is used. The relationship between pH and g _CPL when the pH of a solution containing a complex of an aromatic hydrocarbon derivative and cyclodextrin is changed is shown for the case where 1-pyrenebutyric acid is used. It is a figure which shows the synthetic route of Poly-1. The case where 1-pyrenebutyric acid is used shows the measurement results of CPL and PL when the pH of the solution containing the complex of the aromatic hydrocarbon derivative and cyclodextrin is 7 or 14. The case where 1-pyrenesulfonic acid is used shows the CPL and PL measurement results when the pH of the solution containing the complex of the aromatic hydrocarbon derivative and cyclodextrin is 7 or 14. It is a figure which shows the cyclic structure of (gamma) -cyclodextrin. It is a schematic diagram which shows the mode of inclusion of the aromatic hydrocarbon derivative by a cyclodextrin. It is a figure which shows an example of the structure of a polymer (d). The PL measurement result of the composite_body | complex which included 1-pyrene butyric acid in Poly-1 is shown. The PL measurement result of the composite_body | complex which included 1-pyrenesulfonic acid in Poly-1 is shown. The PL measurement result of the composite_body | complex which included 1-pyrenecarboxylic acid in Poly-1 is shown.

  An embodiment of the present invention will be described as follows, but the present invention is not limited to this. In the present specification, “A to B” indicating a range indicates that the range is A or more and B or less.

(1. Method of emitting left circularly polarized light or right circularly polarized light from a complex formed by including an aromatic hydrocarbon derivative in cyclodextrin)
According to the present embodiment, the method of emitting left circularly polarized light from a complex obtained by inclusion of an aromatic hydrocarbon derivative in cyclodextrin includes the following (a) inclusion of the aromatic hydrocarbon derivative in cyclodextrin. The pH of the solution containing the complex is adjusted to 12 or lower, or the pH of the solution containing the complex formed by including the aromatic hydrocarbon derivative (b) below in cyclodextrin is adjusted to 14 or higher. This is a method of emitting left circularly polarized light.

  In addition, the method of emitting right circularly polarized light from a complex formed by inclusion of an aromatic hydrocarbon derivative in cyclodextrin according to the present embodiment includes the following (a) inclusion of the aromatic hydrocarbon derivative in cyclodextrin. The pH of the solution containing the complex formed is adjusted to 14 or higher, or the pH of the solution containing the complex formed by including the aromatic hydrocarbon derivative (b) below in cyclodextrin is 12 or lower. In this method, right circularly polarized light is emitted by adjusting.

  (A) a functional group having a skeletal structure composed of two or more and five or less six-membered rings, wherein one of the six-membered rings has an oxygen atom or hydrogen atom capable of hydrogen bonding with a hydroxyl group of cyclodextrin (Hereinafter also simply referred to as “functional group A”), and is located closest to the carbon atom of the six-membered ring to which the functional group is bonded, among the oxygen atoms or hydrogen atoms. Oxygen atom or hydrogen atom (hereinafter simply referred to as “nearest oxygen atom or hydrogen atom”) is an odd-numbered fragrance where the carbon atom of the six-membered ring to which the functional group is bonded is defined as zero. Group hydrocarbon derivatives.

  (B) having a skeletal structure composed of two or more and five or less six-membered rings, and one of the six-membered rings has one functional group A, and the nearest oxygen atom or An aromatic hydrocarbon derivative in which a hydrogen atom is located even when the carbon atom of the six-membered ring to which the functional group is bonded is defined as zero.

  The skeleton structure (aromatic hydrocarbon) of the aromatic hydrocarbon derivatives (a) and (b) is not particularly limited as long as it is a structure composed of 2 or more and 5 or less 6-membered rings. If it is the said structure, in view of the size of the cavity which the cyclic structure of cyclodextrin has, the dimer of an aromatic hydrocarbon derivative can fully be included per cyclodextrin molecule. As the skeleton structure, for example, naphthalene, anthracene, pyrene, benzopyrene, chrysene, naphthacene, triphenylene, pentacene, or the like can be used. Especially, since the volume of a pyrene 2 molecule is the optimal size with respect to the cavity size of cyclodextrin, pyrene can be used especially preferably.

  In the method according to the present embodiment, the "nearest oxygen atom or hydrogen atom" is located at an odd number when the carbon atom of the six-membered ring to which the functional group A is bonded is zero. This is based on the finding that the light emission direction of the circularly polarized light emitted from the composite is determined by the combination of the regularity of whether it is located evenly and the pH of the solution containing the composite.

  One of the six-membered rings has one functional group A. That is, one of the 6-membered rings of 2 or more and 5 or less has one functional group A. As long as it is one of the two or more and five or less six-membered rings, there is no particular limitation as to which six-membered ring is the six-membered ring to which the functional group A is bonded. Further, the position of carbon on the six-membered ring to which the functional group A is bonded is not particularly limited.

  In the present specification, conventionally known cyclodextrins can be used. The degree of polymerization of cyclodextrin is not particularly limited, and may be any of α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, δ-cyclodextrin, and ε-cyclodextrin.

  The “hydroxy group of cyclodextrin” may be either a primary hydroxyl group or a secondary hydroxyl group. Here, “primary hydroxyl group” refers to a hydroxyl group in which one carbon atom is bonded to the carbon atom to which the hydroxyl group is bonded, and “secondary hydroxyl group” refers to a carbon atom to which the hydroxyl group is bonded. A hydroxyl group in which two carbon atoms are bonded. FIG. 11 is a diagram showing a cyclic structure of γ-cyclodextrin. The primary hydroxyl group is, for example, the hydroxyl group indicated by reference numeral 1 in FIG. 11, and the secondary hydroxyl group is the hydroxyl group indicated by reference numeral 2 in FIG.

  The hydroxyl group of cyclodextrin may be partially substituted with other functional groups. As the substituent, for example, an alkoxy group, an amino group, a mercapto group, or the like can be used. By the substitution, the solubility of cyclodextrin in an organic solvent can be increased, and as a result, the effect of improving the inclusion ability of cyclodextrin can be obtained. In addition, the substitution ratio of the hydroxyl group by these substituents is not limited, It may not be substituted at all and all the hydroxyl groups may be substituted.

  The functional group A has an oxygen atom or hydrogen atom capable of hydrogen bonding with the hydroxyl group of cyclodextrin. The functional group A is not particularly limited, and examples thereof include a carboxyl group, a carboxylic acid group, a sulfonic acid group, an amino group, an aminoalkyl group, and a hydroxyl group. Examples of the oxygen atom or hydrogen atom include a carbonyl oxygen atom in a carboxyl group, a sulfonyl oxygen atom in a sulfonic acid group, a hydrogen atom constituting an amino group, and the like.

  Examples of the aromatic hydrocarbon derivatives (a) and (b) include 1-pyrenecarboxylic acid, 1-pyrenesulfonic acid, 1-pyrenemethylamine hydrochloride, 1-pyreneethanoic acid, 1-pyrenepropanoic acid, Pyrenebutyric acid, 1-pyrenepentanoic acid, 1-pyrenehexanoic acid and the like can be mentioned. Among them, a pyrene derivative having one carboxyl group, carboxylic acid group, sulfonic acid group, or aminoalkyl group is preferable.

  The aromatic hydrocarbon derivatives (a) and (b) may be commercially available. In addition, a functional group A may be introduced into the above skeleton structure such as pyrene by a conventionally known method. For example, the functional group A can be introduced into the skeleton structure by using a technique such as Friedel-Crafts reaction.

  “The nearest oxygen atom or hydrogen atom is located at an odd number when the carbon atom of the six-membered ring to which the functional group A is bonded is zero” means that the functional group A is bonded as a substituent. The oxygen atom or hydrogen atom that can form a hydrogen bond with the hydroxyl group of cyclodextrin when the carbon atom of the six-membered ring is zero and the atom on the functional group A adjacent to the carbon atom is counted as the first. Among them, the position of the oxygen atom or hydrogen atom closest to the zeroth carbon atom is an odd number.

  For example, 1-methylamine hydrochloride represented by the chemical formula (1) has a zero carbon atom bonded to the aminomethyl group as a substituent, and a first carbon atom on the aminomethyl group adjacent to the carbon atom. When counted, the nitrogen atom of the aminomethyl group is second, the hydrogen atom bonded to the nitrogen atom is third, and the hydrogen atom can hydrogen bond with the hydroxyl group of cyclodextrin. This corresponds to the aromatic hydrocarbon derivative (a).

  In the aromatic hydrocarbon derivative of (b) above, “the nearest oxygen atom or hydrogen atom is even-numbered when the carbon atom of the six-membered ring to which the functional group A is bonded as a substituent is zero-th. "Position" is the same, when the carbon atom of the six-membered ring to which the functional group A is bonded as a substituent is the zeroth, and the atom on the functional group A adjacent to the carbon atom is counted as the first In addition, among oxygen atoms or hydrogen atoms capable of hydrogen bonding with the hydroxyl group of cyclodextrin, the position of the oxygen atom or hydrogen atom closest to the zeroth carbon atom is the even number.

  For example, in 1-pyrenesulfonic acid represented by chemical formula (2), the carbon atom on the six-membered ring to which the sulfonic acid group is bonded as a substituent is the zeroth, and the sulfur atom adjacent to the carbon atom is the first. When counted, the sulfonyl oxygen is second, and the sulfonyl oxygen can hydrogen bond with the hydroxyl group of cyclodextrin, so 1-pyrenesulfonic acid corresponds to the aromatic hydrocarbon derivative of (b) above.

  In the method of emitting left-handed circularly polarized light from a complex formed by inclusion of an aromatic hydrocarbon derivative in cyclodextrin according to this embodiment, the aromatic hydrocarbon derivative in (a) is included in cyclodextrin. The pH of the solution containing the complex is adjusted to 12 or less, or the pH of the solution containing the complex formed by including the aromatic hydrocarbon derivative (b) below in cyclodextrin is 14 or more. By adjusting, left circularly polarized light is emitted.

  The complex can be obtained by a conventionally known method. For example, the complex can be obtained by dissolving cyclodextrin in a conventionally known pH buffer or the like and then adding and mixing an aromatic hydrocarbon derivative. In the cavity derived from the cyclic structure of one cyclodextrin molecule, molecules of two aromatic hydrocarbon derivatives form excimers and emit circularly polarized light.

The concentration of the cyclodextrin and the aromatic hydrocarbon derivative is not particularly limited, but the solution containing the complex includes 10 ⁻² M to 10 ⁻³ M of cyclodextrin and 10 ⁻⁴ M to 10 ^{−3 of} the aromatic hydrocarbon derivative. It is preferable that ^{-5M is} dissolved.

  FIG. 12 is a schematic view showing a state of inclusion of an aromatic hydrocarbon derivative by cyclodextrin. The dimer is hydrophobically taken up into a cavity derived from the cyclic structure of cyclodextrin. In FIG. 12, 3 represents a dimer of an aromatic hydrocarbon derivative, and 4 represents cyclodextrin.

  As an aspect of inclusion, the dimer may be incorporated into only one molecule of cyclodextrin as shown in (a) of FIG. 12, or as shown in (b) of FIG. A portion of the dimer that protrudes from the cavity may be further incorporated into another cyclodextrin. That is, a dimer of an aromatic hydrocarbon derivative may be included per cyclodextrin molecule.

  The light emission direction of circularly polarized light is affected by the regularity of the position of the “nearest oxygen atom or hydrogen atom”. When the aromatic hydrocarbon derivative is included in cyclodextrin, the “nearest oxygen atom or hydrogen atom” in functional group A is fixed to the hydroxyl group of cyclodextrin by hydrogen bonding. Then, depending on whether the “nearest oxygen atom or hydrogen atom” is located odd-numbered or even-numbered when the carbon atom of the six-membered ring to which the functional group A is bonded is zeroth The conformational torsion angle of the aromatic hydrocarbon moiety will be different. For example, when the functional group A is a butanoic acid group and when the functional group A is a pentanoic acid group, the conformational twist angles of the aromatic hydrocarbon moieties are opposite to each other.

  Thus, regularity occurs in the emission direction of circularly polarized light based on the fact that the twist angles of the conformations of the aromatic hydrocarbon portion are opposite to each other depending on the position of the “nearest oxygen atom or hydrogen atom”. It is considered a thing. Furthermore, the present inventor has clarified that the regularity of the emission direction of circularly polarized light is affected by the pH of the solution containing the complex.

  The pH of the solution containing the complex formed by inclusion of the aromatic hydrocarbon derivative (a) in cyclodextrin is adjusted to 12 or less if the pH of the solution is 12 or less. For example, it is based on the finding that the circularly polarized light emitted from the composite is left circularly polarized light and constant.

  The pH of the solution containing the complex formed by inclusion of the aromatic hydrocarbon derivative (b) in cyclodextrin is adjusted to 14 or more by the present inventor because the pH of the solution is 12 or less. In this case, the circularly polarized light emitted from the complex is constant right-handed circularly polarized light, but there is a point where the reversal of the emission direction is observed when the pH is raised to be greater than 12. Is 14 or more, based on the finding that the change to left circularly polarized light is completed.

  In the method of emitting right-handed circularly polarized light from a complex formed by inclusion of an aromatic hydrocarbon derivative in cyclodextrin according to this embodiment, the aromatic hydrocarbon derivative in (a) is included in cyclodextrin. The pH of the solution containing the complex is adjusted to 14 or higher, or the pH of the solution containing the complex formed by including the aromatic hydrocarbon derivative (b) in cyclodextrin is 12 or lower. The right circularly polarized light is emitted by adjusting.

  The inventors adjust the pH of the solution containing the complex formed by inclusion of the aromatic hydrocarbon derivative (a) in cyclodextrin to 14 or more by the present inventor. If the pH of the solution containing the complex of the derivative and cyclodextrin is 12 or less, the circularly polarized light emitted from the complex is constant as left-handed circularly polarized light, but the pH is raised so as to be greater than 12. As a result, there is a point where the reversal of the emission direction is observed, and when the pH is 14 or more, it is based on the finding that the change to the right circularly polarized light is completed.

  The pH of the solution containing the complex formed by inclusion of the aromatic hydrocarbon derivative (b) in cyclodextrin is adjusted to 12 or less by the present inventor by the aromatic carbonization (b). It is based on the finding that when the pH of the solution containing the complex of hydrogen derivative and cyclodextrin is 12 or less, the circularly polarized light emitted from the complex is right circularly polarized light and constant.

  In addition, although the minimum of pH in case pH is 12 or less is not specifically limited, when the simplicity of pH adjustment is considered, it is preferable that a minimum is pH = 0. Further, the upper limit of the pH when the pH is 14 or more is not particularly limited, but the upper limit is preferably pH = 15 in consideration of the simplicity of pH adjustment.

  In this way, the “nearest neighbor oxygen atom or hydrogen atom” is positioned oddly or evenly when the carbon atom of the six-membered ring to which the functional group A is bonded is zero. It is clear for the first time by the present invention that the emission direction of circularly polarized light emitted from the complex can be controlled by a combination of the regularity of the position and the pH of the solution containing the complex of the aromatic hydrocarbon derivative and cyclodextrin. It became. Thereby, the circularly polarized light which has a desired light emission direction can be obtained easily only by selecting the functional group and pH of an aromatic hydrocarbon derivative according to a use.

  As an application of the method of emitting right circularly polarized light or left circularly polarized light according to the present invention, for example, security improvement of banknotes, documents and the like can be mentioned. For example, when pyrene is used as the aromatic hydrocarbon, the circularly polarized light emitted from the pyrene derivative is green light regardless of the emission direction. However, if the functional group and pH are selected and the light emission direction of circularly polarized light is adjusted to the right or left in advance, the composite is included in banknotes, documents, etc. as a security paint, and the inspection object emits light. By comparing the direction of circularly polarized light that is emitted and the direction of circularly polarized light that is emitted by a genuine product, the accuracy of authenticity determination can be improved as compared with the case where the presence or absence of light emission is simply confirmed.

  In addition, since the light emission direction of circularly polarized light can be determined by selecting the functional group and pH, for example, the light emission direction can be added as an element of quantum communication encryption. Therefore, the confidentiality of communication can be improved.

(2. Method of reversing the direction of emission of circularly polarized light)
The method of reversing the light emission direction of circularly polarized light according to the present invention is a method of reversing the light emission direction of circularly polarized light emitted from a complex formed by inclusion of an aromatic hydrocarbon derivative (c) below in cyclodextrin. In this method, the light emission direction of circularly polarized light is reversed by adjusting the pH of the solution containing the complex to a value of 12 or less or a value of 14 or more.

  (C) having a skeletal structure composed of two or more and five or less six-membered rings, and one of the six-membered rings is a functional group having an oxygen atom or hydrogen atom capable of hydrogen bonding with a hydroxyl group of cyclodextrin One aromatic hydrocarbon derivative.

  The skeleton structure of (c) is not particularly limited as long as it is a structure composed of 2 or more and 5 or less 6-membered rings, like the aromatic hydrocarbon derivatives (a) and (b). . Especially, since the volume of a pyrene 2 molecule is the optimal size with respect to the cavity size of cyclodextrin, pyrene can be used especially preferably. The functional group having an oxygen atom or hydrogen atom capable of hydrogen bonding with the hydroxyl group of cyclodextrin, the degree of polymerization of cyclodextrin, and the hydroxyl group of cyclodextrin are as described in the above section (1.).

  The method of reversing the light emission direction of circularly polarized light according to the present embodiment is a method of reversing the light emission direction of circularly polarized light by adjusting the pH of the solution containing the complex. .)) “The nearest oxygen atom or hydrogen atom” may be an odd-numbered one when the carbon atom of the six-membered ring to which the functional group A is bonded is zero. Alternatively, even-numbered ones may be used.

The solution containing the complex may be a solution in which a complex formed by inclusion of the aromatic hydrocarbon derivative (c) in cyclodextrin is dissolved. Examples thereof include a solution in which the complex is dissolved in a conventionally known pH buffer solution. Although a density | concentration is not specifically limited, It is preferable that cyclodextrin is 10 ^<-2 > M-10 ^{< -3} > M, and the said (c) is 10 < ^-4 > M-10 < ^-5 > M melt | dissolving. The solution can be prepared, for example, by dissolving cyclodextrin in a pH buffer solution, adding two molecules of the aromatic hydrocarbon derivative of (c) per molecule of cyclodextrin, and adjusting the pH with an acid or base. .

  When the pH of the solution is 12 or less, and when the solution is 14 or more, the inventor does not change the light emission direction of circularly polarized light as long as the pH is within the range, but the pH is more than 12 and less than 14 It was found that there exists a pH at which the emission direction is reversed in the range of. Therefore, the emission direction of the circularly polarized light emitted from the complex can be reliably reversed by adjusting the pH of the solution containing the complex to 12 or less or 14 or more.

  For example, when the pH of the solution containing the complex is 12 or less, the emission direction of circularly polarized light does not change even if the pH is lowered, but the emission direction is reversed by setting the pH to 14 or more. Can do. In addition, when the pH of the solution containing the complex is 14 or more, the emission direction of circularly polarized light does not change even if the pH is increased, but the emission direction can be reversed by setting the pH to 12 or less. it can. When the pH of the solution containing the complex is greater than 12 and less than 14, the emission direction of circularly polarized light can be reversed by adjusting the pH to be 12 or less or 14 or more.

  Note that the inversion is reversible, and the right circularly polarized light and the left circularly polarized light can be freely switched by adjusting the pH.

  The complex has a relatively symmetric structure due to the intramolecular hydrogen bond between the secondary hydroxyl groups of cyclodextrin and the hydrogen bond between the functional group and the primary or secondary hydroxyl group of cyclodextrin. . However, when an external stimulus is applied to adjust the pH to 12 or less or 14 or more, deprotonation from the secondary hydroxyl group occurs, and the structure of cyclodextrin changes due to electrostatic repulsion between oxygen atoms. This is thought to change the orientation of the aromatic hydrocarbon derivative molecules incorporated into the cyclic structure of cyclodextrin, resulting in reversal of the emission direction of circularly polarized light emission.

  In A. Ueno et al. J. Am. Chem. Soc., 111, 6391-6397 (1989), pyrene is covalently bonded to the primary hydroxyl group of γ-cyclodextrin and pyrene: γ-cyclodextrin = 2: 2. It is disclosed that when an aggregate is formed and the pH is changed, the associated dimer is decomposed and an aggregate of pyrene: γ-cyclodextrin = 1: 1 is formed. However, since circularly polarized light is excimer emission, it is not generated from the 1: 1 aggregate. Therefore, the method according to the present invention is completely different from the technique disclosed in A. Ueno et al.

  The above “inversion of the light emission direction” means that when circularly polarized light is right circularly polarized light, it is changed to left circularly polarized light, and when circularly polarized light is left circularly polarized light, it is changed to right circularly polarized light. The method for adjusting the pH is not particularly limited, and can be appropriately adjusted using, for example, a conventionally known acid or alkali.

  If the pH of the solution is 12 or less, the light emission direction does not change even if the pH is further lowered, so the lower limit value of the pH is not particularly limited, but considering the ease of pH adjustment The lower limit is preferably 0. In addition, if the pH of the solution is 14 or more, the light emission direction does not change even if the pH is further raised, so the upper limit value of the pH is not particularly limited. In view of this, the upper limit is preferably 15.

  According to the above method, as in Non-Patent Document 3, the circularly polarized light emitted from the complex is right-handed circularly polarized light or left-handed circular light without chemically modifying γ-cyclodextrin, which is a very difficult technique. Regardless of whether it is polarized light, the light emission direction of circularly polarized light can be easily reversed only by a simple operation of adjusting the pH of the solution containing the complex. Therefore, it is considered that the present invention can be applied to organic EL displays that can control the light emission direction of circularly polarized light, various light emitting devices, sensors, organic polarizing plates, multi-element memory devices, security paints, and the like.

(3. Method for controlling the intensity of circularly polarized light generated from a polymer)
In one embodiment, the method for controlling the intensity of circularly polarized light according to the present invention is a method of adjusting the pH of a solution containing the following polymer (d) to 7, and resulting from the following polymer (d), having a wavelength of 430 nm or more and 490 nm or less. The absolute value of the emission spectrum intensity exhibited by the circularly polarized light is increased more than the absolute value of the intensity when the pH of the solution containing the following polymer (d) is 14, and the pH of the solution containing the following polymer (d) is increased. By adjusting to 14, the absolute value of the emission spectrum intensity exhibited by the circularly polarized light having a wavelength of 430 nm or more and 490 nm or less generated from the following polymer (d) is the above when the pH of the solution containing the following polymer (d) is 7 This is a method of reducing the absolute value of the intensity.

  (D) A polymer in which a complex formed by inclusion of 1-pyrenebutyric acid in cyclodextrin is bonded via a polymer having a hydroxyl group or an amino group.

  In another embodiment, the method of controlling the intensity of circularly polarized light according to the present invention is a wavelength of 450 nm that is generated from the following polymer (e) by adjusting the pH of the solution containing the following polymer (e) to 7. The solution containing the following polymer (e) by increasing the absolute value of the emission spectrum intensity exhibited by the circularly polarized light of 550 nm or less above the absolute value of the intensity when the pH of the solution containing the following polymer (e) is 14 The pH of the solution containing the following polymer (d) is 7 with the absolute value of the emission spectrum intensity exhibited by the circularly polarized light having a wavelength of 450 nm or more and 550 nm or less generated from the following polymer (e) by adjusting the pH of In this case, the absolute value of the intensity is reduced.

  (E) A polymer in which a complex formed by inclusion of 1-pyrenesulfonic acid in cyclodextrin is bonded via a polymer having a hydroxyl group or an amino group.

  The polymer (d) or (e) has a structure in which a complex in which 1-pyrenebutyric acid or 1-pyrenesulfonic acid is included in cyclodextrin is bonded via a polymer having a hydroxyl group or an amino group, respectively. have. FIG. 13 is a diagram showing an example of the structure of the polymer (d) or (e). In the figure, the composite is shown in a simplified form as a quadrangle, and as an example of the polymer (d) or (e), a structure in which the composite is bound via polyethyleneimine is shown.

  The polymer having a hydroxyl group or an amino group is not limited to polyethyleneimine, and a conventionally known polymer can be used. For example, polyamine, polyacrylamide, polyacrylic acid, polymethacrylic acid, polyvinyl alcohol and the like can be used.

  The polyamine is not particularly limited. For example, a chain aliphatic polyamine such as polyethyleneimine, diethylenetriamine, and triethylenetetramine, a cyclic aliphatic polyamine such as mensendiamine, isophoronediamine, and derivatives or modified derivatives thereof. Products, aromatic polyamines such as metaphenylenediamine and diaminodiphenylsulfone, and modified products thereof.

  The molecular weight of the polymer having a hydroxyl group or an amino group is preferably from 1,000 to 1,000,000, and more preferably from 10,000 to 500,000.

  In order to prepare the polymer (d) or (e), 1-pyrenebutyric acid or 1-pyrenesulfonic acid, cyclodextrin, and a polymer having a hydroxyl group or an amino group are added in an excess of polymer (for example, mol The ratio is preferably 1: 100).

  The method for preparing the polymer (d) or (e) is not particularly limited, and may be a conventionally known method. For example, it can be prepared by dissolving a polymer having a hydroxyl group or an amino group and cyclodextrin in a solvent such as dimethyl sulfoxide, and further adding and mixing 1-pyrenebutyric acid or 1-pyrenesulfonic acid.

The solution containing the polymer (d) or (e) can be prepared by dissolving the polymer (d) or (e) in, for example, a conventionally known pH buffer solution. The concentration of the polymer (d) or (e) contained in the solution is preferably 10 ⁻⁴ M to 10 ⁻⁵ M, for example.

  By using the composite as the polymer (d) or (e), the form can be formed into a film or gel. Therefore, according to the method of this embodiment, the polymer (d) or (e) can be used more easily when the circularly polarized light-emitting material is in the form of a film or gel, such as an organic polarizing plate or a device for liquid crystal display. For example, the intensity of circularly polarized light in these applications can be controlled by adjusting the pH. The method for forming the polymer (d) or (e) into a film or gel is not particularly limited. For example, methods such as drop casting, spin coating, alternate dipping, and spraying can be used.

  By making the complex into the polymer (d) or (e), deprotonation of the polymer having a hydroxyl group or amino group or change in the inclusion direction of the aromatic hydrocarbon occurs, so that the polymer (d ) Or (e) is considered to be able to control the intensity of circularly polarized light by adjusting the pH of the solution.

  Adjustment of pH can be suitably performed using an acid or a base. In the case of film formation, after dissolving in an appropriate organic solvent, an acid or base that can be dissolved in the organic solvent (for example, trifluoroacetic acid, organic acid, organic base, etc.) may be used to adjust the pH. In the case of a gel (eg, hydrogel), the pH can be adjusted by using acid or alkali in a buffer solution. Further, the increase and decrease in the strength are reversible, and the increase and decrease in the strength can be arbitrarily performed by adjusting the pH of the solution.

  In another embodiment, the method of controlling the intensity of circularly polarized light according to the present invention results from the following polymer (f) by increasing the temperature of the solution containing the following polymer (f) from 5 ° C. to 65 ° C. By reducing the intensity of the fluorescence spectrum exhibited by circularly polarized light having a wavelength of 450 nm or more and 600 nm or less in a temperature-dependent manner and decreasing the temperature of the solution containing the following polymer (f) from 65 ° C. to 5 ° C., the following polymer (f) This is a method for increasing the intensity of the fluorescence spectrum generated by the circularly polarized light having a wavelength of 450 nm to 600 nm in a temperature-dependent manner.

  (F) a polymer obtained by bonding a complex formed by inclusion of an aromatic hydrocarbon derivative in cyclodextrin via a polymer having a hydroxyl group or an amino group, wherein the aromatic hydrocarbon derivative is It has a skeletal structure composed of 2 or more and 5 or less six-membered rings, and one of the six-membered rings is one functional group having an oxygen atom or hydrogen atom capable of hydrogen bonding with a hydroxyl group of cyclodextrin Have.

  By using the complex as the polymer (f), the molecular motion becomes intense and it becomes difficult to insert the aromatic hydrocarbon derivative. Therefore, by adjusting the temperature of the solution containing the polymer (f), the polymer (f) It is considered that the intensity of circularly polarized light from can be controlled.

  As the “aromatic hydrocarbon derivative”, the same derivative as described in (2.) can be used, and it is a pyrene derivative having one carboxyl group, carboxylic acid group, sulfonic acid group or aminoalkyl group. Preferably there is. The functional group having an oxygen atom or hydrogen atom capable of hydrogen bonding with the hydroxyl group of cyclodextrin, the degree of polymerization of cyclodextrin, and the hydroxyl group of cyclodextrin are as described in the above section (1.). The “polymer having a group or an amino group” is as described in (3).

  The polymer (f) is preferably prepared using the above aromatic hydrocarbon derivative, cyclodextrin, and a polymer having a hydroxyl group or an amino group in excess of the polymer (for example, 1: 100 in a molar ratio).

  The method for preparing the polymer (f) is not particularly limited and may be a conventionally known method. For example, it can be prepared by dissolving a polymer having a hydroxyl group or an amino group and cyclodextrin in a solvent such as dimethyl sulfoxide, and further adding and mixing the aromatic hydrocarbon derivative.

The solution containing the polymer (f) can be prepared by dissolving the polymer (f) in, for example, a conventionally known pH buffer solution. The concentration of the polymer (f) contained in the solution is preferably 10 ⁻⁴ M to 10 ⁻⁵ M, for example.

  The temperature of the solution containing polymer (f) is increased from 5 ° C to 65 ° C or decreased from 65 ° C to 5 ° C. Thereby, the intensity of the circularly polarized light generated from the polymer (f) can be increased or decreased in a temperature-dependent manner. That is, when the temperature is increased in the range from 5 ° C. to 65 ° C., the intensity of the circularly polarized light is decreased accordingly, and when the temperature is decreased in the range from 65 ° C. to 5 ° C., the circularly polarized light is accordingly increased. The strength of the increases.

  The method for adjusting the temperature is not particularly limited, and can be performed by using a conventionally known Peltier method, a cryostat, a hot water bath, or the like. Increasing or decreasing the intensity of the circularly polarized light is reversible, and the intensity can be increased or decreased arbitrarily by adjusting the temperature of the solution containing the polymer (f).

  Such increase / decrease in the intensity of circularly polarized light by adjusting the temperature of the solution does not occur when the complex is not the polymer (f), and can be performed only by preparing the polymer (f). Is.

(4. Circularly polarized light emitting material)
In one embodiment, the circularly polarized light emitting material according to the present invention (hereinafter referred to as “circularly polarized light emitting material A”) has a carboxyl group, a carboxylic acid group having 2, 3, 5, 6 or 10 carbon atoms, and a sulfonic acid. Group or pyrene or naphthalene having one aminoalkyl group (hereinafter referred to as “aromatic hydrocarbon derivative A”) is included in cyclodextrin.

  As described above, these functional groups have an oxygen atom or a hydrogen atom that can form a hydrogen bond with the hydroxyl group of cyclodextrin, and therefore the oxygen atom or the hydrogen atom is bonded to the functional group. The circularly polarized light-emitting material according to the combination of the regularity of whether the carbon atom of the member ring is positioned at the odd-numbered or even-numbered carbon atoms and the pH of the solution containing the circularly polarized light-emitting material The light emission direction of circularly polarized light emitted from can be specified.

  Examples of the aromatic hydrocarbon derivative A include 1-pyrenecarboxylic acid, 1-pyrenesulfonic acid, 1-pyrenemethylamine hydrochloride, 1-pyreneethanoic acid, 1-pyrenepropanoic acid, 1-pyrenepentanoic acid, Examples include pyrenehexanoic acid and 1-pyrenedecanoic acid.

  The method for performing the inclusion is not particularly limited. For example, cyclodextrin is dissolved in a conventionally known pH buffer solution, and the aromatic hydrocarbon derivative A is added and mixed.

  In another embodiment, the circularly polarized light-emitting material according to the present invention is obtained by bonding a plurality of the above circularly polarized light-emitting materials A via a polymer having a hydroxyl group or an amino group, and the above (3.). It corresponds to the polymer (d), (e) or (f) described in 1.

  As described above, the polymers (d) to (f) are prepared by adjusting the pH or temperature of the solution containing the polymers (d), (e), or (f), so that the polymers (d), (e), or ( The intensity of circularly polarized light resulting from f) can be varied. Moreover, since the form can be a film or a gel, it can be used as a circularly polarized light-emitting material capable of changing the intensity of circularly polarized light in, for example, an organic polarizing plate and a liquid crystal display device.

  The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. Is also included in the technical scope of the present invention.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this.

(Example 1: Selection of functional group and control of circularly polarized light emission direction by pH)
A circularly polarized light emission spectrum (CPL) and a fluorescence spectrum (PL) of a complex obtained by including various pyrene derivatives in gamma cyclodextrin (γ-CD, manufactured by JUNSEI) were measured. 1-pyrenecarboxylic acid (manufactured by TCI), 1-pyrenesulfonic acid (manufactured by ALDRICH), 1-pyrenemethyl in a predetermined pH buffer solution (3 ml) in which γ-CD (38.91 mg, 0.01 M) was dissolved. Amine hydrochloric acid (manufactured by ALDRICH) or 1-pyrenebutyric acid (manufactured by TCI) is dissolved at 2.0 × 10 ⁻⁴ M, respectively, and the pH is adjusted to 7 or 14 using an aqueous sodium hydroxide solution (manufactured by WAKO) or hydrochloric acid (manufactured by WAKO). After adjustment, CPL and PL were measured. The pH was measured with a pH meter (manufactured by HORIBA, Navih, D-51).

  As the predetermined pH buffer solution, 51.0 ml of 0.2M sodium dihydrogen phosphate (manufactured by WAKO) and 49.0 ml of 0.2M sodium hydrogen phosphate (manufactured by WAKO) are prepared and mixed. The phosphate buffer solution (pH = 6.8) obtained by adjusting the final volume to 200 ml using deionized water, or 50 ml of 0.1 M glycine (manufactured by WAKO) and 0.1 M water A glycine buffer solution (pH = 10.6) obtained by preparing and mixing 45.5 ml of sodium oxide (manufactured by WAKO) and adjusting the final volume to 100 ml with deionized water was used.

  CPL and PL were all measured using a 1 cm × 1 cm quartz cell, and a JASCO CPL-200 CPL measuring device was used as the measuring device. All measurement conditions were set at a temperature of 5 ° C. The scanning speed is 200 nm / min, the response is 1 sec, the bandwidth is 10.0 nm (Em), 10.0 nm (Ex), the excitation wavelength is 280 nm, the measurement range is 700-350 nm, and the data acquisition interval is 2 nm.

  1 to 4 respectively show CPL and PL from a complex in which 1-pyrenecarboxylic acid, 1-pyrenesulfonic acid, 1-pyrenemethylamine hydrochloride, and 1-pyrenebutyric acid are included in cyclodextrin, respectively. The cases where the pH of the solution containing the complex is 7 and 14 are shown. In the figure, the thin dotted line indicates the CPL intensity when the pH is 7, the thick dotted line indicates the CPL intensity when the pH is 14, the thin solid line indicates the PL intensity when the pH is 7, and the thick solid line indicates the PL intensity when the pH is 14. Is shown. The horizontal axis represents the wavelength of circularly polarized light emitted from the composite, and the vertical axis represents CPL intensity on the left and PL intensity on the right.

  In 1-pyrenecarboxylic acid, when the carbon atom of pyrene to which the carboxyl group is bonded as a substituent is the zeroth, and the carboxy carbon atom adjacent to the carbon atom is counted as the first, the carbonyl oxygen is the second. The carbonyl oxygen can hydrogen bond with the hydroxyl group of cyclodextrin. From FIG. 1, it can be seen that in almost all wavelength bands, CPL shows a negative value when the pH of the solution is 7, and CPL shows a positive value when the pH of the solution is 14. In particular, at about 480 to about 600 nm, when the pH of the solution is 7, CPL shows a remarkable negative value, and when the pH of the solution is 14, CPL shows a remarkable positive value. .

  FIG. 1 shows that right circularly polarized light is emitted when the pH of the solution is 7, and left circularly polarized light is emitted when the pH is 14, as seen in the entire wavelength band shown in FIG. .

  In 1-pyrenesulfonic acid, when the carbon atom of pyrene to which the sulfonic acid group is bonded as a substituent is the zeroth, and the sulfur atom adjacent to the carbon atom is counted as the first, the sulfonyl oxygen is the second. The sulfonyl oxygen can hydrogen bond with the hydroxyl group of cyclodextrin. From FIG. 2, it can be seen that in almost all wavelength bands, CPL shows a negative value when the pH of the solution is 7, and CPL shows a positive value when the pH of the solution is 14. In particular, at about 450 to about 530 nm, when the pH of the solution is 7, CPL shows a remarkable negative value. When the pH of the solution is 14, CPL shows a remarkable positive value.

  FIG. 2 shows that the right circularly polarized light is emitted when the pH of the solution is 7 and the left circularly polarized light is emitted when the pH is 14, as seen in the entire wavelength band shown in FIG. .

  1-Pyrenemethylamine hydrochloric acid is defined as zero when the carbon atom of the pyrene to which the aminomethyl group is bonded as a substituent is zero, and the carbon atom on the aminomethyl group adjacent to the carbon atom is counted as the first. The hydrogen atom constituting the terminal amino group of the aminomethyl group is the third, and this hydrogen atom can hydrogen bond with the hydroxyl group of cyclodextrin. From FIG. 3, it can be seen that, in almost all wavelength bands, when the pH of the solution is 7, the CPL shows a positive value, and when the pH of the solution is 14, the CPL shows a negative value. In particular, at about 420 to about 550 nm, when the pH of the solution is 7, CPL shows a remarkable positive value, and when the pH of the solution is 14, CPL shows a marked negative value.

  FIG. 3 shows that the left circularly polarized light is emitted when the pH of the solution is 7, and the right circularly polarized light is emitted when the pH is 14, as seen in the entire wavelength band shown in FIG. .

  1-pyrenebutyric acid is a carbonyl oxygen atom when the carbon atom of the pyrene to which the butanoic acid group is bonded as a substituent is zero and the carbon atom on the butanoic acid group adjacent to the carbon atom is counted as the first. Becomes the fifth and the carbonyl oxygen can hydrogen bond with the hydroxyl group of cyclodextrin. From FIG. 4, it can be seen that in almost all wavelength bands, CPL shows a positive value when the pH of the solution is 7, and CPL shows a negative value when the pH of the solution is 14. In particular, at about 450 to about 520 nm, when the pH of the solution is 7, CPL shows a remarkable positive value, and when the pH of the solution is 14, CPL shows a marked negative value.

  FIG. 4 shows that the left circularly polarized light is emitted when the pH of the solution is 7 and the right circularly polarized light is emitted when the pH is 14, as seen in the entire wavelength band shown in FIG. .

  As described above, the oxygen atom or hydrogen atom capable of hydrogen bonding with the hydroxyl group of cyclodextrin is odd-numbered when the carbon atom of the six-membered ring to which the functional group of the aromatic hydrocarbon derivative is bonded is zero-numbered. The emission direction of circularly polarized light emitted from the complex by the combination of the regularity of the position of whether it is positioned or even-numbered and the pH of the solution containing the complex of the aromatic hydrocarbon derivative and cyclodextrin It can be seen that can be controlled.

Next, CPL was obtained by changing the pH of the solution containing the complex in a wider range, and the CPL was normalized with an asymmetry factor (g _CPL ) and quantitatively evaluated. g _CPL is expressed by the following Equation 1.

_{g CPL = ΔI / I = 2} (I L -I R) / I L + I R ··· (1)
Here, I _L and I _R indicate the intensity of left and right circularly polarized light emission, respectively.

FIGS. 5 to 7 show the relationship between pH and g _CPL when the pH of the solution containing the complex (hereinafter, simply referred to as “pH” in this section) is changed, respectively, 1-pyrenesulfonic acid, 1- The case where pyrenemethylamine hydrochloric acid and 1-pyrenebutyric acid are used is shown. 5 is a wavelength at which the PL intensity has a maximum value in FIG. 2 (484 nm when pH is less than 12 and 490 nm when the pH is 12 or more), and FIG. 6 is a wavelength at which the PL intensity has a maximum value in FIG. 3 (480 nm when the pH is less than 12). FIG. 7 shows the measurement target of circularly polarized light having a wavelength at which the PL intensity has a maximum value in FIG. 4 (480 nm when the pH is less than 12, 486 nm when the pH is 12 or more).

As shown in FIG. 5, when 1-pyrenesulfonic acid is used, g _CPL shows a substantially constant negative value up to pH 12.5, and shows a positive value when pH is 14.

As shown in FIGS. 6 and 7, when 1-pyrenemethylamine hydrochloride and 1-pyrenebutyric acid are used, g _CPL shows a substantially constant positive value until pH is 12.5, and pH is 14. When it shows a negative value. When g _CPL is negative, right circularly polarized light is emitted, and when g _CPL is positive, left circularly polarized light is emitted.

  5-7, it turns out that the light emission direction of the circularly polarized light from the said composite can be reversed by adjusting the said pH to the value of 12 or less, or the value of 14 or more.

(Example 2: Control of intensity of circularly polarized light by pH)
Branched polyethyleneimine (28.2 mg, 1.13 × 10 ⁻³ mM, manufactured by ALDRICH, Mw = 25000) and 6-mono-tosyl-γ-CD (250 mg, 0.17 mM, manufactured by TCI) in 10 ml of dimethyl sulfoxide Dissolved in (DMSO) and allowed to stir at 65 ° C. for 72 hours. The obtained reaction product was fractionated by a gel filtration column to obtain γ-CD-graft-polyethylenemine (hereinafter referred to as Poly-1). FIG. 8 is a diagram showing a synthesis route of Poly-1.

CPL and PL of a complex in which 1-pyrenesulfonic acid or 1-pyrenebutyric acid was included in Poly-1 were measured. All measurements were performed in a 1 cm × 1 cm quartz cell, and all measurement conditions were set at a temperature of 5 ° C. Various 1-pyrenesulfonic acid or 1-pyrenebutyric acid (2.0 × 10 ⁻⁴ M) is dissolved in a predetermined pH buffer solution (3 ml) in which Poly-1 is dissolved, and a JASCO CPL-200 CPL measuring device , Measurement of CPL and PL under conditions of scanning speed 200 nm / min, response 1 sec, bandwidth 10.0 nm (Em), 10.0 nm (Ex), excitation wavelength 280 nm, measurement range 700-350 nm, data acquisition interval 2 nm Went.

  FIGS. 9 and 10 show the measurement results of CPL and PL when 1-pyrenebutyric acid and 1-pyrenesulfonic acid are used, respectively, when the pH of the solution containing the complex is 7 or 14. FIG. The horizontal axis represents the wavelength of emitted circularly polarized light, and the vertical axis represents CPL intensity on the left and PL intensity on the right.

  From FIG. 9, when 1-pyrenebutyric acid is used, when the pH is 7, the CPL intensity is positive at 430 to 490 nm and left circularly polarized light is emitted, but when the pH is 14, The strength was significantly lower than in the case of pH 7 and was about 0-1. That is, it was found that by changing the pH from 7 to 14 at 430 to 490 nm, the circularly polarized light that was emitted could be almost quenched.

  Further, as shown in FIG. 10, when 1-pyrenesulfonic acid was used, when pH was 7, the CPL intensity was negative at 420 to 550 nm, and right circularly polarized light was emitted. On the other hand, when the pH was 14, the emission direction of CPL was opposite to that at pH 7 at 420 to 550 nm. Further, in the range of 450 nm to 540 nm, the absolute value of the CPL intensity was larger at pH 7 than at pH 14. In particular, in the range of 450 to 520 nm, the absolute value of the CPL intensity is significantly larger at pH 7. By changing the pH from 7 to 14 at 450 to 520 nm, the emitted circularly polarized light is almost It was found that it can be quenched.

  From the above results, a complex in which 1-pyrenesulfonic acid or 1-pyrenebutyric acid is included in Poly-1, that is, a complex in which 1-pyrenesulfonic acid or 1-pyrenebutyric acid is included in cyclodextrin is obtained. It was found that the intensity of circularly polarized light can be controlled by adjusting the pH of a solution containing a polymer formed by bonding a plurality of polymers via polyethyleneimine.

(Example 3: Control of intensity of circularly polarized light by temperature)
PL of a complex in which 1-pyrenebutyric acid, 1-pyrenesulfonic acid or 1-pyrenecarboxylic acid was included in Poly-1 was measured. All measurements were performed in a 1 cm × 1 cm quartz cell. 1-pyrenebutyric acid, 1-pyrenesulfonic acid or 1-pyrenecarboxylic acid (2.0 × 10 ⁻⁴ M) is dissolved in a predetermined pH buffer solution (3 ml) in which Poly-1 is dissolved, and the temperature of the solution 5 ° C, 25 ° C, 45 ° C, 65 ° C, using JASCO CPL-200 CPL measuring device, scanning speed 200nm / min, response 1sec, bandwidth 10.0nm (Em), 10.0nm (Ex), excitation CPL was measured under the conditions of a wavelength of 280 nm, a measurement range of 700 to 350 nm, and a data acquisition interval of 2 nm.

  14 to 16 show the PL measurement results of the complexes in which 1-pyrenebutyric acid, 1-pyrenesulfonic acid or 1-pyrenecarboxylic acid is included in Poly-1, respectively. The horizontal axis represents the wavelength of circularly polarized light emitted from the composite, and the vertical axis represents CPL intensity. As is clear from the figure, as the temperature of the solution decreases, the intensity of excimer emission is significantly reduced at 450 nm to 600 nm. This indicates that the intensity of circularly polarized light emission can be controlled by the temperature of the solution.

  In the method according to the present invention, the functional group of the aromatic hydrocarbon derivative to be included in the cyclodextrin is selected according to the regularity, and the pH of the solution containing the complex of cyclodextrin and the aromatic hydrocarbon derivative is adjusted. Thus, the light emission direction of circularly polarized light emitted from the complex can be specified. Moreover, the light emission direction of the circularly polarized light emitted from the composite can be freely changed to a desired direction only by adjusting the pH of the composite.

  Therefore, the method according to the present invention can be applied to organic EL displays capable of controlling the light emission direction of circularly polarized light, various light emitting devices, sensors, organic polarizing plates, multiple memory devices, security systems, and the like.

1 Primary hydroxyl group 2 Secondary hydroxyl group 3 Dimer of aromatic hydrocarbon derivative 4 Cyclodextrin

Claims (11)

A method of emitting left circularly polarized light from a complex formed by inclusion of an aromatic hydrocarbon derivative in cyclodextrin,
Adjusting the pH of the solution containing the complex formed by inclusion of the aromatic hydrocarbon derivative of the following (a) in cyclodextrin to 12 or lower, or converting the aromatic hydrocarbon derivative of the following (b) into cyclodextrin A method of emitting left circularly polarized light by adjusting the pH of a solution containing a complex formed by inclusion to 14 or more:
(A) a functional group having a skeletal structure composed of two or more and five or less six-membered rings, wherein one of the six-membered rings has an oxygen atom or hydrogen atom capable of hydrogen bonding with a hydroxyl group of cyclodextrin Of the oxygen atoms or hydrogen atoms, the oxygen atom or hydrogen atom located closest to the carbon atom of the six-membered ring to which the functional group is bonded is bonded to the functional group. An aromatic hydrocarbon derivative located at an odd number when the carbon atom of the six-membered ring is zero.
(B) a functional group having a skeletal structure composed of 2 or more and 5 or less 6-membered rings, wherein one of the 6-membered rings has an oxygen atom or hydrogen atom capable of hydrogen bonding with a hydroxyl group of cyclodextrin Of the oxygen atoms or hydrogen atoms, the oxygen atom or hydrogen atom located closest to the carbon atom of the six-membered ring to which the functional group is bonded is bonded to the functional group. An aromatic hydrocarbon derivative located at an even number when the carbon atom of the six-membered ring is zero. A method of emitting right circularly polarized light from a complex comprising an aromatic hydrocarbon derivative in a cyclodextrin,
The pH of the solution containing the complex formed by including the aromatic hydrocarbon derivative of the following (a) in cyclodextrin is adjusted to 14 or more, or the aromatic hydrocarbon derivative of the following (b) is added to the cyclodextrin Right circularly polarized light is emitted by adjusting the pH of the solution containing the complex formed by inclusion to 12 or less:
(A) a functional group having a skeletal structure composed of two or more and five or less six-membered rings, wherein one of the six-membered rings has an oxygen atom or hydrogen atom capable of hydrogen bonding with a hydroxyl group of cyclodextrin Of the oxygen atoms or hydrogen atoms, the oxygen atom or hydrogen atom located closest to the carbon atom of the six-membered ring to which the functional group is bonded is bonded to the functional group. An aromatic hydrocarbon derivative located at an odd number when the carbon atom of the six-membered ring is zero.
(B) a functional group having a skeletal structure composed of 2 or more and 5 or less 6-membered rings, wherein one of the 6-membered rings has an oxygen atom or hydrogen atom capable of hydrogen bonding with a hydroxyl group of cyclodextrin Of the oxygen atoms or hydrogen atoms, the oxygen atom or hydrogen atom located closest to the carbon atom of the six-membered ring to which the functional group is bonded is bonded to the functional group. An aromatic hydrocarbon derivative located at an even number when the carbon atom of the six-membered ring is zero.   The method according to claim 1 or 2, wherein the aromatic hydrocarbon derivative is a pyrene derivative having one carboxyl group, carboxylic acid group, sulfonic acid group or aminoalkyl group. A method for reversing the direction of emission of circularly polarized light emitted from a complex formed by inclusion of an aromatic hydrocarbon derivative of the following (c) in cyclodextrin,
A method comprising reversing the light emission direction of circularly polarized light by adjusting the pH of the solution containing the complex to a value of 12 or less or a value of 14 or more:
(C) having a skeletal structure composed of two or more and five or less six-membered rings, and one of the six-membered rings is a functional group having an oxygen atom or hydrogen atom capable of hydrogen bonding with a hydroxyl group of cyclodextrin One aromatic hydrocarbon derivative.   The method according to claim 4, wherein the aromatic hydrocarbon derivative is a pyrene derivative having one carboxyl group, carboxylic acid group, sulfonic acid group or aminoalkyl group. By adjusting the pH of the solution containing the following polymer (d) to 7, the absolute value of the emission spectrum intensity exhibited by the circularly polarized light having a wavelength of 430 nm or more and 490 nm or less generated from the following polymer (d) is expressed by the following polymer (d): Increasing the absolute value of the intensity when the pH of the solution containing is 14;
By adjusting the pH of the solution containing the following polymer (d) to 14, the absolute value of the emission spectrum intensity exhibited by the circularly polarized light having a wavelength of 430 nm or more and 490 nm or less generated from the following polymer (d) is expressed by the following polymer (d): A method for controlling the intensity of circularly polarized light, characterized by reducing the absolute value of the intensity when the pH of the containing solution is 7:
(D) A polymer in which a complex formed by inclusion of 1-pyrenebutyric acid in cyclodextrin is bonded via a polymer having a hydroxyl group or an amino group. By adjusting the pH of the solution containing the following polymer (e) to 7, the absolute value of the emission spectrum intensity exhibited by the circularly polarized light having a wavelength of 450 nm or more and 550 nm or less generated from the following polymer (e) is expressed by the following polymer (e): Increasing the absolute value of the intensity when the pH of the solution containing is 14;
By adjusting the pH of the solution containing the following polymer (e) to 14, the absolute value of the emission spectrum intensity exhibited by the circularly polarized light having a wavelength of 450 nm or more and 550 nm or less generated from the following polymer (e) is represented by the following polymer (d): A method for controlling the intensity of circularly polarized light, characterized by reducing the absolute value of the intensity when the pH of the containing solution is 7:
(E) A polymer in which a complex formed by inclusion of 1-pyrenesulfonic acid in cyclodextrin is bonded via a polymer having a hydroxyl group or an amino group. By increasing the temperature of the solution containing the following polymer (f) from 5 ° C. to 65 ° C., the intensity of the fluorescence spectrum of circularly polarized light having a wavelength of 450 nm to 600 nm generated from the following polymer (f) is reduced in a temperature-dependent manner. Let
By decreasing the temperature of the solution containing the following polymer (f) from 65 ° C. to 5 ° C., the intensity of the fluorescence spectrum exhibited by the circularly polarized light having a wavelength of 450 nm to 600 nm generated from the following polymer (f) is increased in a temperature-dependent manner. A method for controlling the intensity of circularly polarized light, characterized by:
(F) a polymer obtained by bonding a complex formed by inclusion of an aromatic hydrocarbon derivative in cyclodextrin via a polymer having a hydroxyl group or an amino group, wherein the aromatic hydrocarbon derivative is It has a skeletal structure composed of 2 or more and 5 or less six-membered rings, and one of the six-membered rings is one functional group having an oxygen atom or hydrogen atom capable of hydrogen bonding with a hydroxyl group of cyclodextrin Have.   The method according to claim 8, wherein the aromatic hydrocarbon derivative is a pyrene derivative having one carboxyl group, carboxylic acid group, sulfonic acid group or aminoalkyl group.   A circularly polarized light emitting material obtained by including pyrene or naphthalene having a carboxyl group, a carboxylic acid group having 2, 3, 5, 6 or 10 carbon atoms, a sulfonic acid group, or an aminoalkyl group in a cyclodextrin.   A circularly polarized light-emitting material obtained by bonding a plurality of the circularly polarized light-emitting materials according to claim 10 via a polymer having a hydroxyl group or an amino group.

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