KR20220109158A - Chiral polymer, composition including the same and organic light-emitting device including the composition - Google Patents

Abstract

A chiral polymer, a composition containing the same and an organic light emitting device are disclosed. According to one aspect, provided is the chiral polymer including a first repeating unit represented by a chemical formula 1. An object of the present invention is to provide the chiral polymer, the composition having improved circularly polarized light emitting properties, and the organic light emitting device including the same.

Description

Chiral polymer, composition including the same and organic light-emitting device including the composition

It relates to a chiral polymer, a composition comprising the same, and an organic light emitting device.

An organic light emitting device is a self-luminous device, and compared to a conventional device, a viewing angle is wide and the contrast is excellent, and the response time is fast, and the luminance, driving voltage and response speed characteristics are excellent, and multicolor is improved. It is possible.

On the other hand, the importance of circularly polarized light emitting materials that can add new functionality to various light applications such as sensors, light emitting devices, spin communication, and asymmetric photoreaction is emerging.

To provide a chiral polymer, a composition and an organic light emitting device having improved circularly polarized light emitting properties including the same.

According to one aspect, there is provided a chiral polymer comprising a first repeating unit represented by the following formula (1):

<Formula 1>

In Formula 1,

R ₁ To R ₁₀ are each independently hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, an amino group, a cyano group, a nitro group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, Substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, substituted or unsubstituted C ₂ -C ₂₀ alkenyl group, substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, substituted or unsubstituted C ₆ -C ₂₀ aryl a group, a substituted or unsubstituted C ₆ -C ₂₀ aralkyl group, or a substituted or unsubstituted C ₁ -C ₂₀ heteroaryl group,

R ₈ to R ₁₀ are different from each other,

* is the stereocenter.

According to an embodiment, the chiral polymer may include a first repeating unit represented by the following Chemical Formula 1A:

<Formula 1A>

In Formula 1A,

For a description of R ₁ to R ₇ , refer to the above description, respectively,

R ₈ is deuterium, -F, -Cl, -Br, -I, a hydroxyl group, an amino group, a cyano group, a nitro group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, substituted or unsubstituted C ₂ -C ₂₀ alkenyl group, substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, substituted or unsubstituted C ₆ -C ₂₀ aryl group, or substituted or unsubstituted C ₁ -C ₂₀ is a heteroaryl group,

For the description of R ₁₁ and R ₁₂ , refer to the description of R ₁ in claim 1, respectively,

그룹은 서로 상이하고,R ₈ and

groups are different,

* is the stereocenter.

According to one embodiment, the chiral polymer may have a helical sense of any one of left-rotation and right-rotation properties stronger than the other helical sense.

According to an embodiment, the chiral polymer may have a clockwise helical sense stronger than a left rotatory helical sense.

According to an embodiment, the chiral polymer may further include an achiral second repeating unit.

According to an embodiment, the second repeating unit may be represented by the following Chemical Formula 2:

<Formula 2>

In Formula 2,

R ₂₁ to R ₂₈ are each independently hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, an amino group, a cyano group or a nitro group, a C ₁ -C ₂₀ alkyl group not including a stereocenter , C ₁ -C ₂₀ alkoxy group without stereocenter, C ₂ -C ₂₀ alkenyl group without stereocenter, C ₂ -C ₂₀ alkynyl group without stereocenter, C ₆ -C ₂₀ aryl group or a C ₁ -C ₂₀ heteroaryl group.

According to another aspect, a chiral polymer comprising the first repeating unit represented by the above-described formula (1); and a (R)-platinum complex represented by the following formula (3) and a (S)-platinum complex represented by the following formula (4); a composition comprising:

<Formula 3>

<Formula 4>

.

.

According to an embodiment, the composition including the (R)-platinum complex may emit left circularly polarized light (LCPL), and the composition including the (S)-platinum complex may emit right circularly polarized light (RCPL).

According to one embodiment, the size (|g _abs |) of the Kuhn asymmetry factor of the composition containing the (R)-platinum complex is the size of the Kuhn asymmetry factor of the composition containing the (S)-platinum complex ( It can be more than 10 times larger than |g _abs |).

According to another aspect, the first electrode; a second electrode facing the first electrode; and an organic layer disposed between the first electrode and the second electrode and including a light emitting layer, wherein the light emitting layer includes the above-described chiral polymer.

According to an embodiment, the chiral polymer included in the light-emitting layer is a host, and the light-emitting layer contains a dopant selected from (R)-platinum complex represented by Formula 3 and (S)-platinum complex represented by Formula 4 may include more.

According to an embodiment, right circularly polarized light or left circularly polarized light may be emitted from the emission layer of the organic light emitting device.

The chiral polymer according to one aspect may exhibit predominantly any one of helical properties of right-rotation and left-rotation. The chiral polymer may improve the chiral optical properties of the dopant by diastereoselective interaction with the chiral dopant.

The chiral polymer can amplify circularly polarized light emitted from the chiral dopant, and the organic light emitting device including the chiral polymer can emit circularly polarized light with high luminance and high efficiency, and can be utilized in various optical applications.

1 is a schematic diagram for explaining the principle of a chiral polymer according to an embodiment having left-rotation or right-rotation in the main chain.
2 is a view showing a UV-vis absorption spectrum of a JY _n polymer film according to an embodiment.
3 is a diagram illustrating a normalized photoluminescence (PL) spectrum (excitation light λ _exc = 339 nm) of a JY _n polymer film according to an embodiment.
4 is a view showing a graph of the Kuhn asymmetry factor (g _abs ) according to the wavelength of the JY _n polymer film according to an embodiment and the UV-Vis absorption spectrum of Compound 2 together.
Figure 5 is a plot of the normalized Kuhn asymmetry factor (λ = 304 nm) versus the fraction of chiral repeat units.
6A is a JY ₀ polymer film, (R)-Pt 10 wt% doped JY ₀ polymer film, (S)-Pt 10 wt% doped JY ₀ polymer film, (R)-Pt, and (S)-Pt is a diagram showing the UV-vis absorption spectrum of
6B shows the Kuhn asymmetry factor (g _abs ) as a function of wavelength for JY ₀ polymer films, (R)-Pt 10 wt % doped JY ₀ polymer films and (S)-Pt 10 wt % doped JY ₀ polymer films. It is one graph.
Figure 6c shows the Kuhn asymmetry factor (g abs) of the (R)-Pt 10 wt% doped JY ₀ polymer film and the (S)-Pt 10 wt% doped JY ₀ polymer film (g _abs ) and the Kuhn asymmetry factor of the JY ₀ polymer film ( g _abs ) is a graph showing the difference (Δg _abs ) according to the wavelength.
7A is a JY ₁₀₀ polymer film, (R)-Pt 10 wt% doped JY ₁₀₀ polymer film, (S)-Pt 10 wt% doped JY ₁₀₀ polymer film, (R)-Pt, and (S)-Pt is a diagram showing the UV-vis absorption spectrum of
Figure 7b shows the Kuhn asymmetry factor (g _abs ) as a function of wavelength for JY ₁₀₀ polymer film, (R)-Pt 10 wt% doped JY ₁₀₀ polymer film and (S)-Pt 10 wt% doped JY ₁₀₀ polymer film; It is one graph.
Figure 7c shows the Kuhn asymmetry factor (g _abs ) of the JY ₁₀₀ polymer film doped with (R)-Pt 10 wt% and the JY ₁₀₀ polymer film doped with 10 wt% (S)-Pt and the Kuhn asymmetry factor of the JY ₁₀₀ polymer film ( g _abs ) is a graph showing the difference (Δg _abs ) according to the wavelength.
8 is a graph showing the Kuhn asymmetry factor according to wavelength of a JY _n polymer film doped with 10 wt% of (R)-Pt.
9A is a view showing photoluminescence spectra of a JY ₀ polymer film doped with (R)-Pt or (S)-Pt and a JY ₁₀₀ polymer film doped with (R)-Pt or (S)-Pt.
9B is a diagram showing CPL spectra of a JY ₀ polymer film doped with (R)-Pt or (S)-Pt and a JY ₁₀₀ polymer film doped with (R)-Pt or (S)-Pt.
Figure 9c shows the photoluminescence asymmetry constant (g) of the JY ₀ polymer film doped with (R)-Pt or (S)-Pt and the JY ₁₀₀ polymer film doped with (R)-Pt or (S)-Pt as a function of wavelength. _PL ) is a diagram showing.
10A and 10B are PL spectra of JY ₀ and JY ₁₀₀ polymer films with different (R)-Pt doping concentrations, respectively.
11 shows titration isotherms of I ₀ /I as a function of doping concentration of (R)-Pt or (S)-Pt of (R)-Pt:JY and (S)-Pt:JY polymer films. it is one drawing
12A and 12B are transient PL spectra of JY ₀ and JY ₁₀₀ polymer films with different doping concentrations of (R)-Pt, respectively.
13 is a line graph showing the energy transfer rate from a JY _n polymer host to a platinum complex dopant.
14A and 14B are confocal laser scanning micrographs of JY ₀ and JY ₁₀₀ polymer films with different doping concentrations of (S)-Pt, respectively.
14c and 14d are energy dispersive X-ray spectra and TEM images (inset) of a 50 wt% (S)-Pt:JY ₀ film and a 50 wt% (S)-Pt:JY ₁₀₀ film, respectively.
FIG. 15 is a voltammogram of argon saturated THF containing JY ₀ , JY ₁₀₀ , (R)-Pt and (S)-Pt.
16 is a diagram illustrating an energy diagram of an organic light emitting diode according to an exemplary embodiment.
17 is a diagram illustrating an electroluminescence (EL) spectrum of an organic light emitting diode according to an exemplary embodiment.
18 is a diagram illustrating current density-voltage-luminance (JVL) characteristics of an organic light emitting diode according to an exemplary embodiment.
19 is an external quantum efficiency-current density (EQE-J) curve of an organic light emitting diode according to an exemplary embodiment.
20 is a diagram illustrating an electroluminescence asymmetry constant (g _EL ) according to a wavelength of an organic light emitting diode according to an exemplary embodiment.

Hereinafter, a chiral polymer, a composition including the same, and an organic light emitting device according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings. The following is presented by way of example, and the present invention is not limited thereto, and the present invention is only defined by the scope of the claims to be described later.

When describing with reference to the drawings, the same or corresponding components are given the same reference numerals, and overlapping descriptions thereof will be omitted.

In the following examples, the singular expression includes the plural expression unless the context clearly dictates otherwise.

In the following embodiments, terms such as include or have means that the features or components described in the specification are present, and the possibility that one or more other features or components may be added is not excluded in advance.

In the following embodiments, when it is said that a part such as a film, region, or component is on or on another part, not only when it is directly on the other part, but also another film, region, component, etc. is interposed therebetween. Including cases where there is

In the drawings, the size of the components may be exaggerated or reduced for convenience of description. For example, since the size and thickness of each component shown in the drawings are arbitrarily indicated for convenience of description, the present invention is not necessarily limited to the illustrated bar.

The chiral polymer according to an embodiment includes a first repeating unit represented by the following Chemical Formula 1:

<Formula 1>

In Formula 1,

R ₁ To R ₁₀ are each independently hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, an amino group, a cyano group, a nitro group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, Substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, substituted or unsubstituted C ₂ -C ₂₀ alkenyl group, substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, substituted or unsubstituted C ₆ -C ₂₀ aryl a group, a substituted or unsubstituted C ₆ -C ₂₀ aralkyl group, or a substituted or unsubstituted C ₁ -C ₂₀ heteroaryl group,

R ₈ to R ₁₀ are different from each other,

* is the stereocenter.

According to an embodiment, one of R ₈ to R ₁₀ may be hydrogen.

According to another embodiment, one of R ₈ to R ₁₀ may be hydrogen, and the other one of R ₈ to R ₁₀ may be a substituted or unsubstituted C ₆ -C ₂₀ aralkyl group. For example, the substituted or unsubstituted C ₆ -C ₂₀ aralkyl group may be a substituted or unsubstituted benzyl group, a substituted or unsubstituted 2-phenylethyl group, or a substituted or unsubstituted 3-phenylpropyl group.

According to another embodiment, one of R ₈ to R ₁₀ is hydrogen, the other of R ₈ to R ₁₀ is a substituted or unsubstituted C ₆ -C ₂₀ aralkyl group, and the other one of R ₈ to R ₁₀ is deuterium, -F, -Cl, -Br, -I, a hydroxyl group, an amino group, a cyano group, a nitro group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, a substituted or unsubstituted C ₂ -C ₂₀ alkenyl group, a substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, a substituted or unsubstituted C ₆ -C ₂₀ aryl group, or a substituted or unsubstituted C ₁ -C ₂₀ may be a heteroaryl group.

According to an embodiment, the chiral polymer may include a first repeating unit represented by the following Chemical Formula 1A:

<Formula 1A>

In Formula 1A,

For the description of R ₁ to R ₇ , refer to the description in the present specification, respectively,

R ₈ is deuterium, -F, -Cl, -Br, -I, a hydroxyl group, an amino group, a cyano group, a nitro group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, substituted or unsubstituted C ₂ -C ₂₀ alkenyl group, substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, substituted or unsubstituted C ₆ -C ₂₀ aryl group, or substituted or unsubstituted C ₁ -C ₂₀ is a heteroaryl group,

For the description of R ₁₁ and R ₁₂ , refer to the description of R ₁ in the present specification, respectively,

그룹은 서로 상이하고,R ₈ and

groups are different,

* is the stereocenter.

According to an embodiment, the R ₁ to R ₇ , R ₁₁ and R ₁₂ may be hydrogen, and R ₈ may be a C ₁ -C ₅ alkyl group.

According to an embodiment, the chiral polymer may include a first repeating unit represented by Formula 1A-1 or 1A-2 below:

<Formula 1A-1>

<Formula 1A-2>

In Formulas 1A-1 and 1A-2, the descriptions of R ₁ to R ₈ , R ₁₁ and R ₁₂ are the same as described above.

The absolute configuration of the stereocenter in Formula 1A-1 may be (S)-configuration, and the absolute configuration of the stereocenter in Formula 1A-2 may be (R)-configuration.

According to an embodiment, R ₈ in Formulas 1A-1 and 1A-2 may be a C ₁ -C ₅ alkyl group. Accordingly, the absolute configuration of the stereocenter in Formula 1A-1 may be (S)-configuration, and the absolute configuration of the stereocenter in Formula 1A-2 may be (R)-configuration.

In the chiral polymer according to an embodiment, the main chain may have a helical sense due to a helical sense formed between adjacent carbazole pendants. The helical sense includes a right-handed helical sense (also referred to as (P)-helical) and a left-handed helical sense (also referred to as (M)-helical).

In the chiral polymer according to an embodiment, any one helical sense of left rotation and right rotation may be stronger than the other helical sense. For example, the chiral polymer may be a (P)-helical sense excess polymer in which a right-handed helical sense ((P)-helical) is stronger than a left-handed helical sense ((M)-helical).

According to an embodiment, the chiral polymer in which the absolute configuration of the stereocenter is (S)-configuration may be a (P)-helical sense excess polymer.

According to an embodiment, the chiral polymer may further include an achiral second repeating unit.

For example, the achiral second repeating unit may be represented by the following Chemical Formula 2:

<Formula 2>

In Formula 2,

R ₂₁ to R ₂₈ are each independently hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, an amino group, a cyano group, a nitro group, or a C ₁ -C ₂₀ alkyl group not including a stereocenter , C ₁ -C ₂₀ alkoxy group without stereocenter, C ₂ -C ₂₀ alkenyl group without stereocenter, C ₂ -C ₂₀ alkynyl group without stereocenter, C ₆ -C ₂₀ aryl group or a C ₁ -C ₂₀ heteroaryl group.

In the second repeating unit, the pendant carbazole group does not include a stereocenter. For example, R ₂ may be a methyl group, an ethyl group, an isopropyl group, an isobutyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, a neo-pentyl group, or a 3-pentyl group.

The chiral polymer according to an embodiment may have higher photoluminescence quantum yields (PLQY) than the achiral homopolymer made of the second repeating unit. For example, the chiral polymer may exhibit a tendency for PLQY to increase as the fraction of the first repeating unit in the polymer main chain increases.

The composition according to another embodiment includes the above-described chiral polymer; and a platinum complex selected from (R)-platinum complex represented by the following formula (3) and (S)-platinum complex represented by the following formula (4):

<Formula 3>

<Formula 4>

In the present specification, the (R)-platinum complex may be represented by (R)-Pt, and the (S)-platinum complex may be represented by (S)-Pt.

According to an embodiment, the (R)-platinum complex and (S)-platinum complex may each generate circularly polarized light emission.

Circularly polarized luminescence (CPL) is light emission in which the oscillation axis of luminescence rotates right or left along a vertical plane in the traveling direction, and the degree of circularly polarized luminescence is quantified by a luminescence dissymmetry factor (g _lum ). . The luminescence asymmetry constant (g _lum ) is defined as Equation 1 below:

<Formula 1>

g _lum = 2(I _LCPL -I _RCPL ) / (I _LCPL + I _RCPL ),

Here, I _LCPL and I _RCPL are the emission intensities of left circularly polarized light (LCPL) and right circularly polarized light (RCPL), respectively.

The light emission asymmetry constant in which the circularly polarized light is photoluminescence is a photoluminescence asymmetry constant (g _PL ), and the emission asymmetry constant in which the circularly polarized light is electroluminescence is an electroluminescence asymmetry constant (g _EL ).

According to an embodiment, the (R)-platinum complex emits left circularly polarized light (LCPL), and the (S)-platinum complex emits right circularly polarized light (RCPL), thereby exhibiting chiral optical rotation properties. .

The chiral polymer may amplify chiral optical rotation of the platinum complex by providing a chiral asymmetric environment around the platinum complex. For example, the composition according to an embodiment may have a higher photoluminescence asymmetry constant (g _PL ) than a composition using the achiral homopolymer composed of the second repeating unit as a host. The circularly polarized light emission characteristics of the achiral homopolymer host and the chiral polymer host will be described in more detail with reference to FIG. 9 to be described later.

The chiral polymer according to an embodiment may diastereoselectively interact with the (R)-platinum complex or the (S)-platinum complex to affect the chiral photorotation behavior of the platinum complex. For example, the size of the Kuhn asymmetry factor (|g _abs |) of the composition containing the (R)-platinum complex is the size of the Kuhn asymmetry factor of the composition containing the (S)-platinum complex (|g) can be more than 10 times larger than _abs |).

The Kuhn asymmetry factor (g _abs ) is defined as in Equation 2 below, and is a quantified value of the difference in photon absorbance for left and right circularly polarized light of a compound:

<Formula 2>

g _abs = 2(ε _LCPL - ε _RCPL ) /(ε _LCPL + ε _RCPL )

Here, ε _LCPL and ε _RCPL are the molar absorption coefficients of left circularly polarized light (LCPL) and right circularly polarized light (RCPL), respectively.

An organic light emitting device according to another embodiment includes a first electrode; a second electrode facing the first electrode; and an organic layer disposed between the first electrode and the second electrode and including an emission layer, wherein the emission layer may include the above-described chiral polymer.

According to one embodiment, the chiral polymer included in the light-emitting layer is a host, and the light-emitting layer is a dopant selected from (R)-platinum complex represented by the following formula (3) and (S)-platinum complex represented by the following formula (4) may include more.

<Formula 3>

<Formula 4>

According to an embodiment, right circularly polarized light or left circularly polarized light may be emitted from the emission layer. For example, an organic light emitting device in which the light emitting layer includes (R)-platinum complex may emit left circularly polarized light, and an organic light emitting device in which the emission layer includes (S)-platinum complex may emit right circularly polarized light.

The content of the dopant included in the emission layer may be about 0.01 to about 49.99 parts by weight based on 100 parts by weight of the emission layer.

In an embodiment, the first electrode is an anode, the second electrode is a cathode, and the organic layer is a hole transport region disposed between the first electrode and the light emitting layer and between the light emitting layer and the second electrode. It may further include an electron transport region.

The hole transport region includes a hole injection layer, a hole transport layer, a light emitting auxiliary layer, an electron blocking layer, or any combination thereof, and the electron transport region includes a buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, or any thereof. may include a combination of

The first electrode may be formed, for example, by providing a material for the first electrode on the substrate using a deposition method or a sputtering method. When the first electrode is an anode, the material for the first electrode may be selected from materials having a high work function to facilitate hole injection. The first electrode may be a reflective electrode, a transflective electrode, or a transmissive electrode. As the material for the first electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), zinc oxide (ZnO), or the like may be used. Alternatively, a metal such as magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), or magnesium-silver (Mg-Ag) may be used. .

The hole transport region may include a known hole transport material. Examples of the hole transporting material include m-MTDATA, TDATA, 2-TNATA, NPB, β-NPB, TPD, Spiro-TPD, Spiro-NPB, methylated-NPB, TAPC, HMTPD, TCTA (4,4',4" -tris(N- carbazolyl )triphenylamine(4,4',4"-tris(N-carbazolyl)triphenylamine)), PANI:DBSA (Polyaniline/Dodecylbenzenesulfonic acid), PEDOT:PSS(Poly(3,4 -ethylenedioxythiophene):Poly(4-styrenesulfonate)), PANI:CSA (Polyaniline:Camphor sulfonicacid), PANI:PSS (Polyaniline:Poly(4-styrenesulfonate)), or any combination thereof.

The electron transport region may include a known electron transport material. Examples of the electron transporting material may include BCP, Bphen, Alq ₃ , BAlq, TAZ, NTAZ, TPBi, or any combination thereof.

The second electrode may be a cathode. As the material for the second electrode, a metal having a low work function, an alloy, a conductive compound, or a combination thereof may be used. For example, as the material for the second electrode, lithium (Li), silver (Ag), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg) -In), magnesium-silver (Mg-Ag), ytterbium (Yb), silver-ytterbium (Ag-Yb), ITO, IZO, or any combination thereof may be used. The second electrode may be a transmissive electrode, a transflective electrode, or a reflective electrode.

In the present specification, a substituent is induced by exchanging one or more hydrogens with another atom or a functional group in an unsubstituted mother group.

For example, substituted C ₁ -C ₂₀ alkyl group, substituted C ₁ -C ₂₀ alkoxy group, substituted C ₂ -C ₂₀ alkenyl group, substituted C ₂ -C ₂₀ alkynyl group, substituted C ₆ -C ₂₀ At least one of the substituents of the aryl group, the substituted C ₆ -C ₂₀ aralkyl group, and the substituted C ₆ -C ₂₀ heteroaryl group,

Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group and C ₁ - C ₂₀ alkoxy group;

Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, C ₃ -C ₁₀ cycloalkyl group, C ₁ -C ₁₀ heterocycloalkyl group, C ₆ -C ₂₀ aryl group, C ₆ -C ₂₀ aryloxy group, C ₁ -C ₂₀ heteroaryl group, -Si(Q ₁₁ )(Q ₁₂ )(Q ₁₃ ), -N(Q ₁₁ )(Q ₁₂ ), -B(Q ₁₁ )( C ₁ substituted with at least one selected from Q ₁₂ ), -C(=O)(Q ₁₁ ), -S(=O) ₂ (Q ₁₁ ), and -P(=O)(Q ₁₁ )(Q ₁₂ ) -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group and C ₁ -C ₂₀ alkoxy group;

C ₃ -C ₁₀ cycloalkyl group, C ₁ -C ₁₀ heterocycloalkyl group, C ₆ -C ₂₀ aryl group, C ₆ -C ₂₀ aryloxy group and C ₁ -C ₂₀ heteroaryl group;

Deuterium, -F, -Cl, -Br, -I, hydroxyl group, cyano group, nitro group, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₁ - C ₂₀ alkoxy group, C ₃ -C ₁₀ cycloalkyl group, C ₁ -C ₁₀ heterocycloalkyl group, C ₆ -C ₂₀ aryl group, C ₆ -C ₂₀ aryloxy group, C ₁ -C ₂₀ heteroaryl group, -Si (Q ₂₁ )(Q ₂₂ )(Q ₂₃ ), -N(Q ₂₁ )(Q ₂₂ ), -B(Q ₂₁ )(Q ₂₂ ), -C(=O)(Q ₂₁ ), -S(= O) ₂ (Q ₂₁ ) and -P(=O)(Q ₂₁ )(Q ₂₂ ), C ₃ -C ₁₀ cycloalkyl group, C ₁ -C ₁₀ heterocycloalkyl group, C ₆ -C substituted with at least one selected from ₂₀ aryl group, C ₆ -C ₂₀ aryloxy group and C ₁ -C ₂₀ heteroaryl group; and

-Si(Q ₃₁ )(Q ₃₂ )(Q ₃₃ ), -N(Q ₃₁ )(Q ₃₂ ), -B(Q ₃₁ )(Q ₃₂ ), -C(=O)(Q ₃₁ ), -S (=O) ₂ (Q ₃₁ ) and -P(=O)(Q ₃₁ )(Q ₃₂ );

can be selected from

The Q ₁₁ to Q ₁₃ , Q ₂₁ to Q ₂₃ and Q ₃₁ to Q ₃₃ are each independently hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a nitro group, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₁ -C ₂₀ alkoxy group, C ₆ -C ₂₀ aryl group and C ₁ -C ₂₀ heteroaryl group may be selected from have.

In the present specification, a and b of "carbon number a to b" or "C _a -C _b " mean the number of carbon atoms of a specific functional group (group). That is, the functional group may include carbon atoms a to b. For example, "a C 1 to C 4 alkyl group" or "C ₁ -C ₄ alkyl group" means an alkyl group having 1 to 4 carbons.

As used herein, the term "alkyl" refers to a branched or unbranched aliphatic hydrocarbon. For example, the alkyl group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, and the like.

As used herein, the term "alkenyl" refers to a branched or unbranched hydrocarbon having at least one carbon-carbon double bond. Non-limiting examples of alkenyl groups include vinyl, allyl, butenyl, isopropenyl, or isobutenyl.

As used herein, the term "alkynyl" refers to a branched or unbranched hydrocarbon having at least one carbon-carbon triple bond. Non-limiting examples of alkynyl groups include ethynyl, butynyl, isobutynyl, isopropynyl, and the like.

As used herein, the term "cycloalkyl" refers to a saturated hydrocarbon cyclic group, and the term "heterocycloalkyl" refers to a cyclic group further comprising, in addition to carbon atoms, at least one hetero atom as a ring-forming atom. it means.

As used herein, the term "alkoxy" refers to an alkyl or aryl, respectively, bound to an oxygen atom.

As used herein, the term "aryl" refers to an aromatic ring in which the ring backbone contains only carbon, a ring system (ie, two or more fused rings sharing two adjacent carbon atoms), or a plurality of aromatic rings is a single bond, -O-, -S-, -C(=O)-, -S(=O) ₂ -, -Si(R _a )(R _b )-(R _a and R _b are each independently an alkyl group having 1 to 10 carbon atoms), an alkylene group having 1 to 10 carbon atoms substituted or unsubstituted with halogen, or a ring connected to each other by -C(=O)-NH-. If the aryl group is a ring system, then each ring in the system is aromatic. For example, the aryl group includes, but is not limited to, a phenyl group, a biphenyl group, a naphthyl group, a phenalthrenyl group, a naphthacenyl group, and the like. The aryl group may be substituted or unsubstituted.

As used herein, the term "heteroaryl" includes at least one heteroatom selected from N, O, P or S as a ring-forming atom, and the remaining ring-forming atoms are carbon. (bicyclic) refers to a monovalent group having an aromatic system. The heteroaryl group may include, for example, 1-5 heteroatoms, and may include 5 to 10 ring members. The heteroaryl group may be substituted or unsubstituted.

Non-limiting examples of “heteroaryl” include thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxa Diazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl group, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5- Thiadiazolyl, 1,3,4-thiadiazolyl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, oxazol-2-yl, oxazol-4- yl, oxazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, 1,2,4-triazol-3-yl, 1,2, 4-triazol-5-yl, 1,2,3-triazol-4-yl, 1,2,3-triazol-5-yl, tetrazolyl, pyrid-2-yl, pyrid-3- yl, 2-pyrazin-2yl, pyrazin-4-yl, pyrazin-5-yl, 2-pyrimidin-2-yl, 4-pyrimidin-2-yl, or 5-pyrimidin-2-yl can be heard

As used herein, the term "aralkyl group" refers to an aryl group connected as a substituent via an alkylene group, such as an aralkyl group having 6 to 20 carbon atoms. Non-limiting examples of the aralkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, a naphthylalkyl group, and the like. In one embodiment, the alkylene group is a lower alkylene group (ie, an alkylene group having 1 to 4 carbon atoms).

As used herein, "hydroxyl group" is -OH.

As used herein, the "amino group" is -NH ₂ .

As used herein, "cyano group" is -CN.

As used herein, "nitro group" is -NO ₂ .

Hereinafter, a principle of inducing a helical sense in a chiral polymer according to an embodiment will be described with reference to FIG. 1 .

Polymers synthesized by general radical polymerization have point chirality including both (R)-configuration and (S)-configuration in the main chain. As such, the presence of a mixture of (R)- and (S)-configuration in the main chain leads to the formation of a half-sandwich conformer in which neighboring carbazole pendants partially overlap. The conformation can give rise to different helical senses between adjacent carbazole pendants, i.e., (M)-helical and (P)-helical sense.

For example, if the carbazole pendant is achiral, the point chirality of the backbone is that the (R)-configuration and (S)-configuration are formed in a 50:50 ratio, so the polymer backbone is (M)-helical and (P)- The helicals cancel each other out, so they don't have a helical sense.

On the other hand, in the chiral polymer according to an embodiment, the formation ratio of the point chiral (R)-configuration and (S)-configuration of the main chain deviates from 50:50 due to the mutual attraction of adjacent chiral carbazole pendants. Accordingly, as for the point chirality of the main chain, the formation rate of any one of the (R)-configuration and the (S)-configuration may be dominant.

As mentioned above, since either the (R)- or (S)-configuration predominates in the viscochirality of the main chain, the helical sense induced by the partially overlapping carbazole conformations is either clockwise or left-rotating. one prevails. Accordingly, the polymer backbone may also have a helical sense that is enriched with a right-rotating or left-rotating helical sense. That is, in the chiral polymer according to an embodiment, due to an asymmetry bias of the helical sense caused by the chiral carbazole pendant, the helical sense of any one of the main chains may be strongly displayed.

For example, in the chiral polymer according to an embodiment shown in FIG. 1 , a carbazole form having a (P)-helical sense may be favored by asymmetrical deflection of the chiral carbazole pendant. Accordingly, the chiral polymer according to an embodiment may be a polymer having an excess of (P)-helical sense.

In the present specification, the chiral polymer according to an embodiment may be represented as "JY _n polymer". The JY _n polymer can be synthesized via conventional free radical polymerization using the following chiral monomer A and achiral monomer B, where n is the molar percentage of chiral monomer A in the monomer feed (i.e. 100*[A]/( [A] + [B])), and 0<n≤100.

Table 1 below shows structural parameters and thermal property data of exemplary homopolymer JY ₀ and chiral polymers JY ₁ , JY ₂ , JY ₁₀ , JY ₄₀ , JY ₇₀₀ and JY ₁₀₀ according to an embodiment.

In Table 1 below, the molar ratio of the chiral repeat unit (M*) and the achiral repeat unit (M) was measured using ¹ H NMR spectroscopy (300 MHz, CD ₂ Cl ₂ ), and the number average molecular weight (M _n ) and weight The average molecular weight (M _w ) was determined by GPC using Shodex ^® respectively. The cracking temperature (T _d,90 ) is defined as the temperature at which the residual weight during cracking reaches 90% of the original weight.

Monomer feed molar ratio
([A]:[B]) transference number
(%) repeat unit molar ratio
([M*]:[M]) glass transition temperature
(T _g ) (°C) cracking temperature
(T _d,90 ) (°C) number average molecular weight
(M _n ) weight average molecular weight
(M _w ) polydispersity index
(PDI) JY ₀ 0:100 80 0:100 194 408 13000 30000 2.3 JY ₁ 1:99 79 2:98 190 411 10000 18000 1.8 JY ₂ 2:98 82 4:96 190 411 10000 18000 1.8 JY ₁₀ 10:90 71 7:93 170 401 7400 14000 2.0 JY ₄₀ 40:60 62 30:70 164 398 8700 19000 2.2 JY ₇₀ 70:30 73 53:47 150 401 8800 21000 2.4 JY ₁₀₀ 100:0 68 100:0 140 399 12000 30000 2.5

In Table 1, the nonlinearity between the mole fraction of M* in the polymer chain and the mole fraction of A during the monomer supply indicates that the polymerization reactivity of the chiral monomer is inferior to that of the achiral monomer.

Hereinafter, the JY _n polymer according to an embodiment will be described with reference to FIGS. 2 to 4 .

2 is a UV-vis absorption spectrum of a JY _n polymer film according to an embodiment, and FIG. 3 is a normalized photoluminescence (PL) spectrum (excitation light λ _exc = 339 nm) of a JY _n polymer film according to an embodiment. ), and FIG. 4 is a normalized electron circular dichroism (ECD) curve expressed as a Kuhn asymmetry factor (g _abs ) of a JY _n polymer film according to an embodiment and a UV-Vis absorption spectrum of Compound 2 (bottom dotted line) It is a drawing showing together.

As the JY _n polymer film, a neat film in which JY _n polymer was spin-coated on a quartz substrate was used.

Referring to FIG. 2 , the absorption spectrum of the JY _n polymer includes electron transition bands with peaks at 265 nm, 308 nm, and 352 nm. The spectrum shown by the dotted line is the absorption spectrum of the compound 2 ((S)-9-(1-phenylpropan-2-yl)-9H-carbazole) solution. Comparing the absorption spectra of Compound 2 and the JY _n polymer film, it can be seen that the electron transition of each peak wavelength is the intrinsic transition of the carbazole moiety. According to quantum chemical calculation, the absorption band of the 308 nm wavelength of the JY _n polymer film contains the long-axis electronic transition of the carbazole moiety, and the absorption band of the 352 nm wavelength contains the short-axis electronic transition of the carbazole moiety.

Referring to FIG. 3 , the PL spectrum of chiral compound 2 maintains the characteristic vibrational progression of carbazole with a peak wavelength of 350 nm, whereas the PL spectrum of the JY _n polymer has a broad peak emission band with a peak wavelength of 420 nm. indicates The JY ₄₀ , JY ₇₀ and JY ₁₀₀ polymer films exhibit shoulder emission bands in the region of about 380 nm to 384 nm. The peak emission band and shoulder emission band result from the excimer transition of the full-sandwich carbazole pair and the excimer of the half-sandwich carbazole pair, respectively. The emission intensity of the shoulder emission band increases with n, which is expected to be due to the undesirable isotacticity of JY _n due to the larger steric bulk of the chiral repeating unit M*.

Asymmetric exciton coupling of JY _n polymer according to an embodiment will be described with reference to FIG. 4 .

Referring to FIG. 4 , in the ECD spectrum of the JY ₄₀ , JY ₇₀ and JY ₁₀₀ polymer films, a negative cotton effect at about 263 nm and a positive cotton effect at about 290 nm appear. The Cotton effect refers to a phenomenon in which the sign of the ECD spectrum is changed. When the absorption spectrum of Compound 2 indicated by the dotted line in FIG. 4 and the ECD spectrum of the JY _n polymer film are matched, it can be seen that the positive cotton effect at 290 nm of the ECD spectrum corresponds to the long-axis transition of carbazole. That is, along the main chain of the chiral polymer of one embodiment, it can be seen that there is asymmetric exciton coupling between the long-axis transition excitons of adjacent carbazole pendants. According to the exciton chirality rule of Nakanishi and Harada, the carbazole long-axis transition of 290 nm originates from a half-sandwich conformation with (P)-helical sense. The presence of the half-sandwich excimer indicates that there is an axial chiral alignment of the carbazole along the chiral polymer backbone.

In FIG. 4 , the g _abs value increases with n of JY _n , and the largest |g _abs | of 3.1×10 ⁻⁴ at 255 nm for the JY ₁₀₀ polymer film. have a value |g _abs | as n increases The increase is similar to the tendency that the relative emission intensity of the half-sandwich excimer shown in FIG. 3 increases as n increases. From this tendency, it can be seen that electron circular dichroism and excimer emission are derived from the helical carbazole form.

Hereinafter, the chiral amplification phenomenon of the chiral polymer according to an embodiment will be described with reference to FIG. 5 . 5 shows the normalized Kuhn asymmetry factor (g _abs (JY _n )/g _abs (JY ₁₀₀ ), λ=304 nm) to the fraction of chiral repeat units ([M*] / [M*]+[M]). It is a diagram showing The red curve in FIG. 5 represents the least squares approximation curve of the data values indicated by the red dots. Referring to FIG. 5 , the normalized Kuhn asymmetry factor is larger than the linear relationship for the fraction of chiral repeat units. This non-linearity indicates that the chirality repeat unit transfers chirality to the achiral monomer during polymerization of the polymer (see inset in Figure 5).

This chirality transfer is an example of the sergeant-soldier principle, in which the achiral monomer acts as the soldier molecule and the chiral polymer backbone acts as the sergeant. In the present invention, chirality amplification is expected to be amplified by the principle that point chirality of the carbazole pendant is transferred to the polymer main chain and then chirality is cooperatively propagated along the main chain in the chain growth process. It is not limited.

Table 2 below shows the photophysical and chiral chiroptical property parameters of JY _n polymers.

In Table 2 below, the emission extinction rate ( k _r ) was calculated according to the equation k _r = PLQY/ τ _obs , and the specific emission extinction rate ( k _nr ) was calculated according to the equation k _nr = (1-PLQY)/ τ _obs . .

absorption peak wavelength
(λ _abs )
(nm) emission peak wavelength
(λ _em )
(nm) Kuhn asymmetry factor (g _abs )
(10 ^-4 , λ _obs = 304 nm) photoluminescence lifetime
(τ _obs , ns) Absolute PLQY
k _r
(10 ⁷ s ^-1 ) k _nr
(10 ⁷ s ^-1 ) JY ₀ 308, 353 418 0.063 15 0.18 (±0.046) 1.2 5.5 JY ₁ 308, 353 418 0.13 15 0.12 (±0.004) 0.73 5.9 JY ₂ 308, 353 420 0.056 15 0.16 (±0.027) 1.1 5.6 JY ₁₀ 308, 353 420 0.29 9.1 0.23 (±0.029) 2.5 8.5 JY ₄₀ 308, 353 384 (shoulder), 417 0.92 12 0.20 (±0.025) 1.7 6.7 JY ₇₀ 308, 352 382 (shoulder), 417 1.5 10 0.26 (±0.015) 2.6 7.4 JY ₁₀₀ 308, 352 380 (shoulder), 417 2.0 15 0.26 (±0.008) 1.7 4.9

In this specification and the description below, (R)-Pt:JY _n means a JY _n polymer film doped with (R)-Pt, and (S)-Pt:JY _n is doped with (S)-Pt. JY _n means polymer film.

The effect of the chiral polymer of the present invention on the chiral photorotation of the chiral dopant will be described with reference to FIGS. 6 and 7 .

6A is a JY ₀ polymer film, (R)-Pt 10 wt% doped JY ₀ polymer film, (S)-Pt 10 wt% doped JY ₀ polymer film, (R)-Pt, and (S)-Pt is a diagram showing the UV-vis absorption spectrum of

Referring to FIG. 6a , the UV-vis absorption spectrum of the JY ₀ polymer film is hardly affected by whether (R)-Pt or (S)-Pt is doped. This indicates that the formation of ground state species between the JY ₀ polymer acting as a host and (R)-Pt or (S)-Pt acting as a dopant is hardly seen.

Figure 6b plots the Kuhn asymmetry factor (g _abs ) of JY ₀ polymer film, (R)-Pt 10 wt % doped JY ₀ polymer film and (S)-Pt 10 wt % doped JY ₀ polymer film as a function of wavelength. 6c is a graph showing the Kuhn asymmetry factor (g _abs ) of the JY _{0 polymer film doped with (R)-Pt 10 wt % and (S)-Pt 10 wt % doped JY 0 polymer} film and the JY ₀ polymer film. It is a graph showing the difference (Δg _abs ) of the Kuhn asymmetry factor (g _abs ) according to the wavelength.

Referring to FIG. 6B , electron circular dichroism signals of the JY ₀ polymer film doped with (R)-Pt and the JY ₀ polymer film doped with (S)-Pt exhibited mirror images of each other. Through this, it can be seen that the chiral photorotation observed in each film is due to the platinum complex.

6b and 6c, the electron transition at 316 nm (|g _abs | = 1.37×10 ⁻⁴ ) overlaps the ligand-centered (LC) transition band of the platinum complex, and at 372 nm (|g _abs ) | = 2.2×10 ⁻⁴ ) overlapped with the metal-to-ligand charge transfer (MLCT) transition band of the platinum complex. The fact that the (R)-Pt doped JY ₀ polymer film and the (S)-Pt doped JY ₀ polymer film have the same |g _abs | at 372 nm means that chiral photorotation is inherent in the platinum complex. . On the other hand, it can be seen that the JY ₀ polymer film exhibits Δg _abs of the mirror image in the region of about 250 nm to 400 nm. Through this, it can be confirmed that there is no diastereomeric interaction between the JY ₀ polymer film and the platinum complex.

7a, 7b and 7c are respectively UV-vis absorption spectra measured by replacing the JY ₀ polymer film with a JY ₁₀₀ polymer film, the Kuhn asymmetry factor according to wavelength (g _abs ), and the difference in the Kuhn asymmetry factor according to wavelength ( Δg _abs ).

By comparing the ECD spectra of Fig. 6b and Fig. 7b, the effect of JY ₁₀₀ polymer on the absorption transition of the platinum complex can be explained. Referring to FIG. 7B , it can be seen that the ECD signals of the polymer film doped with (R)-Pt and the film doped with (S)-Pt are out of a symmetric relationship with each other. Looking at the Δg _abs value of FIG. 7c excluding the effect of the EDC signal of the JY ₁₀₀ polymer film, the (R)-Pt:JY ₁₀₀ polymer film and the (S)-Pt: JY ₁₀₀ polymer film are 5.7×10 ⁻⁴ , respectively. and Δg _abs values of 0.50×10 ⁻⁴ (λ=391 nm). The Δg _abs of (R)-Pt was larger in the JY ₁₀₀ polymer film than in the JY ₀ polymer film (Δg _abs = 2.5×10 ⁻⁴ ), whereas the Δg _abs of (S)-Pt was higher in the JY ₀ polymer film (Δg _abs = 1.7). ×10 ^-4 ) in the JY ₁₀₀ polymer film. That is, the stereoselectivity shown in the JY ₁₀₀ polymer film indicates that a diastereoselective interaction exists between the chiral polymer and the chiral platinum complex.

8 is a plot showing the Kuhn asymmetry factor as a function of wavelength of a JY _n polymer film doped with 10 wt % (R)-Pt.

Referring to FIG. 8 , as the fraction of the chiral repeating unit (M*) of the main chain increases, it can be seen that the g _abs value of about 372 nm corresponding to the MLCT transition tends to increase. From the results of FIG. 8 , it can be expected that the diastereoselective interaction between the chiral polymer and the platinum complex originates from the chiral repeating unit of the polymer backbone.

9a, 9b and 9c are PL spectra of a JY ₀ polymer film doped with (R)-Pt or (S)-Pt and a JY ₁₀₀ polymer film doped with (R)-Pt or (S)-Pt, respectively; Fig. 9a), the CPL spectrum (Fig. 9b) and the photoluminescence asymmetry constant (g _PL ) as a function of wavelength (Fig. 9c) are plotted. The dopant concentration of the platinum complex in the JY _n polymer film was 30 wt%.

Measurements of circularly polarized luminescence were performed using the following in-house CPL spectroscopy system. Light emitted from the sample is modulated by a photoelastic modulator (PEM, PEM-100, manufactured by Hinds Instruments) that provides a sine-wave quarter-wave delay oscillating at 47 kHz and then passes through a linear polarizer oriented 45° to the PEM axis. did. The optical power detected by the photomultiplier tube (PMT, R9182-01, manufactured by Hamamatsu) was amplified by a current amplifier (C11184, manufactured by Hamamatsu). The DC and AC components of the amplified signal were measured using a digital multimeter (34410A, manufactured by Agilent) and a locking amplifier (SR830, manufactured by Stanford Research Systems), respectively. The operation of the CPL spectroscopic system was performed by reproducing the g _PL spectrum of 5.5 mM europium tris[3-(trifluoromethylhydroxymethylene)-(+)-camphorate] ([Eu(facam) ₃ ]) diluted in DMSO. Confirmed. g _PL measurements were made by exciting the sample with an LED having a 365 nm peak wavelength.

Referring to FIG. 9A , the JY ₀ and JY ₁₀₀ polymer films exhibit the same emission spectrum regardless of the absolute arrangement of the dopant. The emission bands (R)-Pt and (S)-Pt correspond to phosphorescence emission bands caused by metal-ligand charge transfer (MLCT) transition of the platinum complex.

Referring to FIG. 9B , circularly polarized light emission appears in the same wavelength range as the emission spectrum of FIG. 9A , indicating that the platinum complex generates circularly polarized light emission.

Referring to FIG. 9c , the signs of the photoluminescence asymmetry constants (g _PL ) of the (R)-Pt:JY ₀ film and the (S)-Pt:JY ₀ film are opposite to each other, similar to the ECD signal of FIG. 6b . A mirror image is shown. From this, it can be seen that a typical electronic transition state is involved in the absorption and emission transition of circularly polarized light. On the other hand, the maximum g _PL values of the (R)-Pt:JY ₁₀₀ and (S)-Pt:JY ₁₀₀ polymer films were 1.0×10 ⁻³ (emission wavelength λ _em = 540 nm) and −0.94×10 ⁻³ ( The emission wavelength λ _em = 545 nm), which was larger than the maximum g _PL value of the JY ₀ polymer film, respectively. From the improvement of g _PL in the JY ₁₀₀ polymer film, it can be seen that the circular polarization phosphorescence properties of the chiral platinum complex are amplified by the asymmetric environment of the chiral polymer host.

In addition, in Fig. 9c, the difference in |g _PL | of the (R)-Pt:JY polymer film (that is, the difference between the blue filled circle and the empty circle) is the difference in |g _PL | of the (S)-Pt:JY polymer film. (that is, the difference between the red filled circle and the empty circle). From this, it can be confirmed that the JY ₁₀₀ polymer affects the chiral photorotation by diastereoselective interaction with the chiral platinum complex.

Hereinafter, energy transfer from a polymer host to a chiral platinum complex according to an embodiment will be described with reference to FIGS. 10 to 14 .

10A and 10B are PL spectra of a JY ₀ polymer film and a JY ₁₀₀ polymer film having different (R)-Pt doping concentrations, respectively. 10A and 10B, undoped JY ₀ and JY ₁₀₀ films exhibit carbazole excimer emission at 428 nm (excitation light λ _exc = 339 nm). As the doping concentration of the platinum complex increased, the emission of the host JY ₀ and JY ₁₀₀ polymer decreased and the dopant emission with a peak wavelength of 586 nm appeared. This indicates that activated energy donor-energy acceptor pairs are formed at high doping concentrations. Meanwhile, at the same dopant concentration, the JY ₁₀₀ polymer film exhibits higher luminescence intensity than the JY ₀ polymer film.

11 is a diagram illustrating quantitative curves of I ₀ /I according to doping concentrations of (R)-Pt or (S)-Pt of (R)-Pt:JY and (S)-Pt:JY polymer films. Here, I ₀ is the host emission intensity in the absence of the platinum complex, and I is the host emission intensity in the presence of the platinum complex (emission wavelength λ _em = 420 nm).

Referring to FIG. 11 , it can be seen that the JY ₀ and JY ₁₀₀ polymer films follow a similar rise profile, but the JY ₁₀₀ polymer film exhibits a faster rise in I ₀ /I as the doping concentration increases. This indicates that energy transfer from the JY ₁₀₀ polymer host to the platinum complex dopant occurs faster than in the JY ₀ polymer film.

12A and 12B are transient PL spectra of JY ₀ and JY ₁₀₀ polymer films with different doping concentrations of (R)-Pt, respectively. Transient PL spectra were measured by monitoring host emission decay traces at a wavelength of 420 nm after excitation with a picosecond pulsed laser at 377 nm.

The average photoluminescence lifetime (τ) of the JY ₀ polymer film calculated from the transient PL spectrum is 10 ns. As the doping concentration of (R)-Pt increases, τ decreases due to the increased energy transfer to the dopant. From FIGS. 12A and 12B , it can be seen that the JY ₁₀₀ polymer film has a shorter τ than the JY ₀ polymer film. This indicates that JY ₁₀₀ polymer can transfer energy more efficiently to (R)-Pt.

From the transient PL spectra of FIGS. 12A and 12B , the energy transfer rate (k _ET ) from the JY _n polymer host to the platinum dopant was calculated according to Equation 3 below, and the result is shown as a line graph in FIG. 13 .

<Equation 3>

k _ET = 1/τ - 1/τ ₀

Here, τ is the photoluminescence lifetime in the presence of the dopant, and τ ₀ is the photoluminescence lifetime in the absence of the dopant.

From FIG. 13 , it can be seen that the energy transfer rate increases as the dopant concentration increases. In addition, in the dopant concentration range of 0.2 to 10 wt%, k _ET appears larger in the JY ₁₀₀ film than in the JY ₀ film. However, the energy transfer rate appears to be substantially the same irrespective of the absolute arrangement of the dopant. This indicates that the energy transfer from the JY ₁₀₀ polymer host is independent of the chirality of the dopant.

14A and 14B are diagrams showing confocal laser scanning micrographs of JY ₀ and JY ₁₀₀ polymer films having different (S)-Pt doping concentrations, respectively. The photoluminescence images of each film were visualized using a confocal laser scanning microscope (LSM780 NLO, manufactured by Carl Zeiss). An excitation beam (405 nm) was focused on the film and photoluminescence signals were acquired for the emission range of 500 nm to 700 nm, and the acquired images were analyzed using ZEN 2.3 SP1 version 14.0 imaging software from Carl Zeiss.

14a and 14b, the bright spots correspond to aggregates of (S)-Pt. 14a and 14b, it can be seen that the JY ₀ film contains more dopant aggregates than the JY ₁₀₀ film. Referring to FIGS. 14A and 14B , it can be inferred that the phase homogeneity of the JY ₁₀₀ film contributes to the excellent energy transfer rate of the host.

14c and 14d show together the energy dispersive X-ray spectra and TEM images (inset) of a 50 wt% (S)-Pt:JY ₀ film and a 50 wt% (S)-Pt:JY ₁₀₀ film, respectively, respectively. it is one drawing Each (S)-Pt:JY _n film was prepared in a 1,2-dichloroethane solution containing (S)-Pt and JY _n polymer ((S)-Pt:JY _n = 50:50 w/w) ( A solids concentration of 1.0 wt%) was prepared by spin coating a 200-mesh carbon film on a copper grid.

The black dots appearing in the TEM image of the JY ₀ film indicate poor phase homogeneity of the JY ₀ film. On the other hand, it can be seen that the JY ₁₀₀ film has better phase homogeneity than the JY ₀ film (see the inset of FIGS. 14c and 14d ).

Furthermore, it was confirmed from the energy dispersive X-ray spectrum that the atomic percentage of Pt in the composition of the JY ₀ film and the JY ₁₀₀ film was 1.5 at% and 1.4 at%, respectively. This indicates that there is Pt enrichment in the aggregates that appear as black dots in the TEM image.

From FIG. 14 , it can be seen that the improved energy transfer rate of the JY ₁₀₀ film compared to the JY ₀ film comes from the long Forster radius and the improved compatibility with the platinum complex. The phase homogeneity of the JY ₁₀₀ film can allow for molecular level dispersion of the dopant within the Forster radius of the polymer host. In fact, the Forster radii of the JY ₀ and JY ₁₀₀ films were calculated to be 25 Å and 27 Å, respectively, based on the refractive index 1.047 and the spectral overlap integral with the platinum dopant.

Hereinafter, exciton formation in a chiral dopant according to an embodiment will be described with reference to FIG. 15 .

FIG. 15 is a voltammogram of argon saturated THF containing JY ₀ , JY ₁₀₀ , (R)-Pt and (S)-Pt.

A host and a dopant satisfying Equations 4 and 5 below may undergo Shockley-Read-Hall recombination.

<Formula 4>

E _ox (H) > E _ox (D)

<Formula 5>

E _red (H) < E _red (D)

In Equations 4 and 5, E _ox (H) and E _ox (D) are oxidation potentials of the host and dopant, respectively, and E _red (H) and E _red (D) are reduction potentials of the host and dopant, respectively.

Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were used to measure redox potentials for the JY _n polymer and the platinum complex, and the results are shown in FIG. 15 . The solid line represents the cyclic voltammetry, and the dotted line represents the differential pulse voltammogram.

Referring to FIG. 15 , JY ₀ and JY ₁₀₀ show irreversible oxidation at 1.25 and 1.22 V vs. SCE, respectively. This peak is close to the oxidation potential (1.39 V vs. SCE) of poly(N-vinyl carbazole), indicating that carbazole in JY ₀ and JY ₁₀₀ is responsible for oxidation. The oxidation potential values of (R)-Pt and (S)-Pt are 0.88 V versus SCE, which is more cathodic than that of the JY _n polymer. Therefore, hole traps in the platinum complex are thermodynamically favored over JY ₀ and JY ₁₀₀ . By subtracting the optical bandgap energy from the oxidation potential value, the reduction potential value can be obtained (bandgap energy of JY _n host = 3.43eV, bandgap energy of platinum complex = 2.48eV). The calculated reduction potential values are -2.18V (JY ₀ ), -2.21V (JY ₁₀₀ ) and -1.60V ((R)-Pt and (S)-Pt). The reduction potential value of the platinum complex is more bipolar than the reduction potential value of the JY _n host, suggesting that electron trapping by the dopant is effective due to the thermodynamic driving force. From these electrochemical results, it can be seen that the JY _n polymer can effectively trap charge carriers in the platinum complex.

16 is a diagram illustrating an energy diagram of an organic light emitting diode according to an exemplary embodiment.

An organic light emitting diode according to an embodiment was manufactured according to the following method.

The glass substrate coated with the ITO anode was sequentially washed with detergent, deionized water, acetone and isopropyl alcohol in an ultrasonic cleaner, followed by UV-ozone treatment for 30 minutes. The GraHIL layer was prepared by spinning a solution of PEDOT:PSS (P VP AI 4083, CLEVIOS) and tetrafluoroethylene perfluoro-3,6-dioxa-4-methyl-7-octenesulfonic acid copolymer (Nafion, DuPont). A hole transport layer having a thickness of 50 nm was formed by coating (4500 rpm, 60 seconds) followed by baking on a hot plate at 150° C. for 30 minutes. JY _n polymer and platinum complex (doping concentration 30 wt%) were dissolved in 1,2-dichloroethane at a total solid concentration of 0.5 wt%, and filtered using a 0.45 μm pore size PTFE syringe filter to prepare a solution for forming a light emitting layer . The solution for forming the light emitting layer was spin coated (5000 rpm, 40 seconds) on the hole injection layer in an N ₂ -charged glove box and baked on a hot plate at 100° C. for 30 minutes to form a light emitting layer with a thickness of 50 nm. An organic light emitting device was fabricated by loading a glass substrate formed up to the light emitting layer into a vacuum chamber (about 10 ^-7 torr), and then vacuum-depositing TPBi (50 nm), LiF (1 nm), and Al (100 nm) sequentially. .

17 is a diagram illustrating an electroluminescence (EL) spectrum of an organic light emitting diode according to an exemplary embodiment. Each EL spectrum was measured at a current density of 1.6 mA·cm ^-2 using a spectrometer (SR303i, Shamrock) coupled with a CCD camera (iDus 401, Andor). The organic light emitting device according to the exemplary embodiment exhibits substantially the same EL spectrum and a light emitting form that is substantially the same as the PL spectrum of the polymer film shown in FIG. 9A .

18 is a diagram illustrating a current density-voltage (J-V) curve (left) and a luminance-voltage (L-V) curve (right) of an organic light emitting diode according to an exemplary embodiment. Current density-voltage-luminance characteristics were measured using a source meter (2400 SourceMeter, Keithley, Inc.) and a Si photodiode (818-SL, Newport). 19 is an external quantum efficiency-current density (EQE-J) curve of an organic light emitting diode according to an exemplary embodiment. 18 and 19 , J-V-L characteristics and EQE-J curves show a typical phosphorescent organic light-emitting device, and it can be confirmed that the organic light-emitting device according to an embodiment exhibits normal electroluminescence operation.

20 is a diagram illustrating an electroluminescence asymmetry constant (g _EL ) according to a wavelength of an organic light emitting diode according to an exemplary embodiment. When the same host and dopant materials are used, g _EL of the organic light emitting device has the same sign as g _PL in the entire emission wavelength range. However, the size of g _EL appears to be about 10 times smaller than the size of g _PL , which reverses the rotation direction when circularly polarized light emitted toward the metal electrode is reflected from the metal surface, and is emitted toward the glass substrate. is expected to be offset by

[Synthesis Example]

Synthesis Example 1: JY _n Synthesis of polymers

Synthesis of compound 1

(R)-(-)-1-phenyl-2-propanol (10.4 g, 76.4 mmol) and p-toluenesulfonyl chloride (16.0 g, 83.7 mmol) were combined with pyridine in a 250 mL one-necked round-bottom flask equipped with a magnetic stirring bar. (40 mL). The mixture was stirred at room temperature under argon atmosphere for 1 day. The reaction mixture was poured into EtOAc (400 mL) and washed thoroughly with water (400 mL) 3 times. The recovered organic layer was dried over anhydrous MgSO ₄ and concentrated under reduced pressure. The residue obtained after removal of the solvent was purified by silica gel column chromatography while increasing the polarity of the eluent from EtOAc:hexane=1:9 (v/v) to EtOAc:hexane=1:1 (v/v). Compound 1 as a white powder was obtained in 94% yield.

¹ H NMR (300 MHz, CD ₂ Cl ₂ ) δ (ppm): 1.28 (d, J = 6.3 Hz, 3H), 2.41 (s, 3H), 2.74-2.90 (m, 2H), 4.69 (sextet, J ) = 6.3 Hz, 1H), 7.01-7.05 (m, 2H), 7.17-7.26 (m, 5H), 7.58 (d, J = 9.0 Hz, 2H). ¹³ C[ ¹ H] NMR (126 MHz, CD ₂ Cl ₂ ) δ (ppm): 20.9, 21.9, 43.3, 81.3, 127.1, 128.0, 128.9, 130.0, 130.2, 134.4, 137.0, 145.1. HR MS (FAB, m -NBA): Calcd for C ₁₆ H ₁₈ O ₃ S ([M+H] ⁺ ), 291.1050; found: 291.1053.

Synthesis of compound 2

Potassium carbonate (5.70 g, 102 mmol), carbazole (12.7 g, 76.1 mmol) and 18-crown-6 (25.2 g, 95.3 mmol) were added to a 250 mL two-necked round-bottom flask, and then dissolved in DMSO (50 mL). and the mixture was heated at 80° C. for 1 hour. Compound 1 (14.8 g, 50.8 mmol) dissolved in 30 mL of DMSO was added to the stirred solution and stirred for another 2 days. After the reaction mixture was cooled to room temperature, it was poured into EtOAc (400 mL) and washed thoroughly with water (400 mL) 3 times. The recovered organic layer was dried over anhydrous MgSO ₄ and concentrated in vacuo. The residue obtained after removal of the solvent was subjected to silica gel column chromatography while increasing the polarity of the eluent from CH ₂ Cl ₂ :hexane = 1:19 (v/v) to CH ₂ Cl ₂ :hexane = 1:1 (v/v). performed and purified. Compound 2 as a pale yellow solid was obtained in 7% yield.

R _f = 0.50 (CH ₂ Cl ₂ :hexane = 1:2, v/v).

¹ H NMR (300 MHz, CD ₂ Cl ₂ ) δ (ppm): 1.74 (d, J = 6.9 Hz, 3H), 3.26-3.53 (m, 2H), 5.00 (sextet, J = 6.9 Hz, 1H), 7.01-7.21 (m, 7H), 7.37-7.42 (m, 4H), 8.07 (d, J = 7.8 Hz, 2H). ¹³ C[ ¹ H] NMR (126 MHz, CD ₂ Cl ₂ ) δ (ppm): 19.2, 41.5, 110.6, 119.1, 120.7, 125.9, 126.9, 128.8, 129.4, 139.5. HR MS (FAB, m -NBA): Calcd for C ₂₁ H ₁₉ N ([M] ⁺ ), 285.1517; found: 285.1514.

Synthesis of compound 3

N,N-dimethylformamide (1.53 g, 20.9 mmol) and phosphorus (V) oxychloride (2.15 g, 14.0 mmol) were placed in a 25 mL two-necked round bottom flask, and the mixture was stirred at 0° C. under an argon atmosphere for 1 hour. . Compound 2 (1.00 g, 3.50 mmol) dissolved in 8 mL DMF was slowly added to the stirred solution at 0°C using a syringe, and the mixture was heated at 110°C for 1 day. After the reaction mixture was cooled to room temperature, it was poured into EtOAc (200 mL) and washed thoroughly with water (200 mL) 5 times. The recovered organic layer was dried over anhydrous MgSO ₄ , filtered, and concentrated under reduced pressure. The residue obtained after removal of the solvent was purified by silica gel column chromatography with an eluent CH ₂ Cl ₂ :hexane = 1:1 (v/v). Compound 3 as a yellow solid was obtained in 66% yield.

R _f = 0.20 (CH ₂ Cl ₂ :hexane = 1:1, v/v).

¹ H NMR (300 MHz, CD ₂ Cl ₂ ) δ (ppm): 1.79 (d, J = 7.2 Hz, 3H), 3.28-3.54 (m, 2H), 5.05 (sextet, J = 7.2 Hz, 1H), 6.97-3.99 (m, 2H), 7.05-7.08 (m, 3H), 7.27-7.31 (m, 1H), 7.48-7.50 (m, 3H), 7.89-7.95 (m, 1H), 8.15 (d, J ) = 7.8 Hz, 1H), 8.57 (s, 1H), 10.05 (s, 1H). ¹³ C[ ¹ H] NMR (126 MHz, CD ₂ Cl ₂ ) δ (ppm): 19.3, 30.3, 41.4, 109.7, 112.5, 120.6, 121.1, 124.0, 126.9, 127.0,128.8, 128.9, 129.2, 138.9, 191.9 . HR MS (FAB, m -NBA): Calcd for C ₂₂ H ₁₉ NO ([M+H] ⁺ ), 314.1540; found: 314.1548.

Synthesis of compound 4 (chiral monomorphic A)

Potassium carbonate (13.8 g, 99.6 mmol) and methyltriphosphonium bromide (35.7 g, 99.8 mmol) were dissolved in 1,4-dioxane (50 mL) in a 250 mL two neck round bottom flask equipped with a magnetic stirring bar. Compound 3 (1.3 g, 4.15 mmol) dissolved in 34 mL of 1,4-dioxane was added to the reaction mixture, followed by milli-Q water (7 mL). The mixture was stirred at 110° C. for 4 days under an argon atmosphere. The reaction mixture was cooled to room temperature, poured into EtOAc (400 mL) and washed thoroughly with water (400 mL) 3 times. The recovered organic layer was dried over anhydrous MgSO ₄ , filtered, and concentrated under reduced pressure. The polarity of the eluent was purified by silica gel column chromatography while increasing the polarity of the eluent from CH ₂ Cl ₂ :hexane = 1:49 (v/v) to CH ₂ Cl ₂ :hexane = 1:1 (v/v). Compound 4 as a yellow viscous solid was obtained in 40% yield.

R _f = 0.63 (CH ₂ Cl ₂ :hexane = 1:1, v/v).

¹ H NMR (300 MHz, CD ₂ Cl ₂ ) δ (ppm): 1.74 (d, J = 6.9 Hz, 3H), 3.25-3.50 (m, 2H), 4.82 (sextet, J = 6.9 Hz, 1H), 5.18 (d, J = 10.8 Hz, 1H), 5.77 (d, J = 17.4 Hz, 1H), 6.89 (dd, J = 10.8, 17.6 Hz, 1H), 7.00-7.16 (m, 5H), 7.18-7.21 (m, 1H), 7.37-7.52 (m, 4H), 8.05-8.09 (m 2H). ¹³ C[ ¹ H] NMR (126 MHz, CD ₂ Cl ₂ ) δ (ppm): 19.0, 30.3, 41.4, 110.2, 118.7, 120.6, 123.7, 125.2, 126.0, 126.6, 128.6, 129.3, 136.4, 138.2, 139.5 , 140.4. HR MS (FAB, m -NBA): Calcd for C ₂₃ H ₂₁ N ([M] ⁺ ), 311.1674; found: 311.1674.

Synthesis of compound 5 (achiral monomer B)

Compound 5 was synthesized in the same manner as in the synthesis of compound 4, except that N-ethylcarbazole-3-carboxyaldehyde was used instead of compound 3. Compound 5 was obtained as a white solid in 55% yield.

R _f = 0.63 (CH ₂ Cl ₂ :hexane = 1:1, v/v).

¹ H NMR (300 MHz, CD ₂ Cl ₂ ) δ (ppm): 1.42 (t, J = 7.2 Hz, 3H), 4.37 (q, J = 7.2 Hz, 2H), 5.19 (d, J = 10.8 Hz, 1H), 5.78 (d, J = 17.7 Hz, 1H), 6.92 (dd, J = 17.6, 10.9 Hz, 1H), 7.20-7.25 (m, 1H), 7.38-7.50 (m, 3H), 7.59 (d , J = 8.4 Hz, 1H), 8.08-8.11 (m, 2H). ¹³ C[ ¹ H] NMR (126 MHz, CD ₂ Cl ₂ ) δ (ppm): 14.1, 30.3, 108.6, 118.7, 119.9, 120.7, 122.7, 123.4, 125.4, 136.8, 138.7, 138.9, 140.4, 140.5. HR MS (FAB, m -NBA): Calcd for C ₁₆ H ₁₅ N ([M] ⁺ ), 221.1204; found: 221.1206.

JY _n Synthesis of polymers

Copolymer JY _n was prepared by carrying out free radical polymerization of compound 4 (chiral monomer) and compound 5 (achiral monomer) in the presence of AIBN as a thermal initiator.

For JY ₁ polymer Compound 4 (8.60 mg, 0.028 mmol), Compound 5 (608 mg, 2.76 mmol) and AIBN (9.16 mg, 55.8 mmol) were added to a 4 mL glass ampoule containing a magnetic stir bar. After 2.5 mL of anhydrous 1-methyl-2-pyrrolidinone was added to the glass ampoule, the vacuum-freeze-thaw cycle was repeated to completely degas the solution. The ampoule was sealed with a torch. Polymerization was carried out by heating the solution at 65° C. for 2 days under dark conditions. After the reaction mixture was cooled to room temperature, it was poured into 200 mL of stirred methanol to form a white precipitate. The precipitate was filtered off and washed thoroughly with methanol, and the filter cake was redissolved in CH ₂ Cl ₂ . After concentration, the cycle of reprecipitation and dissolution was repeated. The polymer collected therefrom was dried in a vacuum oven to obtain a JY ₁ polymer.

JY ₀ , JY ₂ , JY ₁₀ , JY ₄₀ , JY ₇₀ and JY ₁₀₀ in the same manner as in the synthesis of the JY ₁ polymer, except that the molar ratio of the compound 4 and the compound 5 during the monomer supply was changed as shown in Table 3 below. The polymer was prepared.

Monomer feed molar ratio
([A]:[B]) transference number
(%) repeat unit molar ratio
([M*]:[M]) JY ₀ 0:100 80 0:100 JY ₁ 1:99 79 2:98 JY ₂ 2:98 82 4:96 JY ₁₀ 10:90 71 7:93 JY ₄₀ 40:60 62 30:70 JY ₇₀ 70:30 73 53:47 JY ₁₀₀ 100:0 68 100:0

Synthesis Example 2: Synthesis of (S)-Pt

Synthesis of compound (S)-6

( S )-3,3'-dibromo-1,1'-bi-2-naphthol (0.958 g, 2.16 mmol) and tetrakis (triphenylphosphine)palladium (0) (0.251 g, 0.217 mmol) were mixed with magnetic stirring bar It was placed in a 100 mL two-necked round bottom flask and dissolved in anhydrous toluene (50 mL). 2-(tributylstannyl)pyridine (2.00 g, 5.43 mmol) dissolved in 2 mL of anhydrous toluene was added to the stirred solution under an argon atmosphere. The solution was stirred at 115° C. for 21 hours. The reaction mixture was cooled to room temperature and then concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography while increasing the polarity of the eluent from CH ₂ Cl ₂ :hexane = 3:1 (v/v) to CH ₂ Cl ₂ :hexane = 7:1 (v/v). Compound (S)-Pt as a yellow powder was obtained in 14% yield.

Synthesis of compound (S)-Pt

Compound (S)-6 ([Pt ₂ ( μ -Cl) ₂ (2-phenylpyridinate) ₂ ] and potassium carbonate were placed in a 50 mL 1-necked round-bottom flask equipped with a magnetic stirring bar and 2-ethoxyethanol ( 25mL).The mixture is stirred under argon atmosphere at 60°C for 16 hours.The reaction mixture is cooled to room temperature, poured into water (400mL) and neutralized with 1N HCl (aq).The crude product is CH ₂ Extract with Cl ₂ (400 mL X 3 times).The extracted organic layer is dried over anhydrous MgSO ₄ , filtered and concentrated in vacuo.The polarity of the eluent is CH ₂ Cl ₂ :CH ₃ OH = 99:1 (v /v) to CH ₂ Cl ₂ :CH ₃ OH = 49: 1 (v/v) was purified by performing silica gel column chromatography to obtain the compound (S)-Pt as an orange powder in a yield of 90%. .

R _f = 0.54 (CH ₂ Cl ₂ :CH ₃ OH = 19:1, v/v).

¹ H NMR (300 MHz, CD ₂ Cl ₂ ) δ (ppm): 6.94-7.08 (m, 5H), 7.14-7.23 (m, 4H), 7.36-751 (m, 5H), 7.68 (broad m, 1H) ), 7.85-7.89 (m, 2H), 7.92 (d, J = 9.0 Hz, 1H), 8.03 (d, J = 6.9 Hz, 1H), 8.13 (d, J = 7.8 Hz, 1H), 8.19 (s) , 1H), 9.11 (d, J = 4.5 Hz, 1H). ¹³ C[ ¹ H] NMR (126 MHz, CD ₂ Cl ₂ ) δ (ppm): 118.2, 119.2, 119.6, 121.3, 122.3, 123.6, 123.8, 124.3, 124.6, 126.1, 126.4, 126.5, 127.5, 127.9, 128.5 , 129.3, 129.4, 129.8, 129.9, 131.0, 132.8, 133.5, 134.9, 137.4, 138.9, 1339.5, 140.5, 146.4, 148.2, 153.1, 154.8, 157.8, 166.8. HR MS (FAB, m -NBA): Calcd for C ₃₆ H ₂₃ BrN ₂ O ₂ Pt ([M(-Br)] ⁺ ), 712.1558; found: 712.1585.

Synthesis Example 3: Synthesis of (R)-Pt

Synthesis of compound (R)-6

Compounds except that ( R )-3,3'-dibromo-1,1'-bi-2-naphthol was used instead of ( S )-3,3'-dibromo-1,1'-bi-2-naphthol Compound (R)-6 was synthesized in the same manner as in the synthesis of (S)-6. Compound (R)-6 as a yellow powder was obtained in 15% yield.

R _f =0.48 (CH ₂ Cl ₂ ).

¹ H NMR (300 MHz, CD ₂ Cl ₂ ) δ (ppm): 5.28 (s, 1H), 7.10 (d, J = 16.8 Hz, 1H), 7.19 (d, J = 15.9 Hz, 1H), 7.27 ( dd, J = 14.5, 5.7 Hz, 1H), 7.29-7.34 (m, 4H), 7.92 (d, J = 8.1 Hz, 1H), 7.96 (d, J = 8.7 Hz, 1H), 8.03-8.05 (m , 2H), 8.34 (d, J = 8.4 Hz, 1H), 8.57 (d, J = 4.8 Hz, 1H), 8.66 (s, 1H), 14.8 (s, 1H). ¹³ C[ ¹ H] NMR (126 MHz, CD ₂ Cl ₂ ) δ (ppm): 114.7, 116.0, 118.2, 120.9, 122.1, 123.2, 123.8, 124.2, 124.6, 125.3, 126.9, 128.4, 128.7, 128.71, 128.9 , 129.6, 129.8, 130.2, 134.3, 135.7, 139.0, 146.5, 152.1, 156.4, 157.8. HR MS (FAB, m -NBA): Calcd for C ₂₅ H ₁₆ BrNO ₂ ([M(-Br)+H] ⁺ ), 364.1333; found: 364.1340.

Synthesis of compound (R)-Pt

Compound (R)-Pt was synthesized in the same manner as in the synthesis of compound (S)-Pt, except that compound (R)- was used instead of compound (S)-6. Compound (R)-Pt as an orange powder was obtained in 96% yield.

R _f = 0.54 (CH ₂ Cl ₂ :CH ₃ OH = 19:1, v/v).

¹ H NMR (300 MHz, CD ₂ Cl ₂ ) δ (ppm): 6.94-7.08 (m, 5H), 7.14-7.23 (m, 4H), 7.36-7.45 (m, 5H), 7.68 (broad m, 1H) ), 7.85-7.89 (m, 2H), 7.98 (d, J = 9.0 Hz, 1H), 8.02 (d, J = 7.2 Hz, 1H), 8.13 (d, J = 8.5 Hz, 1H), 8.19 (s) , 1H), 9.11 (d, J = 6.0 Hz, 1H). ¹³ C[ ¹ H] NMR (126 MHz, CD ₂ Cl ₂ ) δ (ppm): 118.2, 119.2, 119.6, 121.3, 122.3, 123.5, 123.8, 124.3, 124.6, 126.1, 126.4, 126.5, 127.5, 127.9, 128.5 , 129.3, 129.4, 129.8, 129.9, 131.0, 132.8, 133.5, 134.9, 137.4, 138.9, 1339.5, 140.5, 146.4, 148.2, 153.1, 154.8, 157.8, 166.8. HR MS (FAB, m -NBA): Calcd for C ₃₆ H ₂₃ BrN ₂ O ₂ Pt ([M(-Br)] ⁺ ), 712.1558; found: 712.1599.

The photophysical and chiral photorotation characteristics of (S)-Pt and (R)-Pt synthesized in Synthesis Examples 2 and 3 are shown in Table 4 below.

absorption peak wavelength
(λ _abs )
(nm) emission peak wavelength
(λ _em )
(nm) Kuhn asymmetry factor (g _abs )
(10 ^-3 ,λ _obs = 372 nm) photoluminescence lifetime
(λ _obs , μs) Absolute PLQY
k _r
(10 ⁴ s ^-1 ) k _nr
(10 ⁵ s ^-1 ) (R)-Pt 262, 320, 400 590 -2.1 21 0.25 1.2 3.6 (S)-Pt 262, 320, 400 590 2.3 21 0.25 1.1 3.6

Claims (12)

A chiral polymer comprising a first repeating unit represented by the following formula (1):
<Formula 1>

In Formula 1,
R ₁ To R ₁₀ are each independently hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, an amino group, a cyano group, a nitro group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, Substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, substituted or unsubstituted C ₂ -C ₂₀ alkenyl group, substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, substituted or unsubstituted C ₆ -C ₂₀ aryl a group, a substituted or unsubstituted C ₆ -C ₂₀ aralkyl group, or a substituted or unsubstituted C ₁ -C ₂₀ heteroaryl group,
R ₈ to R ₁₀ are different from each other,
* is the stereocenter. According to claim 1,
A chiral polymer comprising a first repeating unit represented by the following formula (1A):
<Formula 1A>

In Formula 1A,
For the description of R ₁ to R ₇ , refer to the description in claim 1, respectively,
R ₈ is deuterium, -F, -Cl, -Br, -I, a hydroxyl group, an amino group, a cyano group, a nitro group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, substituted or unsubstituted C ₂ -C ₂₀ alkenyl group, substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, substituted or unsubstituted C ₆ -C ₂₀ aryl group, or substituted or unsubstituted C ₁ -C ₂₀ is a heteroaryl group,
For the description of R ₁₁ and R ₁₂ , refer to the description of R ₁ in claim 1, respectively,
R ₈ and

groups are different,
* is the stereocenter. According to claim 1,
A chiral polymer in which one helical sense of left rotation and right rotation is stronger than the other helical sense. According to claim 1,
A chiral polymer that has a stronger right-handed helical sense than a left-handed helical sense. According to claim 1,
A chiral polymer further comprising an achiral second repeating unit. According to claim 1,
A chiral polymer further comprising an achiral second repeating unit represented by the following formula (2):
<Formula 2>

In Formula 2,
R ₂₁ to R ₂₈ are each independently hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, an amino group, a cyano group, a nitro group, or a C ₁ -C ₂₀ alkyl group not including a stereocenter , C ₁ -C ₂₀ alkoxy group without stereocenter, C ₂ -C ₂₀ alkenyl group without stereocenter, C ₂ -C ₂₀ alkynyl group without stereocenter, C ₆ -C ₂₀ aryl group or a C ₁ -C ₂₀ heteroaryl group. A chiral polymer comprising a first repeating unit represented by the following formula (1); and
a platinum complex selected from (R)-platinum complexes represented by the following formula (3) and (S)-platinum complexes represented by the following formula (4);
A composition comprising:
<Formula 1>

<Formula 3>

<Formula 4>

In Formula 1,
R ₁ To R ₁₀ are each independently hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, an amino group, a cyano group, a nitro group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, Substituted or unsubstituted C ₁ -C ₂₀ alkoxy group, substituted or unsubstituted C ₂ -C ₂₀ alkenyl group, substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, substituted or unsubstituted C ₆ -C ₂₀ aryl a group, a substituted or unsubstituted C ₆ -C ₂₀ aralkyl group, or a substituted or unsubstituted C ₁ -C ₂₀ heteroaryl group,
R ₈ to R ₁₀ are different from each other,
* is the stereocenter. 8. The method of claim 7,
The composition comprising the (R)-platinum complex emits left circularly polarized light (LCPL),
The composition comprising the (S)-platinum complex emits right circularly polarized light (RCPL). 8. The method of claim 7,
The size of the Kuhn asymmetry factor (|g _abs |) of the composition containing the (R)-platinum complex is greater than the size of the Kuhn asymmetry factor of the composition containing the (S)-platinum complex (|g _abs |) at least ten times greater, the composition. a first electrode;
a second electrode facing the first electrode; and
an organic layer disposed between the first electrode and the second electrode and including a light emitting layer;
The light emitting layer comprising the chiral polymer of claim 1, an organic light emitting device. 11. The method of claim 10,
The chiral polymer included in the light emitting layer is a host,
An organic light emitting device, wherein the light emitting layer further comprises a dopant selected from (R)-platinum complex represented by the following formula (3) and (S)-platinum complex represented by the following formula (4):
<Formula 3>

<Formula 4>

. 12. The method of claim 11,
An organic light emitting device in which right circularly polarized light or left circularly polarized light is emitted from the light emitting layer.

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