JP2007291330A - Porphyrin compound, method for preparation of porphyrin compound, three dimensional optical recording material and three dimensional optical recording medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound suitable for application such as three dimensional optical recording material, etc. <P>SOLUTION: The compound with the structure of the formula (xiii) is exemplified as the compound of the invention. In the formula M<SP>1</SP>is a metal such as Zn, etc., R<SP>1</SP>, R<SP>2</SP>are each a H, an alkyl group etc. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a porphyrin compound, a method for producing a porphyrin compound, a three-dimensional optical recording material, and a three-dimensional optical recording medium.

  Information recording media are used for various purposes such as business use, home use, and personal use. For this reason, information recording media are extremely important in modern industry and society. Among information recording media, an optical recording medium that records information by light is currently widely used. This is because the optical recording medium has ease of information recording, a large recording capacity, and the like. Examples of mainstream optical recording media include CD, MO, and DVD. These optical recording media can record information by including an appropriate optical recording material. In order to further increase the recording capacity of optical recording media, research and development of more excellent optical recording materials has been in progress.

  An example of the optical recording material is a material that records information by a recording method called a heat mode. This heat mode is a method that utilizes a change in refractive index that occurs in the optical recording material due to a thermal effect when light is irradiated. However, the heat mode has a limited recording capacity due to the diffraction limit of light. For this reason, research has been conducted on recording or erasing information by a recording method called a photon mode. According to this photon mode, it is possible to record information with a larger capacity than in the heat mode. In the photon mode, a photochromic material containing a photochromic compound (photochromic molecule) is used as an optical recording material. Then, recording is performed using isomerization of the photochromic compound by absorption of photons.

  A photochromic compound (photochromic molecule) refers to a compound (molecule) that exhibits photochromism. The photochromic material refers to an optical recording material formed from the photochromic compound and capable of recording or erasing information by photochromism. Photochromism is a phenomenon in which a certain chemical species reversibly isomerizes between two states having different absorption spectra by light irradiation. As an example of the usage method of the photochromic material, there is a usage method of repeatedly irradiating light by changing an irradiation wavelength. According to this method of use, it is possible to repeat recording and erasing of information by repeating fading and coloring by isomerization (photochromism) of a photochromic compound. As such a photochromic material, various compounds have been studied for practical use. Among photochromic compounds, particularly organic compounds have been actively researched and developed in recent years.

  Examples of currently known photochromic compounds include azobenzenes, diarylethenes, spiropyrans, fulgides, and indigo. However, these conventional photochromic compounds are capable of two-dimensional recording, but three-dimensional recording is difficult. This is because in these conventional photochromic compounds, the photoisomerization reaction occurs by one-photon absorption. For this reason, optical recording media such as CD, MO, DVD, etc., which are currently mainstream, are two-dimensional optical recording media (two-dimensional optical memory media). In this two-dimensional optical recording medium, information is recorded on a plane, but the thickness direction of the medium is not used. The fact that the thickness direction of the optical recording medium cannot be used for information recording in this way is a limitation on the recording capacity.

  As means for solving this problem, it is conceivable to construct a three-dimensional optical recording medium (three-dimensional optical memory medium). This three-dimensional optical recording medium is a medium in which information is written in layers. Therefore, according to the three-dimensional optical recording medium, a large increase in recording capacity can be expected. In order to construct the three-dimensional optical recording medium, a photochromic compound that isomerizes by two-photon absorption may be used.

  The two-photon absorption is to simultaneously absorb two photons in a wavelength region where no one-photon absorption occurs. According to two-photon absorption, it is possible to generate an excited state corresponding to the sum of two energies. Therefore, two-photon absorption can be selectively caused only in a position having a high light density such as a focal point in the optical recording material. For this reason, according to two-photon absorption, light absorption can be controlled in a three-dimensional position selective manner in the optical recording material. Therefore, three-dimensional recording using the thickness direction of the optical recording material is possible. Thus, if a photochromic compound (photochromic molecule) with high two-photon absorption efficiency is developed and used as an optical recording material, a three-dimensional optical recording medium can be produced.

  Photochromic materials using two-photon absorption have also been proposed in the past (see, for example, Non-Patent Documents 1 and 2). However, these photochromic materials are far from practical use due to low two-photon absorption efficiency (small two-photon absorption cross section).

  In addition, the present inventors have invented a compound in which a porphyrin compound is linked by an ethynylene group (Patent Document 1). This compound has a two-photon absorption efficiency improved by two orders of magnitude or more than the conventional compound. However, this compound has a high two-photon absorption efficiency, but hardly causes isomerization (photochromism) due to light absorption. For this reason, the compound of Patent Document 1 has a problem in use as an optical recording material.

D. A. Parthenopoulos, P. M. Rentzepis, Science 245 (1989) 843, A. S. Dvornikov, Y. Liang, C. S. Cruse, P. M. Rentzepis, J. Phys. Chem. B 108 (2004) 8652 JP 2004-168690 A

  Accordingly, an object of the present invention is to provide a compound suitable for applications such as a three-dimensional optical recording material.

The inventors of the present invention have made extensive studies to solve the above problems. That is, the present inventors have studied to invent a compound having high two-photon absorption efficiency and effectively causing photochromism by light absorption. The present inventors linked a porphyrin ring and a perinaphthothioindigo ring with a linear atomic group. As a result, the present inventors invented a compound capable of π-electron conjugation between the porphyrin ring and the perinaphthothioindigo ring. For example, perinaphthothioindigo changes from a trans form to a cis form upon irradiation with light having a wavelength of about 620 nm, and returns to a trans form from cis form upon irradiation with light having a wavelength of about 508 nm (Scheme 1 below). Thus, perinaphthothioindigo causes a photoisomerization reaction (photochromism) with light having a relatively long wavelength. However, there has been no research to apply this perinaphthothioindigo structure to the improvement of two-photon absorption efficiency.

前記式（１）中、
P¹は、下記式(a¹)、(b¹)または(c¹)で表される原子団であり、

[Y]は、下記式(a²)、(b²)または(c²)で表される原子団であり、

P²は、水素原子、ハロゲン、または、下記式(a³)、(b³)もしくは(c³)で表される原子団であり、

前記式(a¹)、(b¹)、(a²)、(b²)、(a³)および(b³)中、
R¹は、それぞれ、水素原子、置換もしくは無置換のアルキル基、または、置換もしくは無置換のアリール基を表し、前記置換もしくは無置換のアルキル基は、直鎖状でも分枝状でも環状（置換もしくは無置換のシクロアルキル基）でも良く、前記置換アルキル基において、置換基は1でも複数でも良く、複数の場合は同一でも異なっていても良く、前記置換もしくは無置換のアリール基は、単環でも縮合環でも良く、ヘテロ原子を含んでいなくても含んでいても良く、前記置換アリール基において、置換基は1でも複数でも良く、複数の場合は同一でも異なっていても良く、各R¹は同一でも異なっていても良く、
R³は、それぞれ、水素原子、置換もしくは無置換のアルキル基、または、置換もしくは無置換のアリール基を表し、前記置換もしくは無置換のアルキル基は、直鎖状でも分枝状でも環状（置換もしくは無置換のシクロアルキル基）でも良く、前記置換アルキル基において、置換基は1でも複数でも良く、複数の場合は同一でも異なっていても良く、前記置換もしくは無置換のアリール基は、単環でも縮合環でも良く、ヘテロ原子を含んでいなくても含んでいても良く、前記置換アリール基において、置換基は1でも複数でも良く、複数の場合は同一でも異なっていても良く、各R³は同一でも異なっていても良く、

前記式(a¹)、(b¹)、(c¹)、(a³)、(b³)および(c³)中、
L⁰は、L⁰の両端に結合した環とそれぞれ共役可能な直鎖状原子団であり、前記式（１）中にL⁰が複数存在する場合は、各L⁰は同一でも異なっていても良く、

前記式(a¹)、(b¹)、(a³)および(b³)中、
R²は、それぞれ、水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、５〜６員の含窒素配位性ヘテロ芳香族環、またはハロゲンを表し、前記置換もしくは無置換のアルキル基は、直鎖状でも分枝状でも環状（置換もしくは無置換のシクロアルキル基）でも良く、前記置換アルキル基において、置換基は1でも複数でも良く、複数の場合は同一でも異なっていても良く、前記置換もしくは無置換のアリール基は、単環でも縮合環でも良く、ヘテロ原子を含んでいなくても含んでいても良く、前記置換アリール基において、置換基は1でも複数でも良く、複数の場合は同一でも異なっていても良く、前記式（１）中にR²が複数存在する場合は、各R²は同一でも異なっていても良く、
M¹は、金属、金属ハロゲン化物、金属酸化物、金属水酸化物、Si、Ge、もしくはPであるか、または２個の水素原子を表し、前記式（１）中にM¹が複数存在する場合は、各M¹は同一でも異なっていても良く、

前記式(b¹)中、
xは、正の整数であり、

前記式(b³)中、
yは、正の整数であり、

前記式(b¹)および(b³)中、
M²は、金属、金属ハロゲン化物、金属酸化物、金属水酸化物、Si、Ge、もしくはPであるか、または２個の水素原子を表し、M¹とM²は同一でも異なっていても良く、前記式（１）中にM²が複数存在する場合は、各M²は同一でも異なっていても良く、
L¹は、L¹の両端に結合したポルフィリン環とそれぞれ共役可能な直鎖状原子団であり、L⁰とL¹は同一でも異なっていても良く、前記式（１）中にL¹が複数存在する場合は、各L¹は同一でも異なっていても良く、

前記式(a²)および(b²)中、
M³は、金属、金属ハロゲン化物、金属酸化物、金属水酸化物、Si、Ge、もしくはPであるか、または２個の水素原子を表し、M³は前記M¹およびM²とは同一でも異なっていても良く、前記式（１）中にM³が複数存在する場合は、各M³は同一でも異なっていても良く、

前記式(b²)中、
zは、正の整数であり、
L²は、L²の両端に結合したポルフィリン環とそれぞれ共役可能な直鎖状原子団であり、L²は前記L⁰およびL¹とは同一でも異なっていても良く、L²が複数存在する場合は、各L²は同一でも異なっていても良く、

前記式(c¹)、(c²)および(c³)中、
R⁴は、水素原子、またはハロゲンであり、各R⁴は同一でも異なっていても良い。 The compound of the present invention is a porphyrin compound, a tautomer or stereoisomer thereof, or a salt thereof. The porphyrin compound is represented by the following formula (1) and includes one or more porphyrin rings and one or more perinaphthothioindigo rings.

In the formula (1),
P ¹ is an atomic group represented by the following formula (a ¹ ), (b ¹ ) or (c ¹ ),

[Y] is an atomic group represented by the following formula (a ² ), (b ² ) or (c ² ),

P ² is a hydrogen atom, halogen, or an atomic group represented by the following formula (a ³ ), (b ³ ), or (c ³ ),

In the above formulas (a ¹ ), (b ¹ ), (a ² ), (b ² ), (a ³ ) and (b ³ ),
R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and the substituted or unsubstituted alkyl group is linear, branched, or cyclic (substituted) Or a substituted cycloalkyl group). In the substituted alkyl group, one or more substituents may be used, and when there are a plurality of substituents, they may be the same or different. The substituted or unsubstituted aryl group is a single ring. Or a condensed ring, which may or may not contain a heteroatom. In the substituted aryl group, one or a plurality of substituents may be used, and in the case of a plurality, each may be the same or different. ¹ may be the same or different,
R ³ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and the substituted or unsubstituted alkyl group is linear, branched, or cyclic (substituted) Or a substituted cycloalkyl group). In the substituted alkyl group, one or more substituents may be used, and when there are a plurality of substituents, they may be the same or different. The substituted or unsubstituted aryl group is a single ring. Or a condensed ring, which may or may not contain a heteroatom. In the substituted aryl group, one or a plurality of substituents may be used, and in the case of a plurality, each may be the same or different. ³ may be the same or different,

In the above formulas (a ¹ ), (b ¹ ), (c ¹ ), (a ³ ), (b ³ ) and (c ³ ),
L ⁰ is a linear atomic group that can be conjugated to the ring bonded to both ends of L ⁰ , and when there are a plurality of L ⁰ in the formula (1), each L ⁰ is the same or different. Well,

In the formulas (a ¹ ), (b ¹ ), (a ³ ) and (b ³ ),
R ² represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a 5- or 6-membered nitrogen-coordinating heteroaromatic ring, or a halogen, respectively, and the substituted or unsubstituted The alkyl group may be linear, branched or cyclic (substituted or unsubstituted cycloalkyl group). In the substituted alkyl group, one or a plurality of substituents may be used, and in the case of a plurality, they may be the same or different. The substituted or unsubstituted aryl group may be a single ring or a condensed ring, and may or may not contain a hetero atom. In the substituted aryl group, one or more substituents may be included. In the case where a plurality of R ² are present in the formula (1), each R ² may be the same or different.
M ¹ is a metal, metal halide, metal oxide, metal hydroxide, Si, Ge, or P, or represents two hydrogen atoms, and a plurality of M ¹ exist in the formula (1). Each M ¹ may be the same or different,

In the formula (b ¹ ),
x is a positive integer,

In the formula (b ³ ),
y is a positive integer,

In the formulas (b ¹ ) and (b ³ ),
M ² is a metal, metal halide, metal oxide, metal hydroxide, Si, Ge, or P, or represents two hydrogen atoms, and M ¹ and M ² may be the same or different Well, when there are a plurality of M ² in the formula (1), each M ² may be the same or different,
L ¹ are each a porphyrin ring attached to both ends of the L ¹ is a conjugate that can be linear atomic group, L ⁰ and L ¹ may be the same or different, is L ¹ in the formula (1) If there are multiple, each L ¹ may be the same or different,

In the above formulas (a ² ) and (b ² ),
M ³ is a metal, metal halide, metal oxide, metal hydroxide, Si, Ge, or P, or represents two hydrogen atoms, and M ³ is the same as M ¹ and M ² However, when there are a plurality of M ³ in the formula (1), each M ³ may be the same or different,

In the formula (b ² ),
z is a positive integer,
L ² are each a porphyrin ring attached to both ends of the L ² is conjugated possible linear atomic group, L ² may be the same or different from that of the L ⁰ and L ^1, L ² are plurality of Each L ² may be the same or different,

In the formulas (c ¹ ), (c ² ) and (c ³ ),
R ⁴ is a hydrogen atom or halogen, and each R ⁴ may be the same or different.

  The three-dimensional optical recording material of the present invention is a three-dimensional optical recording material containing the compound of the present invention.

  Furthermore, the three-dimensional optical recording medium of the present invention is a three-dimensional optical recording medium having a recording layer capable of recording information. The recording layer contains the three-dimensional optical recording material of the present invention.

  The compound of the present invention has high two-photon absorption efficiency and effectively causes photochromism by light absorption. For this reason, the compound of this invention is suitable for uses, such as a three-dimensional optical recording material. The three-dimensional optical recording material of the present invention can be recorded three-dimensionally by including the compound of the present invention. That is, three-dimensional optical recording can be performed by a method including a step of irradiating the compound of the present invention with light and isomerizing by two-photon absorption. Further, since the three-dimensional optical recording medium of the present invention uses the three-dimensional optical recording material of the present invention, large capacity recording is possible.

  Furthermore, the use of the compound of the present invention is not limited to a three-dimensional optical recording material and a three-dimensional optical recording medium. For example, optical recording can be performed by a method including a step of irradiating the compound of the present invention with light and isomerizing by one-photon absorption. Thereby, the compound of this invention can be used also for the conventional two-dimensional optical recording material or two-dimensional optical recording medium. Specifically, the optical recording material of the present invention is an optical recording material containing the compound of the present invention. Furthermore, the optical recording medium of the present invention is an optical recording medium having a recording layer capable of recording information. The recording layer contains the optical recording material of the invention. Furthermore, the compound of the present invention may be used for any purpose other than the optical recording material and the optical recording medium. For example, the compound of the present invention can also be used as a dye for uses other than optical recording materials.

Hereinafter, the present invention will be described in detail.
First, in the present invention, “halogen” refers to an arbitrary halogen element. Examples of the halogen include fluorine, chlorine, bromine and iodine. In the present invention, the “alkyl group” is not particularly limited. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. The same applies to a group containing an alkyl group in the structure or a group derived from an alkyl group (alkoxy group, carboxyalkyl group, alkoxycarbonylalkyl group, alkoxyalkyl group, alkenoxyalkyl group, etc.).

  When the substituent or the like is a group having a chain structure (eg, an alkyl group, an alkoxy group, a carboxyalkyl group, an alkoxycarbonylalkyl group, an alkoxyalkyl group, an alkenoxyalkyl group, etc.) It may be chained or branched. The same applies to the case where a part of a substituent or the like includes a chain structure, for example, when a substituent in a substituted alkyl group or a substituted aryl group includes a chain structure. When an isomer exists in a substituent or the like, any isomer may be used unless there is a particular limitation. For example, when simply referring to “propyl group”, either an n-propyl group or an isopropyl group may be used. When simply referred to as “butyl group”, any of n-butyl group, isobutyl group, sec-butyl group and tert-butyl group may be used. When simply referred to as “naphthyl group”, either a 1-naphthyl group or a 2-naphthyl group may be used.

前記式(L¹⁰⁰)中、nは、１〜３のいずれかの整数を表す。また、本発明の化合物の製造のし易さ、収率等の観点から、前記式(L¹⁰⁰)がエチニレン基 （-C≡C-） （n=１）であることがより好ましい。L⁰は、前記重合度nが３を超えるポリアセチレン基またはその他の基でも良い。L⁰は、三次元光記録材料として実用可能な程度のフォトクロミック性を本発明の化合物に与える基であることが好ましい。 [Compound of the present invention]
As described above, in the compound of the present invention, when a plurality of L ⁰ are present in the formula (1), each L ⁰ may be the same or different. In the formula (1), L ⁰ is preferably represented by the following formula (L ¹⁰⁰ ).

In the formula (L ¹⁰⁰ ), n represents an integer of 1 to 3. In view of ease of production of the compound of the present invention, yield, etc., the formula (L ¹⁰⁰ ) is more preferably an ethynylene group (—C≡C—) (n = 1). L ⁰ may be a polyacetylene group having a polymerization degree n of more than 3 or other groups. L ⁰ is preferably a group that provides the compound of the present invention with photochromic properties that are practical for use as a three-dimensional optical recording material.

前記式(L²⁰⁰)中、mは、１〜３のいずれかの整数を表す。前記式(L²⁰⁰)は、エチニレン基 （-C≡C-） （m=１）であることがより好ましい。L¹は、前記重合度mが３を超えるポリアセチレン基またはその他の基でも良い。L¹は、三次元光記録材料として実用可能な程度のフォトクロミック性を本発明の化合物に与える基であることが好ましい。 As described above, in the formula (1), when a plurality of L ¹ in the formulas (b ¹ ) and (b ³ ) are present in the formula (1), they may be the same or different. In the formulas (b ¹ ) and (b ³ ), L ¹ is preferably represented by the following formula (L ²⁰⁰ ).

In the formula (L ²⁰⁰ ), m represents an integer of 1 to 3. The formula (L ²⁰⁰ ) is more preferably an ethynylene group (—C≡C—) (m = 1). L ¹ may be a polyacetylene group having a polymerization degree m of more than 3 or other groups. L ¹ is preferably a group that provides the compound of the present invention with photochromic properties that are practical for use as a three-dimensional optical recording material.

前記式(L³⁰⁰)中、lは、１〜３のいずれかの整数を表す。前記式(L³⁰⁰)は、エチニレン基 （-C≡C-） （l=１）であることがより好ましい。L²は、前記重合度lが３を超えるポリアセチレン基またはその他の基でも良い。L²は、三次元光記録材料として実用可能な程度のフォトクロミック性を本発明の化合物に与える基であることが好ましい。 As described above, in Formula (1), L ² in Formula (b ² ) may be the same or different when a plurality of L ² are present in Formula (1). In the formula (b ² ), L ² is preferably represented by the following formula (L ³⁰⁰ ).

In the formula (L ³⁰⁰ ), l represents an integer of 1 to 3. The formula (L ³⁰⁰ ) is more preferably an ethynylene group (—C≡C—) (l = 1). L ² may be a polyacetylene group having a degree of polymerization 1 exceeding 3 or other group. L ² is preferably a group that provides the compound of the present invention with photochromic properties that are practical for use as a three-dimensional optical recording material.

（ii） 前記式（１）中、[Y]が前記式(c²)で表され、P¹が前記式(b¹)で表され、前記式(b¹)中の重合度xが１であり、P²が水素原子である化合物。

（iii） 前記式（１）中、[Y]が前記式(c²)で表され、P¹が前記式(a¹)で表され、P²が前記式(a³)で表される化合物。

（iv） 前記式（１）中、[Y]が前記式(c²)で表され、P¹が前記式(b¹)で表され、前記式(b¹)中の重合度xが１であり、P²が前記式(b³)で表され、前記式(b³)中の重合度ｙが１である化合物。

（ｖ） 前記式（１）中、[Y]が前記式(c²)で表され、P¹が前記式(a¹)で表され、P²が前記式(b³)で表され、前記式(b³)中の重合度ｙが１である化合物。

In the compound of the present invention, the number of perinaphthothioindigo rings may be one or plural. The number of perinaphthothioindigo rings is preferably 1 from the viewpoint of simplification of the photochromism. Among the compounds of the present invention in which the number of perinaphthothioindigo rings is 1, for example, the following (i) to (v) are more preferable.
(I) A compound in which [Y] is represented by the formula (c ² ), P ¹ is represented by the formula (a ¹ ), and P ² is a hydrogen atom in the formula ( ¹ ).

In (ii) above formula (1), [Y] is represented by the formula (c ^2), are represented by P ¹ is the formula (b ^1), a polymerization degree x in the formula (b ¹⁾ is 1 And P ² is a hydrogen atom.

(Iii) In the formula (1), [Y] is represented by the formula (c ² ), P ¹ is represented by the formula (a ¹ ), and P ² is represented by the formula (a ³ ). Compound.

In (iv) above formula (1), [Y] is represented by the formula (c ^2), are represented by P ¹ is the formula (b ^1), a polymerization degree x in the formula (b ¹⁾ is 1 in and, P ² is represented by the formula (b ^3), the formula (b ³⁾ the degree of polymerization y compound is 1 in.

(V) In the formula (1), [Y] is represented by the formula (c ² ), P ¹ is represented by the formula (a ¹ ), and P ² is represented by the formula (b ³ ). A compound having a polymerization degree y of 1 in the formula (b ³ ).

前記式（xi）〜（xv）中、
M¹は、金属イオンまたは２個の水素原子であり、前記式（１）中にM¹が複数存在する場合は、各M¹は同一でも異なっていても良く、

前記式（xii）、（xiv）および（xv）中、
M²は、金属イオンまたは２個の水素原子であり、M¹とM²は同一でも異なっていても良く、前記式（１）中にM²が複数存在する場合は、各M²は同一でも異なっていても良い、
ポルフィリン化合物、その互変異性体もしくは立体異性体、またはそれらの塩である。 The compound of the present invention having the structure (i), (ii), (iii), (iv), or (v) is more preferably, for example,
In the above formulas (a ¹ ), (b ¹ ), (a ³ ) and (b ³ ), R ³ is all a hydrogen atom, L ⁰ is an ethynylene group,
In the formulas (b ¹ ) and (b ³ ), L ¹ is represented by the formula (L ²⁰⁰ ), and when there are a plurality of L ¹ in the formula (1), each L ¹ is the same or different. It ’s okay,
In the formula (c ² ), all R ⁴ are hydrogen atoms,
That is, it is represented by any of the following formulas (xi) to (xv),

In the formulas (xi) to (xv),
M ¹ is a metal ion or two hydrogen atoms, and when there are a plurality of M ¹ in the formula (1), each M ¹ may be the same or different,

In the formula (xii), (xiv) and (xv),
M ² is a metal ion or two hydrogen atoms, M ¹ and M ² may be the same or different, and when there are a plurality of M ² in the formula (1), each M ² is the same But it can be different,
It is a porphyrin compound, its tautomer or stereoisomer, or a salt thereof.

前記式（xxi）〜（xxv）中、
R¹が、それぞれ、水素原子、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、sec-ブチル基、イソブチル基、tert-ブチル基、ペンチル基、ヘキシル基、フェニル基、４−メトキシカルボニルフェニル基、３、５−ビス（メトキシカルボニル）フェニル基、４−エトキシカルボニルフェニル基、および３、５−ビス（エトキシカルボニル）フェニル基からなる群から選択される少なくとも一つであり、各R¹は同一でも異なっていても良く、
M¹は、Zn(II)、Ga(III)、Fe(II)、Fe(III)、Co(II)、Co(III)、Ru(II)、Ru(III)または２個の水素原子であり、前記式（１）中にM¹が複数存在する場合は、各M¹は同一でも異なっていても良く、

前記式（xxii）、（xxiv）および（xxv）中、
M²は、Zn(II)、Ga(III)、Fe(II)、Fe(III)、Co(II)、Co(III)、Ru(II)、Ru(III)または２個の水素原子であり、M¹とM²は同一でも異なっていても良く、前記式（１）中にM²が複数存在する場合は、各M²は同一でも異なっていても良い、
ポルフィリン化合物、その互変異性体もしくは立体異性体、またはそれらの塩である。 The compound of the present invention having the structure (i), (ii), (iii), (iv), or (v) is more preferably, for example,
In the formulas (a ¹ ), (b ¹ ), (a ³ ) and (b ³ ),
L ⁰ is an ethynylene group,
R ² is all a hydrogen atom,
R ³ is all hydrogen atoms,
In the formulas (b ¹ ) and (b ³ ),
L ¹ is an ethynylene group,
In the formula (c ² ),
R ⁴ is all a hydrogen atom,
That is, it is represented by any of the following formulas (xxi) to (xxv)

In the formulas (xxi) to (xxv),
R ¹ is a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, phenyl group, At least one selected from the group consisting of 4-methoxycarbonylphenyl group, 3,5-bis (methoxycarbonyl) phenyl group, 4-ethoxycarbonylphenyl group, and 3,5-bis (ethoxycarbonyl) phenyl group Each R ¹ may be the same or different,
M ¹ is Zn (II), Ga (III), Fe (II), Fe (III), Co (II), Co (III), Ru (II), Ru (III) or two hydrogen atoms Yes, when there are a plurality of M ¹ in the formula (1), each M ¹ may be the same or different,

In the formula (xxii), (xxiv) and (xxv),
M ² is Zn (II), Ga (III), Fe (II), Fe (III), Co (II), Co (III), Ru (II), Ru (III) or two hydrogen atoms Yes, M ¹ and M ² may be the same or different, and when there are a plurality of M ² in the formula (1), each M ² may be the same or different.
It is a porphyrin compound, its tautomer or stereoisomer, or a salt thereof.

Among the compounds of the present invention having the structure of (i), (ii), (iii), (iv), or (v), particularly preferred compounds are, for example, compound numbers 1001 to 1012 in the following compound number table Or a tautomer or stereoisomer thereof, or a salt thereof. However, the particularly preferred compounds are not limited to these. In the following compound number table, the column of “structure” indicates that each porphyrin compound represented by compound numbers 1001 to 1012 is as defined in (i), (ii), (iii), (iv), or (v). Indicates which structure it has. The columns of “R ¹ ”, “R ² ”, “R ³ ”, “R ⁴ ”, “M ¹ ”, “M ² ”, “L ⁰ ”, and “L ¹ ” represent the structures of the respective atomic groups.

（vii） P¹が前記式(c¹)で表され、[Y]が前記式(a²)で表され、P²が前記式(c³)で表される化合物。

また、前記（ｉ）、（ii）、（iii）、（iv）、（ｖ）、（vi）または（vii）の構造を有する本発明の化合物において、特に好ましくは、例えば、R³およびR⁴は全て水素原子であり、M¹は金属イオンまたは水素原子２個であり、M²が存在する場合はM²が金属イオンまたは水素原子２個であり、L⁰はエチニレン基 （-C≡C-） であり、L¹は前記式(L²⁰⁰)で表される。 In the compound of the present invention, the total number of porphyrin rings and perinaphthothioindigo rings is not particularly limited. The total number of porphyrin rings and perinaphthothioindigo rings is preferably 2 to 6 from the viewpoints of ease of production, ease of handling, ease of use as a three-dimensional optical recording material, and the like. . The reason why the total number of the porphyrin ring and perinaphthothioindigo ring is the above-mentioned number is easy to use as a three-dimensional optical recording material is that the one-photon absorption wavelength does not easily overlap with the two-photon absorption wavelength. The total number of the porphyrin ring and the perinaphthothioindigo ring is more preferably 2 to 5, still more preferably 2 to 4, and particularly preferably 3 or less (2 or 3). The two-photon absorption wavelength in the compound of the present invention is considered to exist in the near infrared region, for example. More specifically, the two-photon absorption wavelength is considered to exist in the vicinity of 860 to 890 nm, which is about twice the Soret band wavelength of porphyrin. However, the present invention is not limited to this assumption. The compounds of the present invention in which the total number of porphyrin rings and perinaphthothioindigo rings is 3 or less include the following (vi) and (vii) in addition to the above (i) to (iii).
(Vi) A compound in which P ¹ is represented by the formula (c ¹ ), [Y] is represented by the formula (c ² ), and P ² is represented by the formula (a ³ ).

(Vii) A compound in which P ¹ is represented by the formula (c ¹ ), [Y] is represented by the formula (a ² ), and P ² is represented by the formula (c ³ ).

In the compound of the present invention having the structure (i), (ii), (iii), (iv), (v), (vi) or (vii), particularly preferably, for example, R ³ and R ⁴ are all hydrogen atoms, M ¹ is a two metal ion or a hydrogen atom, if M ² is present is two M ² is a metal ion or a hydrogen atom, L ⁰ is an ethynylene group (-C≡ C-) and L ¹ is represented by the formula (L ²⁰⁰ ).

As described above, in the formula (1), in the formulas (a ¹ ), (b ¹ ), (a ³ ) and (b ³ ), each M ¹ is a metal, a metal halide, a metal oxide, a metal It is a hydroxide, Si, Ge, or P, or represents two hydrogen atoms. M ¹ may be, for example, electrically neutral or ionic. Each M ¹ is preferably, for example, a metal ion or two hydrogen atoms. The metal ion is not particularly limited. The metal ions are more preferably zinc, iron, cobalt, ruthenium or gallium ions, Zn (II), Ga (III), Fe (II), Fe (III), Co (II), Co (III), Ru (II) or Ru (III) is more preferable. When a plurality of M ¹ are present in the formula (1), each M ¹ may be the same or different.

As described above, in the formula (1), in the formulas (b ¹ ) and (b ³ ), each M ² is a metal, a metal halide, a metal oxide, a metal hydroxide, Si, Ge, or P Or represents two hydrogen atoms. M ² may be, for example, electrically neutral or ionic. Each M ² is preferably, for example, a metal ion or two hydrogen atoms. The metal ion is not particularly limited. The metal ions are more preferably zinc, iron, cobalt, ruthenium or gallium ions, Zn (II), Ga (III), Fe (II), Fe (III), Co (II), Co (III), Ru (II) or Ru (III) is more preferable. When a plurality of M ² are present in the formula (1), each M ² may be the same or different. Furthermore, as described above, in the formula (1), in the formulas (a ² ) and (b ² ), each M ³ is a metal, a metal halide, a metal oxide, a metal hydroxide, Si, Ge, Or it is P or represents two hydrogen atoms. M ³ may be, for example, electrically neutral or ionic. Each M ³ is preferably, for example, a metal ion or two hydrogen atoms. The metal ion is not particularly limited. The metal ions are more preferably zinc, iron, cobalt, ruthenium or gallium ions, Zn (II), Ga (III), Fe (II), Fe (III), Co (II), Co (III), Ru (II) or Ru (III) is more preferable. When a plurality of M ³ are present, each M ³ may be the same or different.

The bonding state between each M ¹ , each M ² or each M ³ and the nitrogen atom of the porphyrin ring (pyrrole nucleus) is not particularly limited. When each M ¹ , each M ² or each M ³ is 2 hydrogen atoms, the bonding state is preferably a covalent bond, for example. When each M ¹ , each M ² or each M ³ is other than two hydrogen atoms, for example, when it is a metal, the bonding state is preferably, for example, a coordinate bond.

Hereinafter, preferred examples of R ^{1 in} the formula (a ¹ ), (b ¹ ), (a ² ), (b ² ), (a ³ ), and (b ³ ) in the formula ( ¹ ) will be shown. R ³ and the formula ^{(a 1), (b 1} ), are also preferred examples of R ² in (a ³⁾ and (b ^3), together below.

In R ¹ , the substituted alkyl group is not particularly limited. The substituted alkyl group is preferably at least one selected from the group consisting of, for example, an alkoxycarbonylalkyl group, an alkoxyalkyl group, an alkenoxyalkyl group, an alkenoxycarbonylalkyl group, and a carboxyalkyl group. The same applies to the substituted alkyl group in R ² and R ³ . As described above, the term “substituted or unsubstituted alkyl group” in R ¹ , R ² and R ³ in the formula (1) includes a cyclic structure, that is, a substituted or unsubstituted cycloalkyl group. .

In R ¹ , the number of carbon atoms of the alkyl residue in the substituted or unsubstituted alkyl group is not particularly limited. The number of carbon atoms of the alkyl residue is preferably from 1 to 24, more preferably from 2 to 10, and even more preferably from 3 to 8 from the viewpoint of ease of production of the compound of the present invention, solubility and the like. The same applies to R ^2. From the same viewpoint, in R ¹ , the number of carbon atoms of the substituent in the substituted alkyl group is preferably 1 to 24, more preferably 1 to 10, and further preferably 1 to 5. The same applies to R ^2. Furthermore, from the same viewpoint, in R ¹ , the total number of carbon atoms of the substituted or unsubstituted alkyl group is preferably 1 to 24, more preferably 4 to 18, and still more preferably 4 to 13. The same applies to R ² and R ³ .

The unsubstituted alkyl group for R ¹ is not particularly limited. The unsubstituted alkyl group is particularly preferably, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group. , N-heptyl group, and 2-ethyl-n-pentyl group. The same applies to R ² and R ³ .

The substituted alkyl group for R ¹ is not particularly limited. The substituted alkyl group is particularly preferably, for example, carboxymethyl group, carboxyethyl group, carboxy n-propyl group, carboxyisopropyl group, carboxy n-butyl group, carboxy sec-butyl group, carboxyisobutyl group, carboxy tert-butyl. Group, carboxypentyl group, carboxyhexyl group, methoxycarbonylethyl group, methoxycarbonylethyl-n-propyl group, ethoxycarbonylethyl group, ethoxycarbonylethylpropyl group, allyloxycarbonylethyl group, allyloxycarbonylethyl-n-propyl group , An allyloxypropyl group, an allyloxyethyl group, and an allyloxybutyl group. The same applies to R ² and R ³ .

In R ¹ , the aryl residue in the substituted or unsubstituted aryl group is not particularly limited. The aryl residue is preferably at least one selected from the group consisting of, for example, a phenyl group, a naphthyl group, a pyridyl group, an azulenyl group, and an anthracenyl group. The same applies to R ² and R ³ .

In R ¹ , the number of carbon atoms of the aryl residue in the substituted or unsubstituted aryl group is not particularly limited. The number of carbon atoms of the aryl residue is preferably 5 to 24, more preferably 5 to 10 from the viewpoint of ease of production of the compound of the present invention, solubility and the like. The same applies to R ² and R ³ .

In R ¹ , the number of carbon atoms of the substituent in the substituted aryl group is not particularly limited. The number of carbon atoms of the substituent is preferably 1 to 40 from the viewpoint of ease of production of the compound of the present invention, solubility and the like. The compound of the present invention in which the number of carbon atoms of the substituent in the substituted aryl group falls within this range is relatively easy to produce. The number of carbon atoms of the substituent in the substituted aryl group is preferably 1-20, and more preferably 1-10. The same applies to R ² and R ³ .

In R ¹ , the total number of carbon atoms of the substituted or unsubstituted aryl group is not particularly limited. The total number of carbon atoms is preferably 5 to 24, more preferably 5 to 10 from the viewpoint of ease of production of the compound of the present invention, solubility and the like. The same applies to R ² and R ³ .

In R ¹ , the substituted aryl group is not particularly limited. The substituted aryl group is preferably at least one selected from the group consisting of an alkylaryl group, an alkoxyaryl group, an alkoxycarbonylaryl group, an alkenoxyaryl group, a carboxyaryl group, and an alkenoxycarbonylaryl group. . The same applies to the substituted aryl group in R ² and R ³ .

In R ¹ , the substituent in the substituted aryl group is not particularly limited. The substituent is particularly preferably, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, methoxy group. Group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, carboxymethyl group, carboxyethyl group, carboxy n -Propyl, carboxyisopropyl, carboxy n-butyl, carboxy sec-butyl, carboxyisobutyl, carboxy tert-butyl, carboxypentyl, carboxyhexyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl Group, isopropoxycarbonyl group, n-butoxycarbonyl group, sec- Butoxycarbonyl group, isobutoxycarbonyl group, tert- butoxycarbonyl group, pentyloxycarbonyl group, and at least one selected from the group consisting of hexyl oxycarbonyl group. The same applies to R ² and R ³ .

In R ¹ , the substituted aryl group is particularly preferably a 4-carboxyphenyl group, 3,5-dicarboxyphenyl group, 4-carboxy-2,6-bis (carboxymethoxy) phenyl group, 3,5, and the like. -Bis (tris (carboxyethyl) methylcarboxamido) phenyl group, 4- (tris (carboxyethyl) methylcarboxyamido) -2,6-bis (tris (carboxyethyl) methylcarboxyamidomethoxy) phenyl group, 4-methoxy It is at least one selected from the group consisting of a carbonylphenyl group, a 3,5-bis (methoxycarbonyl) phenyl group, a 4-ethoxycarbonylphenyl group, and a 3,5-bis (ethoxycarbonyl) phenyl group. The same applies to R ² and R ³ .

R ¹ in the formulas (a ¹ ), (b ¹ ), (a ² ), (b ² ), (a ³ ) or (b ³ ) may be the same or different. R ¹ in the formula (a ¹ ) is preferably all the same, for example, from the viewpoint of ease of production of the compound of the present invention. The same applies to the formulas (b ¹ ), (a ² ), (b ² ), (a ³ ) and (b ³ ). When a plurality of R ² are present in the formula (1), they may be the same or different. For example, R ² is preferably all the same in formula (1), more preferably all hydrogen atoms.

In R ² , the number of carbon atoms in the 5- to 6-membered nitrogen-containing heteroaromatic ring is not particularly limited. The number of carbon atoms is preferably 3 to 5 from the viewpoint of ease of production of the compound of the present invention, solubility and the like. In R ² , the number of nitrogen atoms in the 5- to 6-membered nitrogen-containing heteroaromatic ring is not particularly limited. The number of nitrogen atoms is preferably 1 to 2 from the viewpoint of ease of production of the compound of the present invention.

In R ² , the 5- to 6-membered nitrogen-containing heteroaromatic ring is not particularly limited. The 5-6 membered nitrogen-containing coordinating heteroaromatic ring is at least one selected from the group consisting of imidazole, N-methylimidazole, pyridine, pyrazole, and pyrimidine, for example.

In the formula (1), R ³ is not particularly limited in the formulas (a ¹ ), (b ¹ ), (a ² ), (b ² ), (a ³ ) and (b ³ ). From the viewpoint of ease of production of the compound of the present invention, solubility and the like, for example, R ³ is preferably all the same, and more preferably all hydrogen atoms.

In the formula (1), R ⁴ is not particularly limited in the formulas (c ¹ ), (c ² ) and (c ³ ). From the viewpoints of ease of production of the compound of the present invention, solubility and the like, for example, R ⁴ is preferably all hydrogen atoms.

When the porphyrin compound represented by the formula (1) has isomers such as tautomers and stereoisomers, these isomers are also included in the compound of the present invention. More specifically, examples of the isomer include a geometric isomer, a conformer isomer, an optical isomer, and the like. For example, in the formula (1), the perinaphthothioindigo ring is shown as a trans structure. However, the compound of the present invention also includes a compound in which the perinaphthothioindigo ring is isomerized to a cis structure in the formula (1). Further, for example, when an enantiomer is present in the compound of the present invention, both R-form and S-form are included in the compound of the present invention. Furthermore, when the porphyrin compound represented by the formula (1) or an isomer thereof can form a salt, the salt is also included in the compound of the present invention. In the salt, the counter ion of the porphyrin compound represented by the formula (1) is not particularly limited. The counter ion may be, for example, a cation or an anion. Examples of anions include hexafluorophosphate ion (PF ₆ ⁻ ), tetrafluoroborate ion (BF ₄ ⁻ ), hydroxide ion (OH ⁻ ), acetate ion, carbonate ion, phosphate ion, and sulfate ion. , Nitrate ions, halide ions (eg fluoride ions (F ⁻ ), chloride ions (Cl ⁻ ), bromide ions (Br ⁻ ), iodide ions (I ⁻ ) etc.), hypohalite ions (eg Fluorite ion, hypochlorite ion, hypobromite ion, hypoiodite ion, etc.), halogen acid ion (eg, fluorite ion, chlorite ion, bromite ion, iodate ion) Etc.), halogenate ions (eg, fluoric acid ions, chlorate ions, bromate ions, iodate ions, etc.), perhalogenate ions (eg, perfluorate ions, perchlorate ions, perbromate ions, C iodate ion), trifluoromethanesulfonate ion (OSO ₂ CF ₃ ^-), tetrakis pentafluorophenyl borate ion _{[B (C 6 F 5)} 4 -] , and the like. The cation is not particularly limited, but various metal ions such as lithium ion, magnesium ion, sodium ion, potassium ion, calcium ion, barium ion, strontium ion, yttrium ion, scandium ion, lanthanoid ion, hydrogen ion, etc. Can be mentioned. These counter ions may be one type or two or more types may coexist.

As the compound of the present invention, particularly preferred compounds are, for example, porphyrin compounds represented by the following formula (2) or (3), tautomers or stereoisomers thereof, or salts thereof. As described above, for example, porphyrin compounds represented by any of compound numbers 1001 to 1012 in the compound number table, tautomers or stereoisomers thereof, salts thereof, and the like are also particularly preferable as the compounds of the present invention. preferable.

[Method for producing compound of the present invention]
Next, the manufacturing method of the compound of this invention is demonstrated.

  The method for producing the compound of the present invention is not particularly limited. That is, the compound of the present invention may be produced by any method. The compound of the present invention is preferably produced, for example, by the production method of the present invention described below.

The production method of the present invention is a method for producing a porphyrin compound represented by the formula (1), a tautomer or stereoisomer thereof, or a salt thereof. More specifically, the production method of the present invention comprises:
A step of coupling a porphyrin derivative with a halogenated perinaphthothioindigo derivative,
The porphyrin derivative is a derivative in which at least one of hydrogen atoms bonded to the 5-position, 10-position, 15-position and 20-position carbon of the porphyrin ring is substituted with a substituent -L ⁰ -H, and the L ⁰ is claimed. It is the same as L ⁰ described in item 1,
The halogenated perinaphthothioindigo derivative is a derivative in which the para carbon of the carbon bonded to the S atom is halogenated in at least one of two naphthalene rings in the perinaphthothioindigo ring.

Here, in the halogenated perinaphthothioindigo derivative, “para-carbon of carbon bonded to S atom” is a carbon atom indicated by * in the following formula (100). In the following formula (100), X ¹ and X ² may be the same or different. At least one of X ¹ and X ² is halogen. The following formula (100) is merely an example of the structure of the halogenated perinaphthothioindigo derivative. As described above, in the present invention, in the halogenated perinaphthothioindigo derivative, at least one of the two naphthalene rings in the perinaphthothioindigo ring, the para carbon of the carbon bonded to the S atom is halogenated. Is a derivative. Other than that, the structure of the halogenated perinaphthothioindigo derivative is not particularly limited. Examples of the structure of the halogenated perinaphthothioindigo derivative include a structure represented by the following formula (200). In the following formula (200), X ¹ and X ² may be the same or different. At least one of X ¹ and X ² is halogen. R ⁴ is the same as in the above formulas (c ¹ ), (c ² ) and (c ³ ).

In the porphyrin derivative, “the 5-position, 10-position, 15-position and 20-position carbon of the porphyrin ring” refers to carbon atoms given the numbers 5, 10, 15 and 20 in the following formula (300), respectively. The following formula (300) is a diagram simply showing the basic skeleton of the porphyrin ring. The structure of the porphyrin derivative in the present invention is not limited by the following formula (300). As described above, in the present invention, the porphyrin derivative is a derivative in which at least one of hydrogen atoms bonded to the 5-position, 10-position, 15-position and 20-position carbon of the porphyrin ring is substituted with a substituent -L ⁰ -H. It is. Wherein L ⁰ is the same as L ⁰ according to claim 1. Other than that, the structure of the porphyrin derivative is not particularly limited.

The following scheme 2 shows an example of the production method of the present invention. In the following Scheme 2, among the porphyrin compounds represented by the formula (1), [Y] is represented by the formula (c ² ), P ¹ is represented by the formula (a ¹ ), and P ² is hydrogen. It is a scheme which shows an example of the manufacturing method of the porphyrin compound which is an atom (The compound (600) in the following scheme 2, the same as the compound of the said formula (i)). This porphyrin compound can be produced by a coupling reaction between a porphyrin derivative (400) and a halogenated perinaphthothioindigo derivative (500) as shown in Scheme 2 below. In the following scheme 2, R ¹ , R ² , R ³ , M ¹ and L ⁰ are the same as the formula (a ¹ ), R ⁴ is the same as the formula (c ² ), and X ¹ is halogen. It is. Among the porphyrin compounds represented by the formula (1), porphyrin compounds having other structures can be produced according to this. That is, those skilled in the art of the present invention can produce the compound of the present invention from the illustration of the following Scheme 2 and the structure of the compound of the present invention described above without undue trial and error and complicated advanced experiments. it can. Specifically, among the porphyrin compounds represented by the formula (1), the porphyrin ring and the perinaphthothioindigo ring are also linked by L ⁰ in the same manner as the following compound (600). Therefore, the other compounds can also be produced using the same coupling reaction as in Scheme 2 below. Further, for example, instead of the following compound (400), a compound in which a plurality of porphyrin rings are linked by L ¹ or L ² can be used as a raw material. Thereby, a compound containing at least one of the formulas (b ¹ ), (b ² ) and (b ³ ) in the formula ( ¹ ) can be produced. A raw material compound in which a plurality of porphyrin rings are linked by the L ¹ or L ² can be obtained by a person skilled in the art based on the description in the present specification (in some cases, referring to common sense in the technical field to which the present invention belongs). Can be manufactured without trial and error and complicated advanced experiments. Such a compound is disclosed, for example, in Patent Document 1 (Japanese Patent Laid-Open No. 2004-168690). Therefore, the compound can be produced, for example, by the method disclosed in Patent Document 1.

  The production method of the present invention is not limited to the method of Scheme 2. For example, each substituent is introduced in advance in the scheme 2 before the coupling reaction. However, each substituent may be appropriately introduced, converted, protected, deprotected and the like after the coupling reaction. For example, in the scheme 2, the halogenated perinaphthothioindigo derivative (500) may be replaced with the halogenated perinaphthothioindigo derivative represented by the formula (200). Thereby, for example, the compound of the present invention represented by the formula (ii) can be obtained. Further, even when the halogenated perinaphthothioindigo derivative (200) is used in this way, depending on the reaction conditions, the porphyrin derivative of the present invention represented by the formula (600) (the formula (i)) can be obtained. Is possible.

  Furthermore, in the production method of the present invention, the conditions for the coupling reaction are not limited at all. For example, conditions such as the reaction solvent, temperature, and reaction time for the coupling reaction may be appropriately set with reference to known similar reactions. The reaction solvent for the coupling reaction may be water or an organic solvent, for example. Examples of the organic solvent include nitriles such as benzonitrile, acetonitrile, butyronitrile, halogenated solvents such as chloroform, dichloromethane, dichloroethane, carbon tetrachloride, tetrachloroethane, THF (tetrahydrofuran), diethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether. , Ethers such as diethylene glycol monoethyl ether, diethylene glycol diethyl ether, amides such as DMF (dimethylformamide) and DMA (dimethylacetamide), sulfoxides such as DMSO (dimethylsulfoxide), ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, Examples thereof include alcohols such as ethanol and n-propanol. These solvents may be used alone or in combination of two or more. The reaction temperature and reaction time of the coupling reaction can be appropriately set depending on, for example, the structure of the porphyrin derivative and halogenated perinaphthothioindigo derivative as raw materials. The reaction temperature is, for example, −50 to 200 ° C., preferably 0 to 120 ° C., more preferably 20 to 100 ° C. The reaction time is, for example, 1 to 20,000 minutes, preferably 1 to 1,500 minutes, and more preferably 30 to 1,000 minutes. In addition, porphyrin derivatives and halogenated perinaphthothioindigo derivatives used as raw materials for the compounds of the present invention can be determined by those skilled in the art based on the description of the present specification (in some cases, with common knowledge in the technical field to which the present invention belongs). ), Can be easily manufactured without undue trial and error, complicated advanced experiments, etc., or can be obtained as a commercial product. For example, you may synthesize | combine from a commercial item with reference to a well-known literature etc.

In the production method of the present invention, L ⁰ in the porphyrin compound is not particularly limited. L ⁰ is particularly preferably an ethynylene group, for example, from the viewpoint of reaction efficiency in the coupling reaction with the halogenated perinaphthothioindigo derivative. The halogen in the halogenated perinaphthothioindigo derivative is not particularly limited. The halogen is particularly preferably bromine or iodine from the viewpoint of reaction efficiency in the coupling reaction with the porphyrin compound.

The production method of the present invention will be described more specifically by taking the synthesis (production) of the compounds represented by the formulas (2) and (3) as an example. The compounds of the formulas (2) and (3) can be synthesized, for example, according to the following scheme 3. However, the method for producing the compounds of the formulas (2) and (3) is not limited to the following scheme 3. In the compound of the formula (2), in the formula (1), [Y] is represented by the formula (c ² ), P ¹ is represented by the structural formula (a ¹ ), and P ² is represented by the structural formula (a ³ ), R ¹ is all 4-ethoxycarbonylphenyl group, R ² , R ³ and R ⁴ are all hydrogen atoms, M ¹ is zinc, and L ⁰ is ethynylene group. The compound of the formula (3) is the same as the compound of the formula (2) except that P ² is a hydrogen atom. Compounds having other structures in the formula (1) can also be produced, for example, according to Scheme 3.

  Hereinafter, the scheme 3 will be described in detail. Various conditions such as temperature, reaction time, raw material usage, solvent usage, etc. are not limited to the following description.

  Step 1 is a deprotection reaction of TMS group (trimethylsilyl group). In this reaction, for example, 1 mL to 1000 mL of chloroform is preferably used as a reaction solvent with respect to 32.0 mg of compound (4). The amount of chloroform used is particularly preferably 5 mL to 20 mL in consideration of the yield of the reaction. The reaction solvent is not particularly limited as long as the deprotection reaction proceeds. As the reaction solvent, tetrahydrofuran (THF), methylene chloride and the like can be used in addition to chloroform. The deprotecting agent is not particularly limited. The deprotecting agent is particularly preferably tetrabutylammonium fluoride in view of the yield of the reaction. The number of equivalents of the deprotecting agent relative to the TMS group is not particularly limited. The number of equivalents is preferably 3 to 5 equivalents considering the yield of the reaction. The reaction temperature is not particularly limited. The reaction temperature is preferably 20 ° C. to 30 ° C. in consideration of the yield of the reaction.

Step 2 is a coupling reaction between an aryl halide and an ethynyl group, and is known as a Sonogashira reaction. In this Sonogashira reaction, for example, 1 to 1000 mL of tetrahydrofuran (THF) is preferably used as a reaction solvent with respect to 1.9 mg of compound (6). The amount of THF used is particularly preferably 5 mL to 20 mL in consideration of the yield of the reaction. The reaction solvent is not particularly limited as long as the reaction proceeds. As the reaction solvent, chloroform, methylene chloride and the like can be used in addition to THF. There is no restriction | limiting in particular as a base. The base is particularly preferably triethylamine in view of the yield of the reaction. The amount of triethylamine is not particularly limited. The amount of triethylamine is, for example, preferably from 0.1 mL to 5 mL, more preferably from 0.5 mL to 2 mL, relative to 1.9 mg of compound (6). The reaction catalyst is not particularly limited, and may be used alone or in combination of two or more. The reaction catalyst is particularly preferably used in combination with, for example, Pd ₂ (dba) ₃ and AsPh ₃ (dba = dibenzylideneacetone). The number of equivalents of Pd ₂ (dba) ₃ to compound (6) is not particularly limited. In consideration of the yield of the reaction, the above and the number of rainfalls are preferably from 0.1 equivalents to 5 equivalents, and more preferably from 0.1 equivalents to 1 equivalent. The number of equivalents of AsPh ₃ to compound (6) is not particularly limited. The number of equivalents is preferably from 0.8 equivalents to 25 equivalents, more preferably from 0.8 equivalents to 5 equivalents, considering the reaction yield. The reaction temperature is not particularly limited. The reaction temperature is particularly preferably 20 ° C. to 30 ° C. in consideration of the yield of the reaction.

  Among the compounds of the present invention, those having a structure other than the structure described in the above description will be understood by those skilled in the art based on the description in this specification (in some cases, common sense in the technical field to which the present invention belongs). Can be easily manufactured without undue trial and error and complicated advanced experiments. For example, for the porphyrin compounds represented by the formula (1) in general, based on the above description (in some cases, referring to common knowledge in the technical field to which the present invention belongs), a porphyrin derivative and a halogenated perinaphthothioindigo derivative It can be produced by a coupling reaction of Specifically, for example, it can be produced according to the scheme 3. Moreover, the salt of the porphyrin compound represented by the formula (1) can be produced, for example, by appropriately adding an appropriate acid or base after producing the porphyrin compound represented by the formula (1).

[Use of the compound of the present invention]
As described above, in the compound of the present invention, the porphyrin ring and the perinaphthothioindigo ring are connected by a linear atomic group. The compound of the present invention can be π-electron conjugated between the porphyrin ring and the perinaphthothioindigo ring. Thereby, the compound of the present invention has high two-photon absorption efficiency and can effectively cause photochromism by light absorption. For example, when a nanosecond pulse laser is used, the compound of the present invention can have a large two-photon absorption cross section of 10,000 GM or more. The compound of the present invention has such a large two-photon absorption efficiency. However, the numerical value of 10,000 GM or more does not limit the present invention. The two-photon absorption cross-sectional area, two-photon absorption efficiency and the like vary depending on the structure of the compound of the present invention and measurement conditions, and are not particularly limited.

  The compound of the present invention can be used as a three-dimensional optical recording material by causing isomerization, that is, photochromism by two-photon absorption. Specifically, for example, the compound of the present invention is preferably isomerizable by two-photon absorption in the solid state. Further, even when the compound of the present invention can be isomerized by two-photon absorption in a solution state, it can be used as a three-dimensional optical recording material. Two-photon absorption generates a high excited state by simultaneously absorbing two low-energy photons in the near-infrared wavelength region where no one-photon absorption occurs. Therefore, as described above, the two-photon absorption can be selectively caused only in the optical recording material only at a high light density position such as a focal point. For this reason, according to two-photon absorption, light absorption can be controlled in a three-dimensional position selective manner in the optical recording material. Therefore, three-dimensional recording using the thickness direction of the optical recording material is possible. When the compound of the present invention is used as a three-dimensional optical recording material, for example, it can be used by irradiating a laser beam having a wavelength that causes two-photon absorption but does not cause one-photon absorption.

As described above, the compound of the present invention includes a three-dimensional optical recording material and a three-dimensional optical recording medium. Specifically, for example, a rewritable three-dimensional optical memory medium can be provided. In addition, for example, the compound of the present invention has a high two-photon absorption cross-sectional area of 10,000 GM or more as described above, so that a high density of 1 terabit per 1 cm ³ (equivalent to 100,000 floppy (registered trademark) disks). It is also possible to record information. The three-dimensional optical recording medium of the present invention can be expected as a next-generation storage medium by having such a large recording capacity.

  Furthermore, the use of the compound of the present invention is not limited to the three-dimensional optical recording material and the three-dimensional optical recording medium as described above. That is, the compound of the present invention may be used for any application. For example, the compound of the present invention can also be used for a two-dimensional optical recording material or a two-dimensional optical recording medium as described above. Moreover, the compound of this invention can also be used for uses other than an optical recording material as a pigment | dye.

  Next, examples of the present invention will be described. However, the present invention is not limited to the following examples.

In the following examples, the nuclear magnetic resonance (NMR) spectrum is measured by JEM EX270 (trade name) manufactured by JEOL Ltd. (270 MHz at ¹ H measurement), JNM ECP500 (product name) JEOL Ltd. (trade name) ( ¹ MHz measurement at 500 MHz) or JEM ECP600 (trade name) manufactured by JEOL Ltd. ( ¹ MHz measurement at 600 MHz). Chemical shifts are expressed in parts per million (ppm). Tetramethylsilane (TMS) was used for the internal standard of 0 ppm. Coupling constants (J) are in hertz, and the abbreviations s, d, t, q, m, and br are singlet, doublet, triplet, quadruple, respectively. Represents a quartet, a multiplet, and a broad line. Mass spectrometry (MS, Mass) was measured by the MALDI-TOF method using an instrument Voyager DE-STR or AXIMA-LNR (trade name) manufactured by PerSeptive Biosystems or Shimadzu Corporation (Shimadzu / KRATOS). The visible / ultraviolet absorption spectrum was measured using an instrument UV-3100PC (trade name) or UV-1650PC (trade name) manufactured by Shimadzu Corporation. For laser irradiation, a device Surelight I-10 (trade name) manufactured by Continuum was used in combination with Continuum Surelight OPO (trade name). The fluorescence spectrum was measured using an instrument F-4500 (trade name) manufactured by Hitachi, Ltd. All chemical substances are reagent grade and purchased from Wako Pure Chemical Industries, Ltd. or Nacalai Tesque.

[Example 1: Production of porphyrin compounds (2) and (3)]
According to the scheme 3, the porphyrin compounds represented by the formulas (2) and (3) were synthesized (manufactured). Specifically, it is as follows.

1) Synthesis of raw material Compound (4) which is a starting material of the above-mentioned scheme 3 is synthesized according to the description of the literature K. Ogawa, J. Dy, and Y. Kobuke, Journal of Porphyrins and Phthalocyanine 9, 735-744 (2005). did. Specifically, it is as follows. First, dipyrromethane (167.4 mg, 1.14 mmol), 4-ethoxycarbonylbenzaldehyde (204 mg, 1.14 mmol), and chloroform (200 mL) were placed in a 500 mL three-necked flask. Nitrogen gas was bubbled into it for 3 minutes to create a nitrogen gas atmosphere. Trifluoroacetic acid (88.2 μL, 1.14 mmol) was added. The mixture was stirred at room temperature and protected from light for 20 hours, triethylamine (0.5 mL, 3.56 mmol) and chloranil (884 mg, 3.4 mmol) were added, and the mixture was refluxed at 70 ° C. for 1.5 hours. The solvent was distilled off, and the residue was purified by silica gel column chromatography (solvent: chloroform) to obtain Compound (4) as a reddish purple solid (141.1 mg, 40.9%). The instrumental analysis data of the compound (4) is shown below.

Compound (4):
¹ H-NMR (270MHz, CDCl ₃ ) δ10.332 (s, 2H, meso), 9.405 (d, 4H, J = 4.7Hz, β), 9.033 (d, 4H, J = 4.7Hz, β), 8.490 (d, 4H, J = 8.1Hz, Ph), 8.351 (d, 4H, J = 8.1Hz, ph), 4.607 (q, 4H, J = 3.5Hz, -CH _2- ), 1.342 (t, 6H, _{J = 3.5Hz, -CH 3),} MALDI-TOF mass (matrix: dithranol), m / z 606.90, calcd for C 38 H 30 N 4 O 4 606.23.

  4-Ethoxycarbonylbenzaldehyde, which is a starting material of compound (4), was synthesized according to the description in the literature K. Ogawa, J. Dy, and Y. Kobuke, Journal of Porphyrins and Phthalocyanine 9, 735-744 (2005). . Specifically, it is as follows. First, terephthalaldehyde acid (5.5 g, 36.6 mmol), concentrated sulfuric acid (0.91 mL), and ethanol (166.6 mL) were added to a 300 mL eggplant flask and heated to reflux for 18 hours. Return to room temperature, evaporate the organic solvent, dissolve in ethyl acetate (100 mL), wash with saturated sodium bicarbonate (200 mL x 2), saturated brine (200 mL x 2), distilled water (200 mL x 2), and dry It dried with sodium sulfate, and concentrated and dried (5.42 g, 83.1%). The instrumental analysis data of this product is shown below.

4-Ethoxycarbonylbenzaldehyde:
¹ H-NMR (270 MHz, CDCl ₃ ), δ 10.10 (s, 1 H, -CHO), 8.15 (d, 2 H, J = 8.1 Hz), 7.94 (d, 2 h, J = 8.1 Hz), 4.42 (q, _{2H, J = 3.5Hz, -CH 2} -), 1.42 (t, 2H, J = 3.5Hz, -CH 3).

  Further, dipyrromethane which is a starting material of the compound (4) is described in the literature JK Laha, S. Dhanalekshmi, M. Taniguchi, A. Ambroise and JS Lindsey, Org. Process Res. Dev. 2003; 7: 799-812. Was synthesized according to Specifically, it is as follows. First, pyrrole (120 mL, 1.71 mol), paraformaldehyde (1.21 g, 40 mmol), methanol (60.7 mL), and acetic acid (158.8 mL) well-ground in a mortar were added to a 1000 mL eggplant flask in this order. Nitrogen gas was bubbled into the eggplant flask for 10 minutes, and stirred at room temperature for 24 hours under a nitrogen gas atmosphere. Dilute with chloroform (50 mL) and neutralize with saturated aqueous sodium bicarbonate. The mixture was further extracted with chloroform (50 mL), dried over anhydrous sodium sulfate, and the organic layer was distilled off. Distillation was performed to collect pyrrole (30 ° C., 7.3 kpa), and dipyrromethane (120 ° C., 0.1 kpa) was obtained. Purification was performed by silica gel column chromatography (solvent: chloroform: hexane: ethyl acetate = 7: 2: 1) to obtain white crystals (1.36 g, 25.6%). The instrumental analysis data of this product is shown below.

Dipyromethane:
¹ H-NMR (270 MHz, CDCl ₃ ) d 7.78 (brs, 2H, NH), 6.62 (m, 2H), 6.14 (dd, 2H, J = 2.7, 5.9 Hz), 6.03 (m, 2H), 3.95 (s, 2H, meso).

  The starting compound (6) was synthesized according to the document J. Leavitt, Chemical Abstract, 1971, 74, 113187n. Specifically, it is as follows. First, 7-Iodo-benzo-thiochromen-3-one (650 mg, 275 mmol, 1.0 eq) and EtOH (103 mL) were added to a 500 mL three-necked flask. Ultrasonic was applied for 1 minute to make the suspension. 10% NaOH solution (168 mL, 288 mol) was added. Refluxed at 70 ° C. with bubbling air for 8 hours. The solution was collected by filtration and washed with methanol and chloroform to obtain a blue solid (243.3 mg, 75.3%). This solid was insoluble in various solvents (chloroform, methanol, ethanol, ethyl acetate, acetone, benzene, pyridine, hexane, toluene). Although slightly dissolved in THF, NMR measurement was impossible. The instrumental analysis values of the solid (compound (6)) are shown below.

Compound (6):
MALDI-TOF mass (matrix: dithranol), m / z 648.777 [as M + H], calcd for C ₃₈ H ₃₀ N ₄ O ₄ 647.8 [as M].

  In addition, 7-Iodo-benzo-thiochromen-3-one (7-Iodo-benzo-thiochromen-3-one) which is a starting material of the compound (6) is described in the document J. Leavitt, Chemical Abstract, 1971, 74, 113187n. Was synthesized according to Specifically, it is as follows. First, 3-methoxycarbonyl-7-iodo-benzothiochromen (700 mg, 1.9 mmol) and acetic acid (82 mL) were added to a 200 mL eggplant flask and sonicated for 1 minute. In suspension. 35% acetic acid (11.1 mL, 95 mmol) was added and nitrogen gas was bubbled for 2 minutes. Under a nitrogen gas atmosphere, heating and stirring were performed at 40 ° C. for 4 hours and a half. When ice was put into a 300 mL Erlenmeyer flask and the reaction solution was put therein and cooled, a brownish yellow precipitate was deposited. This was collected by filtration, dissolved in chloroform (100 mL), and washed with saturated aqueous sodium hydrogen carbonate solution (200 mL × 2) and water (200 mL × 2). Drying was performed with anhydrous sodium sulfate, the organic layer was taken, concentrated and dried to obtain a brown solid (666 mg, 98%). The instrumental analysis values of this solid are shown below.

7-Iodo-benzo-thiochromen-3-one:
¹ H-NMR (270 MHz, CDCl ₃ ) δ 8.397 (dd, 1H, J = 1.1, 8.6 Hz), 8.251 (dd, 1H, J = 1.1 7.3 Hz), 8.003 (d, 1H, J = 8.6), 7.682 (dd, 1H, J = 7.3 Hz), 7.298 (d, 1H, J = 7.3 Hz).

  In addition, 3-methoxycarbonyl-7-iodo-benzothiochrome (7-Iodo-benzo-thiochromen-3-one) is a starting material of 7-Iodo-benzo-thiochromen-3-one. iodo-benzothiochromen) was synthesized according to the document J. Leavitt, Chemical Abstract, 1971, 74, 113187n. Specifically, it is as follows. First, in a 100 mL eggplant flask, 8-carboxymethylsulfenyl-5-iodo-naphthalene-1-carboxylic acid (370 mg, 0.95 mmol), sodium acetate (100 mg 1.2 mmol) and acetic anhydride (20 mL) were added and heated at 140 ° C. for 2 hours under reflux. Cool and add chloroform (100 mL). Saturated aqueous sodium hydrogen carbonate solution was added little by little to neutralize, and the mixture was washed with saturated aqueous sodium hydrogen carbonate solution (200 mL × 2) and water (200 mL × 2). The organic layer was taken, dried and concentrated to obtain a brown solid (349 mg, 99.9%). The instrumental analysis values of this solid are shown below.

3-methoxycarbonyl-7-iodo-benzothiochromene:
Melting point 114.2-115.7 ° C (Reference value: 112.5-113 ° C), ¹ H-NMR (270 MHz, CDCl ₃ ) δ 7.744 (d, 1 H, J = 8.1 Hz), 7.727 (d, 1 H, J = 7.6 Hz) 7.303 (t, 1H, J = 7.6 Hz), 6.942 (d, 1H, J = 7.6 Hz), 6.795 (d, 1H, J = 8.1 Hz), 2.342 (s, 3H).

  In addition, 8-carboxymethylsulfenyl-5-iodo-naphthalene-1-carboxylic acid (8-carboxyl), which is a starting material of 3-methoxycarbonyl-7-iodo-benzothiochromen (8-carboxymethyl-7-iodo-benzothiochromen). carboxymethylsulfenyl-5-iodo-naphthalene-1-carboxylic acid) was synthesized according to the literature Chemical Abstract, 1969, 70, 3615k. Specifically, it is as follows. First, 6-iodonaphtho [1,8-bc] thiophen-2-one (6-Iodonaptho [1,8-bc] thiophen-2-one) (242 mg, 0.68 mmol, 1.0 eq), 5% was added to a 50 mL eggplant flask. NaOH (11 mL) was added, and the mixture was heated and stirred at 80 ° C. for 1 hour. Thereafter, chloroacetic acid (200 mg, 2.1 mmol, 3.9 eq) was added, and the mixture was further heated at 80 ° C. for 1 hour and stirred. The formation of the target product was confirmed by TLC. After cooling to room temperature and adding hydrochloric acid to pH 1, a yellow precipitate formed. The solid was collected by filtration, washed with chloroform, and dried to give a yellow solid (298 mg, 98.2%). The instrumental analysis values of this solid are shown below.

8-Carboxymethylsulfenyl-5-iodo-naphthalene-1-carboxylic acid:
¹ H-NMR (270 MHz, CDCl ₃ ) δ8.182 (d, 1H, J = 8.1 Hz), 8.174 (d, 1H, J = 8.1 Hz), 7.726 (d, 1H, J = 7.3 Hz), 7.670 ( t, 1H, J = 7.3, 8.1Hz), 7.583 (d, 1H, J = 8.1Hz), 3.661 (s, 2H).

  6-iodonaphtho [1,8-bc] thiophene, which is a starting material of 8-carboxymethylsulfenyl-5-iodo-naphthalene-1-carboxylic acid 2-one (6-Iodonaptho [1,8-bc] thiophen-2-one) was synthesized according to the document Chemical Abstract, 1969, 70, 3615k. Specifically, it is as follows. First, naphtho [1,8-bc] thiophen-2-one (0.7 g, 375 mmol), acetic acid (10 mL) and ICl (5.5 g, 34 mmol) were added. The flask was placed in a 50 mL eggplant flask and refluxed for 3 hours. Water (60 mL) was added, and a saturated aqueous sodium thiosulfate solution was added to precipitate a yellowish green precipitate. The precipitate was collected by filtration and dissolved in chloroform (100 mL). The extract was washed with a saturated aqueous sodium thiosulfate solution (200 mL × 2) and water (200 mL × 2), and dried over anhydrous sodium sulfate. After concentration and drying, recrystallization with ethanol gave a yellow solid (226 mg, 51.8%). The instrumental analysis data of this solid is shown below.

6-Iodonaphtho [1,8-bc] thiophen-2-one:
¹ H-NMR (270 MHz, CDCl ₃ ) δ 8.240 (d, 1H, J = 8.1 Hz), 8.212 (d, 1H, J = 7.3 Hz), 8.128 (d, 1H, J = 7.3 Hz), 7.845 (dd , 1H, J = 8.1 Hz), 7.344 (d, 1H, J = 7.3 Hz).

Naphtho [1,8-bc] thiophen-2-one which is a starting material for 6-iodonaphtho [1,8-bc] thiophen-2-one (Naphtho [1,8-bc] thiophen-2-one) was synthesized according to the literature Synthesis, 1989, 7, 523. Specifically, it is as follows. First,
8-Iodo-1-naphthoic acid (2.8 g, 9.39 mmol) was added to 7N KOH (7.1 mL) and stirred until dissolved. 3-mercaptopropionic acid (2.5 mL, 23.3 mmol) and powdered Cu (94 mg, 1.48 mmol) were mixed with the solution. Nitrogen gas was bubbled for about 1 minute and then refluxed for 5 hours under an argon atmosphere. Further, 7N KOH (2 mL) was added and refluxed for 2 hours. Water (4.9 mL) was added and filtered. When 6N HCl (2.1 mL) was added to the filtrate and the reaction system was acidified (pH 1), a yellow precipitate was deposited. The precipitate was collected by filtration, dissolved in chloroform (100 mL), and washed with a saturated aqueous sodium hydrogen carbonate solution (200 mL × 2) and water (200 mL × 2). The extract was dried over anhydrous sodium sulfate, concentrated and dried to give a yellow solid (1.76 g, 99%). The instrumental analysis data of this solid is shown below.

Naphtho [1,8-bc] thiophen-2-one:
¹ H-NMR (270MHz, CDCl ₃ ) δ 8.188 (d, 1H, J = 7.3Hz), 8.160 (d, 1H, J = 8.1Hz), 7.852 (dd, 1H, J = 3.8, 4.6Hz), 7.784 (dd, 1H, J = 4.6, 7.3Hz), 7.635 (d, 1H, J = 3.8Hz), 7.629 (d, 1H, J = 7.3Hz).

8-Iodo-1-naphthoic acid which is a starting material of naphtho [1,8-bc] thiophen-2-one (Naphtho [1,8-bc] thiophen-2-one) ) Was synthesized according to the literature Baily, RJ; Card, PJ; Shechter, H .; J. Am. Chem. Soc. 1983, 105, 6096-6103. Specifically, it is as follows. First, I ₂ (12.0 g, 47.6 mmol) and anhydrous -8- (hydroxymercury) -1-naphthoic acid (17.0 g, 45.9 mmol) were added to an aqueous KI solution ( 32.4 g / 162 mL). The mixture was refluxed for 15 hours. Cooled and filtered. Hydrochloric acid was added to the filtrate to make it acidic (pH 1) to obtain a milky yellow precipitate. The solution was collected by filtration, dissolved in chloroform (100 mL), and washed with a saturated aqueous sodium thiosulfate solution (200 mL × 2) and water (200 mL × 2). Dried over anhydrous sodium sulfate. The pale yellow organic layer was collected, concentrated and dried to obtain a yellow solid (5.70 g, 42.2%). The instrumental analysis data of this solid is shown below.

8-Iodo-1-naphthoic acid:
¹ H-NMR (270 MHz, CDCl ₃ ) δ 8.271 (dd, 1H, J = 7.6, 8.1 Hz), 7.915 (m, 3H), 7.6 (dd, 1H, J = 7.6, 8.1 Hz), 7.222 (dd, 1H, J = 7.6, 8.1Hz).

  Anhydro-8- (hydroxymercuri) -1-naphthoic acid, which is a starting material for 8-Iodo-1-naphthoic acid Was synthesized according to the literature Baily, RJ; Card, PJ; Shechter, H .; J. Am. Chem. Soc. 1983, 105, 6096-6103. Specifically, it is as follows. First, a commercially available 1,8-Naphthalic anhydride (0.991 g, 5 mmol) and an aqueous sodium hydroxide solution (0.7 g / 30 mL, 17.5 mmol) were added to a 200 mL eggplant flask and stirred. And refluxed until the solid dissolved (1 hour). Neutralized with acetic acid (0.5 mL, 8.3 mmol). To this, mercuric oxide (1.1 g, 5.1 mmol) was dissolved in boiling acetic acid (2.5 mL, 41.5 mmol), and a solution diluted with 18 mL of water to form mercury acetate was added. The mixture was refluxed for 30 minutes, acetic acid (0.9 mL, 14.9 mmol) was added, and the mixture was refluxed for 48 hours. The resulting precipitate was collected by filtration and washed with methanol and water. Drying in vacuo at 105 ° C. for 15 hours gave a tan powder (1.363 g, 74.0%). Since this powder was insoluble in water and organic solvents, it was not analyzed and used for the next reaction (synthesis of 8-iodo-1-naphthoic acid). The literature also does not show instrumental analysis data for anhydrous -8- (hydroxymercury) -1-naphthoic acid.

2) Step 1
Synthesis of Compound (5) Step 1 (synthesis of compound (5)) in Scheme 3 was performed as follows. First, Compound (4) (32.0 mg, 41.8 μmol, 1.0 eq) and chloroform (10 mL) were placed in a 100 mL eggplant flask. To the solution, tetrabutylammonium fluoride (1M in THF) (144 μL, 144 μmol, 3.45 eq) was added and stirred at room temperature for 10 minutes. Thereafter, it was confirmed by TLC and Mass spectrum that the raw material had disappeared from the solution. Next, chloroform (10 mL) was added to the solution, washed with a saturated aqueous sodium hydrogen carbonate solution (50 mL × 2) and water (50 mL × 2), and the organic layer was separated. This was dried over sodium sulfate, and further concentrated and dried (evaporation of the solvent). The obtained residue was purified by silica gel column chromatography (solvent: Hex / AcOH = 4/1) to obtain the target compound (5) as a purple solid. The yield was 20.7 mg, and the yield was 73.0%. The instrumental analysis data of this compound (5) is shown below. In the following ¹ H-NMR data of compound (5), the symbols “a”, “b”, “c”, “d”, “e”, “f”, and “β” are the protons (H) Indicates the position of the carbon atom to which is attached. The positions of these carbon atoms in the compound (5) are represented by the corresponding symbols in the following chemical formula.

Compound (5):
TLC (CHCl ₃ ) Rf = 0.12; ¹ H-NMR (270 MHz, CDCl ₃ ), δ 10.204 (s, 1H, f), 9.8000 (d, 2H, J = 2.16, β), 9.339 (d, 2H, J = 2.16, β), 8.993 (d, 2H, J = 2.16, β), 8.953 (d, 2H, J = 2.16, β), 8.442 (d, 4H, J = 3.78, e), 8.283 (d, 4H, J = 3.78, d), 4.565 (q, 4H, J = 3.24, c), 3.476 (s, 1H, a), 1.560 (t, 6H, J = 3.24, b); MALDI-TOF mass (dithranol ), M / z 693.44 (M + H) ⁺ , calcd for C ₃₈ H ₃₀ N ₄ O ₄ 692.1.

3) Step 2
Synthesis of Compounds (2) and (3) Step 2 in Scheme 3 was performed as follows. First, the inside of a 100 mL Schlenk flask was put under Ar atmosphere. Into this, compound (6) (1.9 mg, 2.9 μmol, 4 eq) and dry THF (9 mL) were added, and ultrasonic waves were suspended for 5 minutes. Triethylamine (1 mL) and compound (5) (0.5 mg, 1.4 μmol, 1 eq) were added to the suspension, and deoxygenated by bubbling with Ar for 10 minutes. Subsequently, Pd ₂ (dba) ₃ (0.2 mg, 0.27 μmol, 0.12 eq) and AsPh ₃ (0.6 mg, 1.8 μmol, 0.8 eq) were added, and the mixture was stirred at room temperature in the dark (dba = dibenzylideneacetone ). The reaction was monitored by MALDI-TOF mass spectrum. After 4 hours from the start of the reaction, the disappearance of the raw material (5) and the formation of compounds (2) and (3) were confirmed, and the reaction was stopped. Thereafter, water (20 mL) was added for quenching, and the solvent was distilled off. Chloroform (10 mL) was added to the resulting residue, washed with a saturated aqueous ammonium chloride solution (50 mL × 2) and water (50 mL × 2), and the organic layer was separated. This was dried over anhydrous sodium sulfate and further concentrated to dryness. The obtained residue was purified by GPC for recycling preparative (solvent: pyridine) to obtain the desired porphyrin compounds (2) and (3). LC-9101 (trade name) manufactured by Japan Analytical Industrial Co., Ltd. was used as the GPC for recycle fractionation. Rt (retention time) of compound (2) was 25 minutes, and Rt of compound (3) was 26 minutes. The obtained compound (2) was a dark green solid, and the yield was 20% and the yield was 0.2 mg. The obtained compound (3) was a dark green solid, and the yield was 40% and the yield was 0.3 mg. The instrumental analysis data of the target compounds (2) and (3) are shown below. In the following ¹ H-NMR data of compounds (2) and (3), the symbols “a”, “b”, “c”, “d”, “e”, and “β” represent the protons (H ) Indicates the position of the bonded carbon atom. The positions of these carbon atoms in the compounds (2) and (3) are represented by the corresponding symbols in the following chemical formula. In the following ¹ H-NMR data, “PNI” indicates a proton signal of the perinaphthothioindigo ring. The perinaphthothioindigo ring in the compounds (2) and (3) is indicated by the symbol “PNI” in the following chemical formula.

Compound (3); ¹ H-NMR (500 MHz, tetrachloroethane-d ₂ / Pyridine-d ₅ ), δ10.07 (s, 1H, a), 9.81 (d, J = 4.5 Hz, 2H, β), 9.31 ( d, J = 8Hz, 1H, PNI), 9.23 (d, J = 4.5Hz, 2H, β), 8.92 (d, J = 4.5Hz, 2H, β), 8.83 (d, J = 4.5Hz, 2H, β), 8.69 (d, J = 8Hz, 1H, PNI), 8.54 (d, J = 8Hz, 1H, PNI), 8.37 (d, J = 8Hz, 4H, e), 8.24 (d, J = 8Hz, 4H, d), 8.20 (d, J = 8Hz, 1H, PNI), 8.08 (d, J = 8Hz, 1H, PNI), 7.98 (t, J = 8Hz, 1H, PNI), 7.77 (d, J = 8Hz, 1H, PNI), 7.70 (d, J = 8Hz, 1H, PNI), 7.68 (t, J = 8Hz, 1H, PNI), 7.62 (PNI, overlaps with pyridine peak), 7.46 (t, J = 8Hz , 1H, PNI), 4.49 (q, J = 7.5Hz, 4H, c), 1.48 (t, J = 7.5Hz, 6H, b); MALDI-TOF mass (dithranol), m / z 1086.5 (M + H ) ⁺ , calcd for C ₆₄ H ₃₈ N ₄ O ₆ S ₂ Zn 1086.2.

Compound (2); ¹ H-NMR (600 MHz, tetrachloroethane-d ₂ ), δ 10.14 (s, 2H, a), 9.80 (br, 2H, β), 9.29 (d, J = 8Hz, 2H, PNI) , 9.29 (br, 2H, β), 8.90 (br, 2H, β), 8.83 (br, 2H, β), 8.70 (d, J = 8Hz, 2H, PNI), 8.37 (d, J = 8Hz, 8H , e), 8.24 (d, J = 8Hz, 8H, d), 8.20 (d, J = 8Hz, 2H, PNI), 7.98 (br, 2H, PNI), 7.73 (d, J = 8Hz, 2H, PNI ), 4.59 (q, J = 7.5Hz, 8H, c), 1.48 (t, J = 7.5Hz, 12H, b); MALDI-TOF mass (dithranol), m / z 1781.8 (M + H) +, calcd for C ₁₀₄ H ₆₄ N ₈ O ₁₀ S ₂ Zn ₂ 1780.2.

[Example 2: Production of cis-porphyrin compound (3 ')]
FIG. 1 shows a visible / ultraviolet absorption spectrum of the porphyrin compound (3), which is a novel photochromic molecule obtained in Example 1. In the figure, the vertical axis represents absorbance and the horizontal axis represents wavelength. This spectrum was measured by dissolving compound (3) in tetrahydrofuran (THF) as a 2.2 μM concentration solution. As shown in the figure, the absorption of the Soret band peculiar to porphyrins is observed at around 440 nm. Further, absorption from the trans structure of the perinaphthothioindigo site is observed from 650 nm to 750 nm.

化合物（３）は、上記スキーム４のように、ペリナフトチオインジゴ部位がトランス構造であるポルフィリン化合物（以下、「トランス体ポルフィリン化合物」または単に「トランス体」ということがある。）である。この化合物（３）に光照射してフォトクロミズムを起こさせ、ペリナフトチオインジゴ部位がシス構造であるポルフィリン化合物（以下、「シス体ポルフィリン化合物」または単に「シス体」ということがある。）（３’）を製造した。さらに、シス体ポルフィリン化合物（３’）に光照射し、フォトクロミズムによりトランス体ポルフィリン化合物（３）に戻ったことを確認した。具体的には、以下の通りである。 As shown in Scheme 4 below, the photoisomerization (photochromism) characteristics of the compound (3) were confirmed. By this isomerization, compound (3 ′) was produced.

Compound (3) is a porphyrin compound in which the perinaphthothioindigo moiety has a trans structure (hereinafter sometimes referred to as “trans-form porphyrin compound” or simply “trans-form”) as shown in Scheme 4 above. This compound (3) is irradiated with light to cause photochromism, and a porphyrin compound having a cis structure at the perinaphthothioindigo site (hereinafter sometimes referred to as “cis-form porphyrin compound” or simply “cis-form”) (3) ') Manufactured. Further, it was confirmed that the cis-porphyrin compound (3 ′) was irradiated with light and returned to the trans-porphyrin compound (3) by photochromism. Specifically, it is as follows.

  That is, first, the trans porphyrin compound (3) synthesized in Example 1 was dissolved in tetrahydrofuran (THF) to prepare a 2.2 μM solution. This solution was irradiated with laser light at room temperature (22 ° C.) to excite the perinaphthothioindigo site of compound (3). And the time-dependent change of the visible-ultraviolet absorption spectrum of the said compound (3) was measured. The irradiation wavelength was 680 nm, the laser beam used was an Nd: YAG-OPO laser with a pulse width of 5 ns, and the average power was 240 μW. The graph of FIG. 2 shows changes with time in the visible / ultraviolet absorption spectrum. In the figure, the vertical axis represents absorbance and the horizontal axis represents wavelength. The spectra are those before laser light irradiation and after 1, 2, 4, 7, 10, 16, 31 minutes from the start of irradiation. In the figure, the white arrow (⇒) indicates the position of 680 nm, which is the wavelength of the irradiation laser beam. A black arrow (→) associated with each absorption band indicates an increase or decrease in absorption due to laser light irradiation in each absorption band. As shown in the figure, with light irradiation, the absorption from 650 nm to 750 nm derived from the perinaphthothioindigo site of the trans form (3) decreased. At the same time, the absorption from 480 nm to 550 nm derived from the perinaphthothioindigo site of the cis form (3 ') increased. After 31 minutes of irradiation, the change in spectrum almost stopped and completely changed to the cis form (3 '). The solution of this cis isomer (3 ') was allowed to stand at room temperature (22 ° C) for 12 hours in the dark and the spectrum was measured. The result of the spectrum measurement was consistent with the spectrum at 31 minutes irradiation. This result shows that the state of the cis isomer (3 ') is maintained even when the solution after irradiation for 31 minutes is allowed to stand for 12 hours. As described above, the trans porphyrin compound (3) was irradiated with a laser beam and isomerized to produce a cis porphyrin compound (3 ').

  Further, this cis isomer (3 ') solution was irradiated with laser light at room temperature (22 ° C) to excite the perinaphthothioindigo site of the cis isomer (3'). And the time-dependent change of the visible-ultraviolet absorption spectrum of the said compound (3 ') was measured. The irradiation wavelength was 500 nm, the laser beam used was an Nd: YAG-OPO laser with a pulse width of 5 ns, and the average power was 200 μW. The graph of FIG. 3 shows changes with time in the visible / ultraviolet absorption spectrum. In the figure, the vertical axis represents absorbance and the horizontal axis represents wavelength. The spectra are those before irradiation and after 1, 2, 3, 4, 5, 6, 7 minutes have elapsed since the start of irradiation. In the figure, the white arrow (⇒) indicates the position of 500 nm that is the wavelength of the irradiation laser beam. A black arrow (→) associated with each absorption band indicates an increase or decrease in absorption due to laser light irradiation in each absorption band. As shown in the figure, the absorption from 650 nm to 750 nm derived from the perinaphthothioindigo site of the trans isomer (3) increased with light irradiation. At the same time, absorption from 480 nm to 550 nm derived from the perinaphthothioindigo site of the cis form (3 ') decreased. The spectral change almost stopped after 7 minutes of irradiation, and the light was in a steady state.

  As described above, the cis-porphyrin compound (3 ') was produced by isomerization of the trans-porphyrin compound (3). At the same time, the photochromism of the trans form (3) and the cis form (3 ') was also confirmed.

[Example 3: Production of cis-porphyrin compound (2 ')]
FIG. 9 shows a visible / ultraviolet absorption spectrum of the porphyrin compound (2), which is a novel photochromic molecule obtained in Example 1. In the figure, the vertical axis represents absorbance and the horizontal axis represents wavelength. In the figure, the curve indicated by the solid line is the spectrum of the porphyrin compound (2). As in Example 2, this spectrum was measured by dissolving compound (2) in tetrahydrofuran (THF) as a 1.8 μM concentration solution. As shown in the figure, absorption in the Sore band specific to porphyrins is observed around 420 nm to 460 nm, and absorption derived from the perinaphthothioindigo site of the trans form from 650 nm to 750 nm.

As shown in the following scheme 5, the photoisomerization (photochromism) characteristics of the compound (2) were confirmed. This isomerization produced compound (2 ′).

  The trans porphyrin compound (2) solution was irradiated with laser light at room temperature (25 ° C.). As a light source, an Nd: YAG-OPO laser having an irradiation wavelength of 700 nm and a pulse width of 5 ns was used. The average power was 30 mW and the irradiation time was 1 minute. By this laser light irradiation, the perinaphthothioindigo site of the trans porphyrin compound (2) was excited. In FIG. 9, the visible / ultraviolet absorption spectrum of the solution after excitation is shown by a broken line. The black arrows in the figure indicate the decrease or increase in absorption associated with light irradiation (excitation). As shown in the figure, after excitation, the absorption from 650 nm to 750 nm derived from the perinaphthothioindigo site of the trans form (2) decreased. In addition, absorption from 480 nm to 550 nm derived from the perinaphthothioindigo site of the cis-porphyrin compound (2 ′) increased.

  The excited cis isomer (2 ′) solution was irradiated with light at room temperature (25 ° C.) to excite the perinaphthothioindigo site. Light irradiation was performed with an irradiation wavelength of 520 nm, a monochromator connected to a 150 W Xe lamp, and an average power of 0.1 mW. FIG. 10 shows the change with time of the visible / ultraviolet absorption spectrum when the cis-form (2 ′) solution is irradiated (excited) with light. In the figure, the vertical axis represents absorbance and the horizontal axis represents wavelength. The black arrows in the figure indicate the decrease or increase in absorption associated with light irradiation (excitation). The spectra are before irradiation and 0.5, 2, 3, 5, 7, 10, 15, 25 minutes after the start of irradiation. As shown in the figure, absorption from 650 nm to 750 nm derived from the perinaphthothioindigo site of the trans isomer (2) increased with light irradiation. In addition, absorption from 480 nm to 550 nm derived from the perinaphthothioindigo site of cis isomer (2) decreased. The change in the spectrum almost stopped after 25 minutes of irradiation.

  As described above, cis-porphyrin compound (2 ') was produced by isomerization of trans-porphyrin compound (2). At the same time, the photochromism of the trans isomer (2) and cis isomer (2 ') was also confirmed.

[Example 4: Three-dimensional optical recording material]
The porphyrin compounds (2) and (3) produced in Example 1 were evaluated for performance as a three-dimensional optical recording material.

(Fluorescence spectrum measurement)
As described above, the fluorescence spectrum was measured using a fluorescence spectrometer F-4500 (trade name) manufactured by Hitachi, Ltd. As the excitation light source, an Xe lamp provided as standard equipment in the same device was used.

  First, under the same conditions as in Example 2, the trans-porphyrin compound (3) solution was irradiated with excitation light to excite the perinaphthothioindigo site. And the fluorescence spectrum of the said solution after excitation was measured. The concentration of the trans isomer (3) solution and the solvent used were the same as in Example 2. The irradiation wavelength was 680 nm. The fluorescence spectrum is shown in the graph of FIG. In the figure, the vertical axis represents fluorescence intensity, and the horizontal axis represents wavelength. The description “excitation light” in the figure indicates that the excitation light used for the irradiation is observed at a wavelength of 680 nm. As shown in the figure, fluorescence was observed from 700 nm to 800 nm.

  Furthermore, the fluorescence observation wavelength was fixed at 800 nm, and the change in fluorescence intensity at 800 nm was measured when the irradiation wavelength was changed from 400 nm to 725 nm (excitation spectrum). And the fluorescence spectrum of the said solution after excitation was measured. The fluorescence spectrum is shown in the graph of FIG. In the figure, the vertical axis represents the fluorescence intensity at 800 nm, and the horizontal axis represents the excitation wavelength. As illustrated, an excitation spectrum corresponding to the absorption spectrum derived from the perinaphthothioindigo site of the trans isomer (3) was obtained from 600 nm to 750 nm. In addition, a spectrum derived from the porphyrin Sore band was obtained around 440 nm. The spectrum derived from the Soret band shows that even when the porphyrin moiety is photoexcited, the excitation energy is collected at the perinaphthothioindigo moiety by energy transfer. This result indicates that the trans isomer can be isomerized to the cis isomer by two-photon excitation of the porphyrin's Soret band.

  The cis isomer (3 ') emitted light from the porphyrin moiety even when excited using any wavelength between 400 and 650 nm. Specifically, the fluorescence spectrum was measured using the same cis-form (3 ′) solution as in Example 2. FIG. 6 shows a fluorescence spectrum when excited at an irradiation wavelength of 570 nm. In the figure, the vertical axis represents fluorescence intensity, and the horizontal axis represents wavelength. As shown in the figure, the luminescence intensity of the cis isomer (3 ') was more than one digit higher than that of the trans isomer (3).

(Isomerization by two-photon absorption (photochromism))
As described above, in the porphyrin compound (3), the one-photon absorption of the porphyrin Soret band has an absorption band near about 440 nm. Therefore, the wavelength of two-photon absorption is about twice that of 440 nm. Therefore, as described below, isomerization (photochromism) of the porphyrin compound (3) by two-photon absorption was performed, and the performance as a three-dimensional recording material was evaluated.

Conversion from the trans isomer (3) to the cis isomer (3 ′) was performed as follows. That is, first, the trans porphyrin compound (3) synthesized in Example 1 was dissolved in THF to prepare a 2.4 μM solution. This solution was two-photon excited by laser light irradiation at room temperature (25 ° C.), and the change with time in the visible / ultraviolet absorption spectrum was measured. The irradiation wavelength was 890 nm, the laser beam used was a titanium sapphire laser with a pulse width of 200 fs, and the peak intensity was 0.53 GW / cm ² . The graph of FIG. 7 shows changes with time in the visible / ultraviolet absorption spectrum. In the figure, the vertical axis represents absorbance and the horizontal axis represents wavelength. The spectrum is a spectrum before irradiation and after 10 minutes, 20 minutes, 40 minutes, 60 minutes, 120 minutes, 180 minutes, and 300 minutes have elapsed since the start of irradiation. In the figure, a black arrow (→) associated with each absorption band indicates an increase or decrease in absorption due to laser light irradiation in each absorption band. As shown in the figure, with light irradiation, the absorption from 650 nm to 750 nm derived from the perinaphthothioindigo site of the trans form (3) decreased. At the same time, the absorption from 480 nm to 550 nm derived from the perinaphthothioindigo site of the cis form (3 ′) increased. The graph of the inset of FIG. 7 (upper right of FIG. 7) shows the ratio of the cis isomer (3 ′) calculated from the spectrum of FIG. In the figure, the vertical axis represents the ratio (%) of the cis isomer (3 ′), and the horizontal axis represents the irradiation time (minutes). As shown in the figure, after 300 minutes (5 hours) of irradiation, 55% of the trans isomer (3) existing before the irradiation was converted to a cis isomer (3 ′).

  Conversion from the cis form (3 ′) to the trans form (3) was performed as follows. That is, first, under the same conditions as in Example 2, the solution of the trans porphyrin compound (3) was irradiated with a laser beam having a wavelength of 680 nm to completely transform the trans isomer (3) in the solution into the cis isomer (3 ′). Converted to. Then, this cis isomer (3 ') solution was irradiated with laser light at room temperature (25 ° C) to excite the cis isomer (3') by two-photon excitation, and the change with time in the visible / ultraviolet absorption spectrum was measured. The irradiation wavelength was 890 nm, the laser beam used was a titanium sapphire laser with a pulse width of 200 fs, and the peak intensity was 0.53 GW / cm2. The graph of FIG. 8 shows changes with time in the visible / ultraviolet absorption spectrum. In the figure, the vertical axis represents absorbance and the horizontal axis represents wavelength. The spectrum is a spectrum before irradiation and after 10 minutes, 20 minutes, 40 minutes, 60 minutes, 120 minutes, 180 minutes, and 300 minutes have elapsed since the start of irradiation. In the figure, a black arrow (→) associated with each absorption band indicates an increase or decrease in absorption due to laser light irradiation in each absorption band. As shown in the figure, the absorption from 650 nm to 750 nm derived from the perinaphthothioindigo site of the trans isomer (3) increased with light irradiation. At the same time, absorption from 480 nm to 550 nm derived from the perinaphthothioindigo site of the cis form (3 ') decreased. The graph of the inset of FIG. 8 (upper right of FIG. 8) shows the ratio of the transformer body (3) calculated from the spectrum of FIG. In the figure, the vertical axis represents the ratio (%) of the transformer body (3), and the horizontal axis represents the irradiation time (minutes). As shown in the figure, after irradiation for 300 minutes (5 hours), 17% of the cis form (3 ′) existing before irradiation was converted to the trans form (3).

  Thus, the photochromism phenomenon of the isomerization from the trans isomer (3) to the cis isomer (3 ′) and the isomerization from the cis isomer (3 ′) to the trans isomer (3) occurs by laser light irradiation at a wavelength of 890 nm. It was. That is, the usefulness of the porphyrin compound (3) as a three-dimensional optical recording material could be confirmed by photochromism by two-photon absorption.

  In addition, the porphyrin compound (2) is also isomerized from the trans isomer (2) to the cis isomer (2 ′) and from the cis isomer (2 ′) to the trans isomer (2) in the same manner as described above. The photochromism phenomenon was confirmed. That is, the usefulness of the porphyrin compound (2) as a three-dimensional optical recording material could be confirmed by photochromism by two-photon absorption.

(Measurement of two-photon absorption cross section)
The two-photon absorption cross sections of the compounds (2) and (3) were measured as follows. In the following, the measurement by open Z-scan method and the analysis of the measurement results are described in the references K. Ogawa, A. Ohashi, Y. Kobuke, K. Kamada, and K. Ohta, J. Phys. Chem. B, 109, 22003-22012 (2005).

上記解析の結果、トランス体ポルフィリン化合物（２）の二光子吸収断面積は22000GMであった。また、トランス体ポルフィリン化合物化合物（３）の二光子吸収断面積は15000GMであった。このように、いずれの化合物も非常に大きな二光子吸収断面積値を示した。これにより、化合物（２）および（３）のいずれも、三次元記録材料として非常に大きな記録容量を示しうることが確認された。 Compounds (2) and (3) were individually converted into THF solutions (2.4 × 10 ⁻⁴ mol / L), and the two-photon absorption cross sections were measured at room temperature (25 ° C.). The measurement was performed by an open Z-scan method using a YAG: Nd laser having a pulse width of 5 nanoseconds. The wavelength of the laser beam was set to 890 nm using an optical parametric oscillator (OPO). The measurement was performed using a 2 mm cell and scanning 45 mm before and after the incident light focus. The laser light output was 25 mW for the compound (2) solution and 23 mW for the compound (3) solution. The pulse repetition frequency was 10 Hz for all solutions. FIG. 11 shows the result of the open Z-scan method (Z-scan) measurement of the trans porphyrin compound (3). FIG. 12 shows the results of the open Z-scan method (Z-scan) measurement of the trans porphyrin compound (2). 11 and 12, the horizontal axis indicates the sample position. The vertical axis represents the normalized transmittance. The transparency, T, is defined by T = I _f / I _i . In the above formula, _If is the laser light intensity after passing through the sample, and I _i is the laser light intensity before passing through the sample. Transmission standardization (normalized transmission) was performed in the analysis described below. The results of FIGS. 11 and 12 were analyzed according to the method described in the above reference. Specifically, curve fitting was performed using the following equation (1).

As a result of the above analysis, the two-photon absorption cross section of the trans porphyrin compound (2) was 22000GM. Moreover, the two-photon absorption cross section of the trans porphyrin compound compound (3) was 15000GM. Thus, all the compounds showed very large two-photon absorption cross section values. Thus, it was confirmed that both of the compounds (2) and (3) can exhibit a very large recording capacity as a three-dimensional recording material.

  In this example, compounds (2) and (3) were produced. However, as described above, the compound of the present invention having a structure other than this, that is, a porphyrin compound represented by the formula (1) and including one or more porphyrin rings and one or more perinaphthothioindigo rings, Regarding those tautomers or stereoisomers, or salts thereof, those skilled in the art will also be able to carry out excessive trial and error and complicated advanced experiments based on the description of the present specification (in some cases, referring to common general technical knowledge). It can be manufactured without In this example, the usefulness of the porphyrin compounds (2) and (3) as a three-dimensional optical recording material was confirmed by photochromism by two-photon absorption. However, it will be apparent to those skilled in the art that similar effects can be obtained with the compounds of the present invention having other structures. Specifically, it is as follows. As described above, in the compound of the present invention, the porphyrin ring and the perinaphthothioindigo ring are connected by a linear atomic group. And pi-electron conjugation is possible between the porphyrin ring and the perinaphthothioindigo ring. By having the porphyrin ring, the compound of the present invention can cause two-photon absorption as in the examples. The perinaphthothioindigo ring can receive the two-photon absorption energy by π electron conjugation. And the photochromism occurs because the perinaphthothioindigo ring is isomerized. That is, as long as the compound of the present invention has the structure of the formula (1), photochromism can be caused by two-photon absorption. As described above, if photochromism occurs due to two-photon absorption, it can be used for three-dimensional recording. Furthermore, the use of the compound of the present invention is not limited to the three-dimensional optical recording material and the three-dimensional optical recording medium, and can be used for other uses.

As described above, the compound of the present invention has a high two-photon absorption efficiency and is suitable for uses such as a three-dimensional optical recording material by effectively causing photochromism by light absorption. The three-dimensional optical recording material of the present invention can be recorded three-dimensionally by including the compound of the present invention. In addition, the three-dimensional optical recording medium of the present invention is capable of recording a large volume by having the above-described configuration. For example, according to the present invention, a rewritable three-dimensional optical memory medium can be provided. In addition, for example, the compound of the present invention has a high two-photon absorption cross-sectional area of 10,000 GM or more as described above, so that a high density of 1 terabit per 1 cm ³ (equivalent to 100,000 floppy (registered trademark) disks). It is also possible to record information. The three-dimensional optical recording medium of the present invention can be expected as a next-generation storage medium by having such a large recording capacity. Furthermore, the application of the compound of the present invention is not limited to the three-dimensional optical recording material and the three-dimensional optical recording medium, and may be used for any application.

FIG. 1 is a graph showing the visible / ultraviolet absorption spectrum of the compound (3) of Example (in a tetrahydrofuran (THF) solution). FIG. 2 is a graph showing changes in the visible / ultraviolet absorption spectrum when the compound (3) of Example is photoisomerized from a trans form to a cis form at room temperature (in a THF solution). FIG. 3 shows changes in the visible / ultraviolet absorption spectrum when the compound (3 ′) of the example was subjected to a photoisomerization reaction from the cis form to the trans form at room temperature (in a THF solution). FIG. 4 is a graph showing the fluorescence spectrum of the trans isomer compound (3) in Examples (excitation wavelength: 680 nm in a THF solution). FIG. 5 is a graph showing the excitation spectrum of the trans isomer compound (3) in the examples (in a THF solution, the fluorescence wavelength is 800 nm). FIG. 6 is a graph showing the fluorescence spectrum of the cis-isomer compound (3 ′) in Examples (excitation wavelength: 570 nm in a THF solution). FIG. 7 is a graph showing the photoisomerization reaction from the trans isomer to the cis isomer by two-photon absorption of the trans isomer compound (3) in the example (excitation wavelength: 890 nm in a THF solution). FIG. 8 is a graph showing the photoisomerization reaction from the cis form to the trans form by two-photon absorption of the cis form compound (3 ′) in the example (excitation wavelength: 890 nm in a THF solution). FIG. 9 is a graph showing changes in the visible / ultraviolet absorption spectrum during the photoisomerization reaction from the trans form to the cis form in the compound (2) of the example (in a THF solution). FIG. 10 is a graph showing changes in the visible / ultraviolet absorption spectrum in the photoisomerization reaction from the cis form to the trans form of the compound (2 ′) of Example (in a THF solution). FIG. 11 is a Z-scan diagram of the trans isomer compound (3) in the examples (THF solution, 5 ns pulse, 10 Hz, 23 mW). FIG. 12 is a Z-scan diagram of the trans isomer compound (2) in the examples (THF solution, 5 ns pulse, 10 Hz, 25 mW).

Claims (20)

A porphyrin compound represented by the following formula (1) and containing one or more porphyrin rings and one or more perinaphthothioindigo rings, a tautomer or stereoisomer thereof, or a salt thereof.

In the formula (1),
P ¹ is an atomic group represented by the following formula (a ¹ ), (b ¹ ) or (c ¹ ),

[Y] is an atomic group represented by the following formula (a ² ), (b ² ) or (c ² ),

P ² is a hydrogen atom, halogen, or an atomic group represented by the following formula (a ³ ), (b ³ ), or (c ³ ),

In the above formulas (a ¹ ), (b ¹ ), (a ² ), (b ² ), (a ³ ) and (b ³ ),
R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and the substituted or unsubstituted alkyl group is linear, branched, or cyclic (substituted) Or a substituted cycloalkyl group). In the substituted alkyl group, one or more substituents may be used, and when there are a plurality of substituents, they may be the same or different. The substituted or unsubstituted aryl group is a single ring. Or a condensed ring, which may or may not contain a heteroatom. In the substituted aryl group, one or a plurality of substituents may be used, and in the case of a plurality, each may be the same or different. ¹ may be the same or different,
R ³ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and the substituted or unsubstituted alkyl group is linear, branched, or cyclic (substituted) Or a substituted cycloalkyl group). In the substituted alkyl group, one or more substituents may be used, and when there are a plurality of substituents, they may be the same or different. The substituted or unsubstituted aryl group is a single ring. Or a condensed ring, which may or may not contain a heteroatom. In the substituted aryl group, one or a plurality of substituents may be used, and in the case of a plurality, each may be the same or different. ³ may be the same or different,

In the above formulas (a ¹ ), (b ¹ ), (c ¹ ), (a ³ ), (b ³ ) and (c ³ ),
L ⁰ is a linear atomic group that can be conjugated to the ring bonded to both ends of L ⁰ , and when there are a plurality of L ⁰ in the formula (1), each L ⁰ is the same or different. Well,

In the formulas (a ¹ ), (b ¹ ), (a ³ ) and (b ³ ),
R ² represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a 5- or 6-membered nitrogen-coordinating heteroaromatic ring, or a halogen, respectively, and the substituted or unsubstituted The alkyl group may be linear, branched or cyclic (substituted or unsubstituted cycloalkyl group). In the substituted alkyl group, one or a plurality of substituents may be used, and in the case of a plurality, they may be the same or different. The substituted or unsubstituted aryl group may be a single ring or a condensed ring, and may or may not contain a hetero atom. In the substituted aryl group, one or more substituents may be included. In the case where a plurality of R ² are present in the formula (1), each R ² may be the same or different.
M ¹ is a metal, metal halide, metal oxide, metal hydroxide, Si, Ge, or P, or represents two hydrogen atoms, and a plurality of M ¹ exist in the formula (1). Each M ¹ may be the same or different,

In the formula (b ¹ ),
x is a positive integer,

In the formula (b ³ ),
y is a positive integer,

In the formulas (b ¹ ) and (b ³ ),
M ² is a metal, metal halide, metal oxide, metal hydroxide, Si, Ge, or P, or represents two hydrogen atoms, and M ¹ and M ² may be the same or different Well, when there are a plurality of M ² in the formula (1), each M ² may be the same or different,
L ¹ are each a porphyrin ring attached to both ends of the L ¹ is a conjugate that can be linear atomic group, L ⁰ and L ¹ may be the same or different, is L ¹ in the formula (1) If there are multiple, each L ¹ may be the same or different,

In the above formulas (a ² ) and (b ² ),
M ³ is a metal, metal halide, metal oxide, metal hydroxide, Si, Ge, or P, or represents two hydrogen atoms, and M ³ is the same as M ¹ and M ² However, when there are a plurality of M ³ in the formula (1), each M ³ may be the same or different,

In the formula (b ² ),
z is a positive integer,
L ² are each a porphyrin ring attached to both ends of the L ² is conjugated possible linear atomic group, L ² may be the same or different from that of the L ⁰ and L ^1, L ² are plurality of Each L ² may be the same or different,

In the formulas (c ¹ ), (c ² ) and (c ³ ),
R ⁴ is a hydrogen atom or halogen, and each R ⁴ may be the same or different. The porphyrin compound, its tautomer or stereoisomer, or a salt thereof according to claim 1, wherein the number of perinaphthothioindigo rings contained in the formula (1) is 1. In the formula (1), [Y] is represented by the formula (c ² ), P ¹ is represented by the formula (a ¹ ), and P ² is a hydrogen atom (represented by the following formula (i) The porphyrin compound according to claim 2, a tautomer or stereoisomer thereof, or a salt thereof.

In the formula (i), R ¹ , R ² , R ³ , R ⁴ , L ⁰ and M ¹ are the same as those in the formula (1). In the formula (1) is represented by [Y] is the formula (c ^2), are represented by P ¹ is the formula (b ^1), a polymerization degree x in the formula (b ¹⁾ is 1, The porphyrin compound according to claim ² , wherein P ² is a hydrogen atom (represented by the following formula (ii)), a tautomer or stereoisomer thereof, or a salt thereof.

In the formula (ii), R ¹ , R ² , R ³ , R ⁴ , L ⁰ , L ¹ , M ¹ and M ² are the same as those in the formula (1). In the formula (1), [Y] is represented by the formula (c ² ), P ¹ is represented by the formula (a ¹ ), and P ² is represented by the formula (a ³ ) (the following formula The porphyrin compound according to claim 2, represented by (iii), a tautomer or stereoisomer thereof, or a salt thereof.

In the formula (iii), R ¹ , R ² , R ³ , R ⁴ , L ⁰ and M ¹ are the same as those in the formula (1). In the formula (1) is represented by [Y] is the formula (c ^2), are represented by P ¹ is the formula (b ^1), a polymerization degree x in the formula (b ¹⁾ is 1, P ² is represented by the formula (b ^3), the formula (b ³⁾ the degree of polymerization y is 1 (the following formula (represented by iv)) porphyrin compound of claim 2, wherein in its tautomeric Sex or stereoisomer, or a salt thereof.

In the formula (iv), R ¹ , R ² , R ³ , R ⁴ , L ⁰ , L ¹ , M ¹ and M ² are the same as those in the formula (1). In the formula (1), [Y] is represented by the formula (c ² ), P ¹ is represented by the formula (a ¹ ), P ² is represented by the formula (b ³ ), and the formula ( polymerization degree y of b ³⁾ in is 1 (the following formula (v) represented by) porphyrin compound of claim 2, wherein, a tautomer or stereoisomer or salt thereof.

In the formula (v), R ¹ , R ² , R ³ , R ⁴ , L ⁰ , L ¹ , M ¹ and M ² are the same as those in the formula (1). In the formula (1),
P ¹ is represented by the formula (c ¹ ),
and,
[Y] is represented by the formula (c ² ) and P ² is represented by the formula (a ³ ) (the following formula (vi)), or [Y] is represented by the formula (a ² ). P ² is represented by the formula (c ³ ) (the following formula (vii)),
The porphyrin compound according to claim 1, its tautomer or stereoisomer, or a salt thereof.

In the formulas (vi) and (vii), R ¹ , R ³ , R ⁴ and L ⁰ are the same as those in the formula (1),
In the formula (vi), R ² and M ¹ are the same as those in the formula (1),
In the formula (vii), M ³ is the same as in the formula (1). In the formula (1),
In the above formulas (a ¹ ), (b ¹ ), (a ² ), (b ² ), (a ³ ) and (b ³ ),
In R ¹ , the substituted alkyl group is at least one selected from the group consisting of an alkoxycarbonylalkyl group, an alkoxyalkyl group, an alkenoxyalkyl group, an alkenoxycarbonylalkyl group, and a carboxyalkyl group, The substituted aryl group is at least one selected from the group consisting of an alkylaryl group, an alkoxyaryl group, an alkoxycarbonylaryl group, an alkenoxyaryl group, a carboxyaryl group, and an alkenoxycarbonylaryl group, and each R ¹ Can be the same or different,

In the above formulas (a ¹ ), (b ¹ ), (c ¹ ), (a ³ ), (b ³ ) and (c ³ ),
L ⁰ is an atomic group represented by the following formula (L ¹⁰⁰ ),

In the formula (L ¹⁰⁰ ), n represents an integer of 1 to 3, and when there are a plurality of L ⁰ in the formula (1), each L ⁰ may be the same or different,

In the formulas (a ¹ ), (b ¹ ), (a ³ ) and (b ³ ),
In R ² , the substituted alkyl group is at least one selected from the group consisting of an alkoxycarbonylalkyl group, an alkoxyalkyl group, an alkenoxyalkyl group, an alkenoxycarbonylalkyl group, and a carboxyalkyl group, The substituted aryl group is at least one selected from the group consisting of an alkylaryl group, an alkoxyaryl group, an alkoxycarbonylaryl group, an alkenoxyaryl group, a carboxyaryl group, and an alkenoxycarbonylaryl group, The 6-membered nitrogen-coordinating heteroaromatic ring is at least one selected from the group consisting of imidazole, N-methylimidazole, pyridine, pyrazole, and pyrimidine, and R ^{2 in the} formula (1) If there are a plurality each R ² be the same or different It may be had,
M ¹ is a metal, metal halide, metal oxide, metal hydroxide, Si, Ge, or P, or represents two hydrogen atoms, and a plurality of M ¹ exist in the formula (1). Each M ¹ may be the same or different,

In the formula (b ¹ ),
x is a positive integer,

In the formula (b ³ ),
y is a positive integer,

In the formulas (b ¹ ) and (b ³ ),
M ² is a metal, metal halide, metal oxide, metal hydroxide, Si, Ge, or P, or represents two hydrogen atoms, and M ¹ and M ² may be the same or different Well, when there are a plurality of M ² in the formula (1), each M ² may be the same or different,
L ¹ is represented by the following formula (L ²⁰⁰ ),

In the formula (L ²⁰⁰ ), m represents an integer of 1 to 3, and when a plurality of L ¹ are present in the formula (1), each L ¹ may be the same or different,

In the above formulas (a ² ) and (b ² ),
M ³ is a metal, metal halide, metal oxide, metal hydroxide, Si, Ge, or P, or represents two hydrogen atoms, and M ³ is the same as M ¹ and M ² However, when there are a plurality of M ³ in the formula (1), each M ³ may be the same or different,

In the formula (b ² ),
z is a positive integer,
L ² is represented by the following formula (L ³⁰⁰ ),

In the formula (L ³⁰⁰ ), l represents any integer of 1 to 3, and when a plurality of L ² are present, each L ² may be the same or different,

In the formulas (c ¹ ), (c ² ) and (c ³ ),
R ⁴ is a hydrogen atom or halogen, and each R ⁴ may be the same or different.
The porphyrin compound according to any one of claims 1 to 8, a tautomer or stereoisomer thereof, or a salt thereof. L ⁰ is a porphyrin compound according to claim 1 which is an ethynylene group (-C≡C-), a tautomer or stereoisomer or salt thereof. In the formula (1),
In the formulas (a ¹ ), (b ¹ ), (a ³ ) and (b ³ ),
M ¹ is an ion of zinc, iron, cobalt, ruthenium or gallium, or two hydrogen atoms, and when there are a plurality of M ¹ in the formula (1), each M ¹ is the same or different. You may,

In the above formulas (b ¹ ) and (b ³ ),
When M ² is an ion of zinc, iron, cobalt, ruthenium or gallium or two hydrogen atoms, and there are a plurality of M ² in the formula (1), each M ² is the same or different. You may,

In the formulas (a ² ) and (b ² ),
Is M ^3, zinc, iron, cobalt, or an ion of ruthenium or gallium, or 2 hydrogen atoms, each M ³ represents the case where M ³ there are a plurality may be the same or different,
The porphyrin compound according to any one of claims 1 to 10, a tautomer or stereoisomer thereof, or a salt thereof. In the formula (1),
In the above formulas (a ¹ ), (b ¹ ), (a ² ), (b ² ), (a ³ ) and (b ³ ),
In R ¹ , the substituted or unsubstituted alkyl group has 1 to 24 carbon atoms in total, and the substituted or unsubstituted aryl group has 6 to 24 carbon atoms in total;
In the formulas (a ¹ ), (b ¹ ), (a ³ ) and (b ³ ),
In R ² , the substituted or unsubstituted alkyl group has 1 to 24 carbon atoms in total, and the substituted or unsubstituted aryl group has 6 to 24 carbon atoms in total.
The porphyrin compound according to any one of claims 1 to 11, a tautomer or stereoisomer thereof, or a salt thereof. The porphyrin compound represented by the formula (1) is
[Y] is represented by the formula (c ² ),
P ¹ is represented by the formula (a ¹ ) or (b ¹ ), the degree of polymerization x in the formula (b ¹ ) is 1,
P ² is the formula (a ³⁾ or (b ³⁾ at or represented by, or a hydrogen atom, represented by P ² is Formula (b ^3), the polymerization degree of the formula (b ³⁾ in y is 1,
In the above formulas (a ¹ ), (b ¹ ), (a ³ ) and (b ³ ), R ³ is all a hydrogen atom, L ⁰ is an ethynylene group,
In the formulas (b ¹ ) and (b ³ ), L ¹ is represented by the following formula (L ²⁰⁰ ),

In the formula (L ²⁰⁰ ), m represents an integer of 1 to 3, and when a plurality of L ¹ are present in the formula (1), each L ¹ may be the same or different,
In the formula (c ² ), all R ⁴ are hydrogen atoms.
A porphyrin compound (represented by any of the following formulas (xi) to (xv)),

In the formulas (xi) to (xv),
M ¹ is a metal ion or two hydrogen atoms, and when there are a plurality of M ¹ in the formula (1), each M ¹ may be the same or different,

In the formula (xii), (xiv) and (xv),
M ² is a metal ion or two hydrogen atoms, M ¹ and M ² may be the same or different, and when there are a plurality of M ² in the formula (1), each M ² is the same But it can be different,
The porphyrin compound according to any one of claims 1 to 7 and 9 to 12, a tautomer or stereoisomer thereof, or a salt thereof. In the formula (1),
The porphyrin compound represented by the formula (1) is
[Y] is represented by the formula (c ² ),
P ¹ is represented by the formula (a ¹ ) or (b ¹ ), the degree of polymerization x in the formula (b ¹ ) is 1,
P ² is represented by the formula (a ³ ) or (b ³ ) or a hydrogen atom, and the degree of polymerization y in the formula (b ³ ) is 1.
In the formulas (a ¹ ), (b ¹ ), (a ³ ) and (b ³ ),
L ⁰ is an ethynylene group,
R ² is all a hydrogen atom,
R ³ is all hydrogen atoms,
In the formulas (b ¹ ) and (b ³ ),
L ¹ is an ethynylene group,
In the formula (c ² ),
R ⁴ is all a hydrogen atom,
A porphyrin compound (represented by any of the following formulas (xxi) to (xxv)),

In the formulas (xxi) to (xxv),
R ¹ is a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, phenyl group, At least one selected from the group consisting of 4-methoxycarbonylphenyl group, 3,5-bis (methoxycarbonyl) phenyl group, 4-ethoxycarbonylphenyl group, and 3,5-bis (ethoxycarbonyl) phenyl group Each R ¹ may be the same or different,
M ¹ is Zn (II), Ga (III), Fe (II), Fe (III), Co (II), Co (III), Ru (II), Ru (III) or two hydrogen atoms Yes, when there are a plurality of M ¹ in the formula (1), each M ¹ may be the same or different,

In the formula (xxii), (xxiv) and (xxv),
M ² is Zn (II), Ga (III), Fe (II), Fe (III), Co (II), Co (III), Ru (II), Ru (III) or two hydrogen atoms Yes, M ¹ and M ² may be the same or different, and when there are a plurality of M ² in the formula (1), each M ² may be the same or different.
The porphyrin compound according to claim 1, its tautomer or stereoisomer, or a salt thereof. The porphyrin compound represented by the formula (1) is a porphyrin compound represented by the following formula (2) or (3), a tautomer or stereoisomer thereof, or a compound thereof. Salt.

A method for producing the porphyrin compound according to claim 1, a tautomer or stereoisomer thereof, or a salt thereof.
A step of coupling a porphyrin derivative with a halogenated perinaphthothioindigo derivative,
The porphyrin derivative is a derivative in which at least one of hydrogen atoms bonded to the 5-position, 10-position, 15-position and 20-position carbon of the porphyrin ring is substituted with a substituent -L ⁰ -H, and the L ⁰ is claimed. It is the same as L ⁰ described in item 1,
The halogenated perinaphthothioindigo derivative is a derivative in which the para carbon of the carbon bonded to the S atom is halogenated in at least one of the two naphthalene rings in the perinaphthothioindigo ring.
Production method. A three-dimensional optical recording material comprising the porphyrin compound according to any one of claims 1 to 15, a tautomer or stereoisomer thereof, or a salt thereof. A three-dimensional optical recording medium having a recording layer capable of recording information, wherein the recording layer includes the three-dimensional optical recording material according to claim 17. An optical recording material comprising the porphyrin compound according to any one of claims 1 to 15, a tautomer or stereoisomer thereof, or a salt thereof. An optical recording medium having a recording layer capable of recording information, wherein the recording layer includes the optical recording material according to claim 19.

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