JP2007015947A - Spherical transition metal complex and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a spherical transition metal complex of a transition metal complex having a hollow shell formed out of n1 transition metal atoms (n1 is an integer of 6-60) and 2n1 organic bidentates having substituents regulated so as to be oriented in the interior of the hollow shell; and to provide a method for producing the complex. <P>SOLUTION: The spherical transition metal complex having the hollow shell is provided. The hollow shell is formed out of the n1 transition metal atoms and 2n1 organic bidentates having the substituents which are regulated so as to be oriented in the interior of the hollow shell. The method for producing the spherical transition metal complex involves reacting the organic bidentates having the substituents in a proportion of 1-5 mol with the transition metal compound of 1 mol. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention has a novel hollow shell formed from a bidentate organic ligand having a substituent and a transition metal atom, and the substituent of the bidentate organic ligand is oriented inside the hollow shell. The present invention relates to a spherical transition metal complex and a method for producing the same.

  Strictly controlled nano-sized hollow structures can be classified into three regions: surface, inner surface, and isolated interior space. So far, the surface and internal space have been extensively studied, but there have been few reports on research using the inner surface in artificial systems.

  In recent years, research using the inner surface of natural nanoscale structures such as globular proteins such as ferritin and globular virus CCMV has been conducted. Even if these structures are decomposed by an artificial stimulus, they are restored to their original structures by self-organization. The functional group is modified on the subunit so that it faces the inner surface of the spherical shell structure (spherical structure having a hollow shell), and the spherical shell structure is formed again by self-organization, so that the functional group is precisely applied to the spherical inner surface. (Non-patent Documents 1 and 2).

However, it is difficult in organic chemistry to simultaneously bond a plurality of functional groups to the inner surface of the spherical structure with a probability of 100%.
Therefore, if a spherical structure is designed by a chemical method and functional functional groups can be introduced therein, it is expected that the structure and function can be freely controlled by molecular design.

Conventionally, dendrimers and micelles are known as functional structures having organic molecules as a basic skeleton.
Dendrimers have a three-dimensional branched structure, and functional parts are densely packed inside. Functions such as inclusion of metal ions and collection of light energy have been found by collecting these functional groups in the sphere (Non-Patent Documents 3 to 7).

In addition, by removing the core after cross-linking the end of the dendrimer, it has a spherical shell structure with a space inside, and the target molecule is selectively recognized by the functional group gathered at the center. It has attracted attention as printing (Non-Patent Documents 8 to 11).
However, the dendrimer has a problem that the synthesis is complicated and it is difficult to expand the internal space.

  On the other hand, a micelle is a spherical shell structure formed by self-assembly of an amphiphilic substance composed of a hydrophilic part and a hydrophobic part by hydrophobic interaction in a solvent. In the case of micelles in water, the hydrophobic part is oriented inside the micelle, and the environment on the inner surface of the micelle can be controlled freely and easily by introducing various functional functional groups into this hydrophobic part. Is possible (Non-patent Documents 12 and 13).

  However, in micelles, since the distribution occurs in the number of constituent components and the density of the assembly, the size and structure cannot be uniquely controlled, and the internal functional groups cannot be precisely arranged. Therefore, it is difficult to define the number of functional groups that accumulate inside.

  In order to aim at advanced functionalization using a hollow structure, it is important to have a wide space inside. Further, it is necessary to precisely control the number and positions of functional groups arranged inside by using a structure whose structure and size are clearly determined and that is uniquely generated.

  In recent years, various structures having a controlled structure and a wide space have been constructed by using self-organization based on the cooperative action of weak bonds as described above.

  The present inventors have also studied self-organization using a coordinate bond between an organic ligand and a transition metal ion. Since the coordinate bond has an appropriate binding force and the directionality is clearly defined, it is possible to spontaneously and quantitatively construct a molecular assembly whose structure is precisely controlled. In addition, since the coordination number and the bond angle can be controlled according to the type of metal and the oxidation number, various coordination bonding structures can be obtained (Patent Documents 14 to 16).

For example, when planar four-coordinate Pd (II) ions are used, the direction of coordination bond can be defined as 90 degrees. In particular, a palladium ethylenediamine nitrate complex [(en) Pd (NO ₃ ) ₂ ] (M) in which the cis position is protected with ethylenediamine and a panel-like organic ligand (L) are various depending on the ligand. The hollow structure self-assembles as the most stable state (Patent Documents 17 to 22).

In addition, a self-assembly of a cubic octahedral spherical complex having a multi-component M ₁₂ L ₂₄ composition has also been found (Non-patent Document 23). Twenty-four bent-type bidentate ligands of about 120 degrees centered on furan or benzene and 12 Pd (II) ions are self-assembled to form a total of 14 faces, 8 equilateral triangles and 6 squares. It is composed. In this case, the number of vertices is 12, the number of sides is 24, which corresponds to the number of metal ions and ligands, respectively.

This structure is clarified by X-ray crystal structure analysis, and has a diameter of about 3.5 nm and an internal space volume of about 22 nm ³ , and a huge three-dimensional hollow structure is constructed. Further, it is known that a spherical complex having a composition of M ₁₂ L ₂₄ is similarly constructed from a bidentate ligand in which the length of the ligand is changed, and a spherical complex having a diameter of 5 nm self-assembles. These complexes have a spherical structure in which the internal space is the widest, and this size is sufficient for inclusion of biomolecules such as proteins and nucleic acids.

In the spherical complex having the M ₁₂ L ₂₄ composition, by introducing a functional group at a predetermined position of the ligand, it is possible to arrange 24 functional groups at once on the nano surface of the spherical capsule through a self-assembly reaction. It is clear. For example, a complex in which porphyrin or fullerene is precisely arranged on the surface has been reported (Non-Patent Document 23), and application to physiological activity and optical properties utilizing a nano-surface having a spherical structure is expected.

In addition, by introducing a cationic trimethylammonium group, a cationic ball having a charge of 48 ⁺ is constructed on the surface, and a unique function of the nanosurface has been found, such as remarkably increasing the protein metamorphism (non-non-functionality). Patent Document 24).

R. M.M. Kramer, C.I. Li, D.D. C. Carter, M.M. O. Stone, R.M. R. Naik, J .; Am. Chem. Soc. , 2004, 126, 13283 T. T. et al. Douglas, E .; Strable, D.M. Willits, A.D. Aitouchen, M.A. Libera, M .; Young, Adv. Mater. , 2002, 14, 415 D. -L. Jiang and T. Aida, Nature, 1997, 388, 454 G. Unger, V.M. Percec, M .; N. Holerca, G .; Johansson, and J.M. A. Heck, Chem. Eur. J. et al. 2000, 6,1258 R. M.M. Crooks, M.M. Zhao, L .; Sun, V.M. Chechik, and L.C. K. Yeung, Acc. Chem. Res. , 2001, 34, 180 S. Naro, S .; Kitagawa, M .; Kondo, K .; Seki, Angew. Chem. Int. Ed. 2000, 39, 2028 M.M. Tominaga, J. et al. Hosogi, K .; Konishi, and T.K. Aida, Chem. Commun. , 2000, 719 M.M. S. Wendland, S.W. C. Zimmerman, J. et al. Am. Chem. Soc. 1999, 121, 1389 S. C. Zimmerman, M .; S. Wendland, Nature, 2002, 418, 399 E. Mertz, S.M. C. Zimmerman, J. et al. Am. Chem. Soc. , 2003, 125, 3424 S. C. Zimmerman, I.D. Zharov, M .; S. Wendlad, N.W. A. Rakow, K .; S. Sudrick, J .; Am. Chem. Soc. , 2003, 125, 13504 Y. Kakizawa and K.K. Kataoka, Adv. Drug Deliv. Rev. , 2002, 54, 203 M.M. L. Adams, A .; Lavasanifar, G.M. S. Kwon, J .; Pharm. Sci. , 2003, 92, 1343 P. J. et al. Stang, B.M. Olynuk, Acc. Chem. Res. 1997, 30, 507 M.M. Fujita, Chem. Soc. Rev. 1998, 27, 417 B. Olynuk, A .; Fechtencotter, P.M. J. et al. Stang, J. et al. Chem. Soc. Dalton Trans. 1998, 1707 M.M. Fujita, K .; Umemoto, M.M. Yoshizawa, N .; Fujita, T .; Kusukawa, K. et al. Biradha, Chem. Commun. , 2001, 509 M.M. Fujita, D .; Oguro, M .; Miyazawa, H .; Oka, K .; Yamaguchi, K .; Ogura, Nature, 1995, 378, 469 N. Takeda, K .; Umemoto, K.M. Yamaguchi, M .; Fujita, Nature, 1999, 398, 794 K. Umemoto, H.M. Tsukui, T .; Kusukawa, K. et al. Biradha, M .; Fujita, Angew. Chem. Int. Ed. , 2001, 40, 2620 M.M. Aoyagi, S .; Tashiro, M .; Tominaga, K .; Biradha, M .; Fujita, Chem. Commun. , 2002, 2036 T. T. et al. Yamaguchi, S .; Tashiro, M .; Tominaga, M .; Kawano, T .; Ozeki, M .; Fujita, J .; Am. Chem. Soc. , 2004, 10818 M.M. Tominaga, K .; Suzuki, M .; Kawano, T .; Kusukawa, T .; Ozeki, S .; Sakamoto, K .; Yamaguchi, M .; Fujita, Angew. Chem. Int. Ed. , 2004, 43, 5621 Kenichiro Yakura, graduation thesis, University of Tokyo

  The present invention has been made as part of the present inventors' research and development, and includes n1 transition metal atoms (n1 represents an integer of 6 to 60), 2n1 substituents, and the like. A transition metal complex having a hollow shell formed from a bidentate organic ligand having a spherical transition metal complex formed so that the substituent is oriented inside the hollow shell, and It is an object to provide a manufacturing method.

The present inventors synthesized a compound in which various substituents were introduced at the 2-position of 1,3-bis (4-pyridylethynyl) benzene, and used this as a bidentate organic ligand to form a compound with a transition metal compound. Attempts were made to form self-assembled spherical transition metal complexes.
As a result, it has been found that a conventional spherical transition metal complex can be obtained efficiently while disposing the substituent inside the hollow shell of the complex, and the present invention has been completed.

Thus, according to the first aspect of the present invention, a spherical transition metal complex according to any one of the following (1) to (9) is provided.
(1) A spherical transition metal complex having a hollow shell, wherein the hollow shell has n1 transition metal atoms (n1 represents an integer of 6 to 60) and 2n1 substituents. A spherical transition metal complex, characterized in that the spherical transition metal complex is formed from a bidentate organic ligand and has the substituent oriented in the hollow shell.
(2) A spherical transition metal complex having a hollow shell, wherein the hollow shell has n2 (n2 is 6, 12, 24, 30 or 60) transition metal atoms and 2n2 A spherical transition metal complex, which is formed from a bidentate organic ligand having a substituent, and is formed so that the substituent is oriented inside the hollow shell.
(3) A formula formed by self-organizing the transition metal compound (M) and the bidentate organic ligand (L) having a substituent so that the substituent is oriented inside the hollow shell. Spherical transition according to (1) represented by M _n1 L _2n1 (n1 represents an integer of 6 to 60, and M and L may be the same or different from each other). Metal complex.

(4) A formula formed by self-organizing the transition metal compound (M) and the bidentate organic ligand (L) having a substituent so that the substituent is oriented inside the hollow shell, (2) represented by M _n2 L _2n2 (n2 is 6, 12, 24, 30 or 60, and M and L may be the same or different from each other). The spherical transition metal complex described.
(5) The spherical transition metal complex according to any one of (1) to (4), which has a hollow shell having a diameter of 3 to 15 nm.
(6) The transition metal atom constituting the transition metal complex is a kind selected from the group consisting of Ti, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Cd, Os, Ir, and Pt. The spherical transition metal complex according to any one of (1) to (5), wherein
(7) The bidentate organic ligand is represented by the formula (I)

{Wherein, R ¹ and R ² each independently represents a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, a cyano group, or a nitro group.
m1 and m2 each independently represents an integer of 0 to 4. m1, m2 is 2 or more, ^{R 1} each other, even ^{R 2} together are each identical or may be different phases.
A represents the following formulas (a-1) to (a-4)

[R ³ represents a substituent.
R ⁴ represents a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, a cyano group, or a nitro group.
m3 represents an integer of 0 to 3, and m4 represents an integer of 0 to 2. When m3 is 2 or more and m4 is 2, the plurality of R ⁴ may be the same or different.
Q is, -Nr1-, (r1 represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group.) - O -, - C (= O) -, - S-, or -SO ₂ - represents a. ]
The group represented by these is shown. }
The spherical transition metal complex according to any one of (1) to (6), which is a kind of a compound represented by formula (1).

(8) wherein ^{R 3} is an optionally substituted alkyl group or wherein _{:-( OCH 2 CH 2) s -OR} 5 [wherein, ^{R 5} is a hydrogen atom, an alkyl group which may be substituted, , An optionally substituted aryl group, an optionally substituted heterocyclic group, a formula: —CO—C (r ₂ ) ═CH ₂ (r ₂ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ) Group represented by the formula: — (CH ₂ ) t—R ⁶ —N═N—R ⁷ (t represents an integer of 0 to 10, R ⁶ represents an optionally substituted arylene group, R ⁷ represents an optionally substituted aryl group.), And s represents an integer of 0-20. The spherical transition metal complex according to (7), which is a group represented by the formula:
(9) The bidentate organic ligand is represented by the formula (I-1)

{Wherein R ⁸ is an optionally substituted alkyl group, or a formula: — (OCH ₂ CH ₂ ) _s —OR ⁵ [wherein R ⁵ is a hydrogen atom, an optionally substituted alkyl group. , An optionally substituted aryl group, an optionally substituted heterocyclic group, a formula: —CO—C (r ₂ ) ═CH ₂ (r ₂ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ) Group represented by the formula: — (CH ₂ ) t—R ⁶ —N═N—R ⁷ (t represents an integer of 0 to 10, R ⁶ represents an optionally substituted arylene group, R ⁷ represents an optionally substituted aryl group.), And s represents an integer of 0-20. ] Is represented. } The spherical transition metal complex according to any one of (1) to (6), which is a compound represented by

According to a second aspect of the present invention, there is provided a method for producing a spherical transition metal complex according to the following (10) and (11).
(10) The transition metal compound (M) and the bidentate organic ligand (L) having a substituent are converted to 1 to 5 with respect to 1 mole of the transition metal compound (M). The method for producing a spherical transition metal complex according to any one of (1) to (9), wherein the reaction is performed in a molar ratio.
(11) The transition metal atom constituting the transition metal compound is a kind selected from the group consisting of Ti, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Cd, Os, Ir, and Pt. (10) The manufacturing method of the spherical transition metal complex as described in (10) characterized by these.

The spherical transition metal complex of the present invention has a hollow shell with a precisely controlled size, and has a special structure in which substituents of the bidentate organic ligand are oriented inside the hollow shell.
According to the present invention, since the functional group of the bidentate organic ligand can be accumulated inside the hollow shell of the spherical transition metal complex, the functions and information of small molecules are amplified inside the spherical transition metal complex. Is expected to be.
In addition, the functional group introduced into the bidentate organic ligand allows the environment inside the hollow space of the spherical transition metal complex to be changed freely, allowing other molecules and ions to be incorporated as guests. It is possible to control the type and number of guests by using the functional group arranged in the.

  According to the production method of the present invention, a nanometer-scale spherical transition metal complex having a functional group inside a spherical structure can be efficiently produced without requiring a complicated step.

Hereinafter, the present invention will be described in detail.
1) Spherical transition metal complex The spherical transition metal complex of the present invention is a spherical transition metal complex having a hollow shell, and the hollow shell has n1 transition metal atoms and 2n1 substituents. Formed from a bidentate organic ligand (hereinafter sometimes referred to as “bidentate ligand (L)”), and formed so that the substituent is oriented inside the hollow shell. It is characterized by.
Here, n1 is an integer of 6-60.

Among them, the spherical transition metal complex of the present invention is a spherical transition metal complex having a hollow shell, and the hollow shell is bidentate having n2 transition metal atoms and 2n2 substituents. It is preferably a spherical transition metal complex formed of a ligand (L) and having the substituents oriented in the hollow shell.
Here, n2 is 6, 12, 24, 30 or 60, preferably 6 or 12, particularly preferably 12.

  The spherical transition metal complex of the present invention is formed by utilizing self-organization utilizing a coordinate bond between a transition metal ion and a bidentate ligand (L). Since the coordinate bond has an appropriate binding force and the directionality is clearly defined, it is possible to spontaneously and quantitatively construct a molecular assembly whose structure is precisely controlled. In addition, since the coordination number and the bond angle can be controlled in accordance with the type of metal and the oxidation number, a variety of coordination bonding structures are possible.

The spherical transition metal complex of the present invention is formed from the transition metal compound (M) and the bidentate ligand (L) in a self-organized manner so that the substituent is oriented inside the hollow shell. wherein: M _{n1 L} 2n1 _{(. n1} is that the same as defined above) is preferably one represented by, because the transition metal compound (M) and the bidentate ligand (L), the shell inside the substituents hollow A compound represented by the formula: M _n2 L _2n2 (n2 represents the same meaning as described above), which is formed in a self-organizing manner so as to be oriented in the direction, is more preferable. Here, M and L may be the same or different from each other, but are preferably the same.

  The size of the hollow shell of the spherical transition metal complex of the present invention is not particularly limited, but the diameter is preferably 3 to 15 nm.

(1) Transition metal atom Although it does not restrict | limit especially as a transition metal atom which comprises the spherical transition metal complex of this invention, Ti, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Cd, Os, Ir And a platinum group atom such as Ru, Rh, Pd, Os, Ir, and Pt is preferable because Ru can be easily formed as a planar four-coordinate complex. , Pd, and Pt are more preferable, and Pd is particularly preferable.
The valence of the transition metal atom is usually 0 to 4, preferably 2. The coordination number is usually 4 to 6, preferably 4.

(2) Bidentate ligand (L)
The bidentate ligand (L) forming the spherical transition metal complex of the present invention has a substituent, and self-organizes with the transition metal atom so that the substituent is oriented inside the hollow shell. Although it will not restrict | limit especially if a spherical transition metal complex can be formed, The compound represented by the formula (I) shown below is preferable. The compound represented by the formula (I) has an acetylene group as a bridge portion adjacent to the pyridyl group, and has a structure having a wide space between the pyridyl groups at both ends while maintaining planarity.

In the formula, R ¹ and R ² each independently represent a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, a cyano group, or a nitro group.
m1 and m2 each independently represents an integer of 0 to 4. m1, m2 is 2 or more, ^{R 1} each other, even ^{R 2} together are each identical or may be different phases.
A represents one type of compounds represented by the following formulas (a-1) to (a-4).

In the formula, R ³ represents a substituent.
The substituent for R ³ is not particularly limited. Specific examples of R ³ include an optionally substituted alkyl group, a formula: — (OCH ₂ CH ₂ ) _s —OR ⁵ , wherein R ⁵ is a hydrogen atom, an optionally substituted alkyl group, An optionally substituted aryl group, an optionally substituted heterocyclic group, a formula: —CO—C (r ₂ ) ═CH ₂ (r ₂ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) A group represented by the formula: — (CH ₂ ) t—R ⁶ —N═N—R ⁷ (t represents an integer of 0 to 10, R ⁶ represents an optionally substituted arylene group, R ⁷ represents an aryl group which may be substituted. s represents the integer of 0-20. ] The group shown by these is mentioned.

R ⁴ represents a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, a cyano group, or a nitro group.
m3 represents an integer of 0 to 3, and m4 represents an integer of 0 to 2. When m3 is 2 or more and m4 is 2, the plurality of R ⁴ may be the same or different.

Examples of the halogen atom for R ¹ , R ² and R ⁴ include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkyl group of the alkyl group which may be substituted for R ¹ , R ² and R ⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-pentyl group, C1-C20 alkyl groups, such as n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, are mentioned.
In addition, examples of the substituent of the alkyl group which may be substituted for R ¹ , R ² and R ⁴ include a halogen atom, an alkoxyl group, and a phenyl group which may have a substituent.

Examples of the alkoxyl group of the alkoxyl group which may be substituted for R ¹ , R ² and R ⁴ include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, t-butoxy group, pentyloxy group, hexyloxy C1-C20 alkoxyl groups, such as group, are mentioned. The substituents of R ^{1, R 2,} optionally substituted alkoxyl group R ^4, a halogen atom, and a phenyl group which may have a substituent.

Q is, -Nr1- (r1 represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group.), - O -, - C (= O) -, - S-, or -SO ₂ - represents a .
Examples of the alkyl group of r1 include a methyl group and an ethyl group, examples of the aryl group include a phenyl group and a p-methylphenyl group, and examples of the acyl group include an acetyl group and a benzoyl group.

  The bidentate ligand (L) used in the present invention is more preferably a compound represented by the following formula (I-1).

In the formula, R ⁸ is an optionally substituted alkyl group, or a formula: — (OCH ₂ CH ₂ ) _s —OR ⁵ [wherein R ⁵ is a hydrogen atom, an optionally substituted alkyl group, An optionally substituted aryl group, an optionally substituted heterocyclic group, a formula: —CO—C (r ₂ ) ═CH ₂ (r ₂ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) A group represented by the formula: — (CH ₂ ) t—R ⁶ —N═N—R ⁷ (t represents an integer of 0 to 10, R ⁶ represents an optionally substituted arylene group, R ⁷ represents an optionally substituted aryl group.), And s represents an integer of 0-20. ] Is represented.

The alkyl group of the alkyl group which may be substituted for R ⁸ is not particularly limited, and examples thereof include an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Can be mentioned. The substituent of the alkyl group is not particularly limited, and examples thereof include an optionally substituted aryl group, halogen atom, alkoxyl group, alkoxycarbonyl group, acyl group, and optionally substituted amino group; carboxyl Group, nitro group, cyano group and the like.

In the group represented by the formula: — (OCH ₂ CH ₂ ) _s —OR ⁵ , the optionally substituted alkyl group of R ⁵ is a specific example of the optionally substituted alkyl group of R ^8. Are similar to those listed.
Examples of the aryl group of the aryl group which may be substituted include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and an anthranyl group.
The heterocyclic group that may be substituted for R ⁵ is not particularly limited, and examples thereof include a furyl group, a thienyl group, a pyrrole group, an imidazolyl group, a thiazolyl group, an oxazoyl group, and a pyridyl group. .
The substituent for the aryl group and heterocyclic group of R ⁵ is not particularly limited, and may be, for example, an optionally substituted aryl group, a halogen atom, an alkoxyl group, an alkoxycarbonyl group, an acyl group, or a substituted group. A good amino group; carboxyl group, nitro group, cyano group and the like.

As the group represented by the formula: —CO—C (r ₂ ) ═CH ₂ , the group represented by the formula: —CO—CH═CH ₂ , the formula: —CO—C (CH ₃ ) ═CH ₂ And the group represented.

In the group represented by the formula: — (CH ₂ ) t—R ⁶ —N═N—R ⁷ , R ⁶ is substituted with a p-phenylene group, an m-phenylene group, a 1,4-naphthalene group, or the like. Represents an arylene group which may be present.
R ⁷ represents an optionally substituted aryl group such as a phenyl group, a 4-methylphenyl group, and a 4-t-butoxyphenyl group.
Moreover, s represents the integer of 0-20, and the integer of 0-5 is preferable.

Preferable specific examples of the compound represented by the formula (I-1) include those in which R ⁸ is represented by the following (Ia) to (Ie), and the bidentate used in the present invention. The ligand (L) is not limited to these.

An example of the spherical transition metal complex of the present invention is shown in FIG. The spherical transition metal complex shown in FIG. 1 is composed of 12 transition metal compounds (M) and 24 bidentate ligands (L).
The spherical transition metal complex shown in FIG. 1 is constructed by self-assembling twelve metal ions and 24 bent bidentate ligands (L), and has a wide space inside. Further, the bidentate ligand (L) has a substituent R, and the substituent R is precisely arranged on the inner surface of the spherical shell.

2) Method for producing spherical transition metal complex The method for producing the spherical transition metal complex of the present invention comprises a transition metal compound (M) and a bidentate ligand (L) with respect to 1 mol of the transition metal compound (M). The bidentate ligand (L) is reacted in a proportion of 1 to 5 mol, preferably 2 to 3 mol.

  The transition metal compound (M) used in the present invention is not particularly limited as long as it can form a spherical transition metal complex with the bidentate ligand (L) in a self-organizing manner, but a divalent transition metal compound is preferable.

  Examples of the transition metal atom constituting the transition metal compound (M) include transition metal atoms such as Ti, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Cd, Os, Ir, and Pt. . Among them, a platinum group atom such as Ru, Rh, Pd, Os, Ir, and Pt is preferable, Ru, Pd, and Pt are more preferable, and Pd is particularly preferable because a planar four-coordinate complex can be easily formed. .

  Specific examples of the transition metal compound (M) include transition metal halides, nitrates, hydrochlorides, sulfates, acetates, methanesulfonates, trifluoromethanesulfonates, p-toluenesulfonates, and the like. It is done. Among these, nitrates and trifluoromethanesulfonates of transition metals are preferred because the desired spherical transition metal complex can be obtained efficiently.

The use ratio of the transition metal compound (M) and the bidentate ligand (L) can be appropriately set according to the composition of the intended spherical transition metal complex. For example, when it is desired to obtain the transition metal complex having the composition of the formula: M ₁₂ L ₂₄ as described above, 2 to 3 mol of the bidentate ligand (L) is added to 1 mol of the transition metal compound (M). What is necessary is just to make it react in a ratio.

The reaction between the transition metal compound (M) and the bidentate ligand (L) can be carried out in a suitable solvent.
Solvents used include nitriles such as acetonitrile; sulfoxides such as dimethyl sulfoxide; amides such as N, N-dimethylformamide; ethers such as diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, 1,4-dioxane Halogenated hydrocarbons such as dichloromethane and chloroform; aliphatic hydrocarbons such as pentane and hexane; aromatic hydrocarbons such as benzene and toluene; alcohols such as methanol, ethanol and isopropyl alcohol; acetone and methyl ethyl ketone Ketones; cellosolves such as ethyl cellosolve; water and the like. These solvents can be used alone or in combination of two or more.

The reaction between the transition metal compound (M) and the bidentate ligand (L) proceeds smoothly in a temperature range from 0 ° C. to the boiling point of the solvent used.
The reaction time is several minutes to several days.
After completion of the reaction, the desired spherical transition metal complex can be isolated by performing usual post-treatments such as filtration, column purification with an ion exchange resin, distillation, recrystallization and the like.

The counter ion of the obtained spherical transition metal complex is usually an anion of the transition metal compound (M) to be used, but the counter ion is used for the purpose of improving crystallinity or improving the stability of the spherical transition metal complex. May be replaced. Examples of such counter ions include PF ₆ ⁻ , ClO ₄ ⁻ , SbF ₄ ⁻ , AsF ₆ ⁻ , BF ₄ ⁻ , SiF ₆ ^{2− and the} like.

The structure of the obtained spherical transition metal complex is known as ¹ H-NMR, ¹³ C-NMR, IR spectrum, mass spectrum, visible light absorption spectrum, UV absorption spectrum, reflection spectrum, X-ray crystal structure analysis, elemental analysis, etc. This can be confirmed by means of analysis.

  As described above, the spherical transition metal complex of the present invention can be efficiently produced by an extremely simple operation. Therefore, mass synthesis on a gram scale is also possible.

The bidentate ligand (L) can be produced by applying a known synthesis method.
For example, among the compounds represented by the formula (I), a compound represented by the following formula (I-2) is prepared by a method known in the literature (K. Sonogashira, Y. Tohda, N. Hagihara, Tetrahedron Lett., 1975, 4467; JF Nguefack, V. Bolitt, D. Sinou, Tetrahedron Lett., 1996, 31, 5527).

In the formula, A, R ¹ and m1 represent the same meaning as described above.
(A-1) represents a compound represented by the formula: X-A-X.
X represents a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom.

That is, the compound represented by the formula (I-2) includes a base, a palladium catalyst such as Pd (PhCN) ₂ Cl ₂ / P (t-Bu) ₃ , Pd (PPh ₃ ) _{4 in} an appropriate solvent, and In the presence of a copper salt such as cuprous iodide, 4-ethynylpyridines (or a salt thereof) represented by the formula (II) are reacted with the compound (A-1) represented by the formula (III). Can be obtained.

  The above reaction is an example in which two 4-ethynylpyridines (or salts thereof) are reacted at once to produce a compound having two identical pyridinylethynyl groups. Compounds having different substituted pyridylethynyl groups can be obtained by reacting the corresponding 4-ethynylpyridines (or salts thereof) stepwise under similar reaction conditions.

  Examples of the base used here include amines such as dimethylamine, diethylamine, diisopropylamine, triethylamine, and diisopropylethylamine.

Examples of the solvent used include ethers such as 1,4-dioxane, diisopropyl ether, tetrahydrofuran, and 1,3-dimethoxyethane; amides such as dimethylformamide; sulfoxides such as dimethyl sulfoxide; nitriles such as acetonitrile; It is done.
The reaction temperature is usually in the temperature range from 0 ° C. to the boiling point of the solvent, preferably 10 ° C. to 70 ° C., and the reaction time is usually several minutes to several tens of hours depending on the reaction scale and the like.

4-Ethynylpyridine (or a salt thereof) can be produced by a known method, but a commercially available product can also be used as it is.
Moreover, the compound represented by Formula (III) can be manufactured by a well-known method.

  The spherical transition metal complex of the present invention has a certain size on the nanometer scale, and a precisely controlled special feature in which the substituent R of the bidentate ligand (L) is oriented inside the spherical structure of the complex. It has a simple structure. That is, since the functional group of the bidentate ligand (L) can be accumulated in the hollow shell of the spherical transition metal complex, the functions and information of small molecules are amplified inside the spherical transition metal complex. It is expected.

  For example, in the spherical transition metal complex of the present invention, when the bidentate ligand (L) is a compound represented by (Ib), the hollow transition metal complex has a Ca inside the hollow shell. A predetermined number of (II) ions, La (III) ions, Eu (III) ions, and Sm (III) ions can be included. In addition, by exchanging the solvent, the inclusion of Ca (II) ions, La (III) ions, Eu (III) ions, Sm (III) ions, and the like can be taken out of the hollow shell again. The number of ions included is usually the same as the number of bidentate ligands (L), that is, the number of alkylene oxide chains.

  Further, in the spherical transition metal complex of the present invention, when the bidentate ligand (L) is a compound represented by the above (Id), the substitution of the bidentate ligand is performed by light irradiation. The internal shape of the hollow shell can be changed by photoisomerizing the nitrogen-nitrogen double bond in the base portion (cis-trans photoisomerization). This indicates the possibility that the spherical transition metal complex of the present invention can be applied as an optical material.

  Furthermore, in the spherical transition metal complex of the present invention, when the bidentate ligand (L) is a compound represented by (Ie), radical polymerization is performed inside the hollow shell of the spherical transition metal complex. The polymerization reaction can be carried out in the presence of an initiator. After completion of the polymerization reaction, an acid can be added to the reaction system to decompose the complex, thereby obtaining a polymer that is a nanoparticle having a uniform particle size. As a similar reaction method, micellar polymerization in which polymerization is carried out inside a micelle is known, but by using the spherical transition metal complex of the present invention, nanoparticles having a much better particle size uniformity than in the case of micelle polymerization Can be obtained.

  As described above, the spherical transition metal complex of the present invention can be expanded to various application fields as a nanometer-scale capsule molecule, as a sensor, a functional material, a drug delivery, a recording medium material, a catalyst, or the like. .

Next, the present invention will be described in more detail by way of examples. In addition, this invention is not limited at all by the Example.
(Equipment)
(1) Measurement of ¹ H-NMR spectrum
^{The 1} H-NMR spectrum was measured by Bruker DRX 500 (500 MHz) NMR spectrometer and JEOL JNM-AL 300 (300 MHz) NMR spectrometer.
When CDCl ₃ or DMSO is used as a solvent, tetramethylsilane (TMS) is used as an internal standard, and when CD ₃ CN is used, a TMS CDCl ₃ solution sealed in a glass capillary is used as an external standard. did.
Chemical shifts were expressed as δ values, and the following abbreviations were used. s (single line), d (double line), t (triple line), br (broad).

(2) Measurement of ¹³ C-NMR spectrum and various two-dimensional NMR spectra
^{The 13} C-NMR spectrum and various two-dimensional NMR spectra were measured using a Bruker DRX 500 (125 MHz) NMR spectrometer.
(3) Measurement of Mass Spectra GC-MS was measured using SHIMADZU GC-CP5050A, and matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOFMAS) was measured with Applied Biosystem Voyager DE-STR.
Cold spray ionization mass spectrometry (CSI-MS) was measured by JEOL JMS-700C.

(Reagents)
As the reaction solvent, a dehydrating solvent for organic synthesis (water content of 0.005% or less) commercially available from Wako Pure Chemical Industries, Ltd. and Kanto Chemical Co., Ltd. was used as it was.
Reagents were used as they were without any purification.
Pd (PPh ₃ ) ₄ used was synthesized by referring to Coulson's literature (DR Coulson, Inorg. Synth., 1972, 13, 121).

Example 1
(1) Synthesis of 2,6-bis (4-pyridylethynyl) toluene

Into a reactor purged with argon, 2,6-dibromotoluene (0.50 g, 2.0 mmol), 4-ethynylpyridine hydrochloride (0.67 g, 4.8 mmol), Pd (PhCN) ₂ Cl ₂ (46 1.0 mg, 0.12 mmol), CuI (15.2 mg, 0.08 mmol), degassed 1,4-dioxane (2 ml) was added, and then tri-t-butylphosphine (0.68 ml, 0.25 mmol). ), Degassed diisopropylamine (0.68 ml, 4.8 mmol) was added, and the mixture was stirred at room temperature for 17 hours. Ethyl acetate (10 ml) was added to the reaction solution and suction filtered to remove insolubles. Subsequently, the filtrate was washed with ethylenediamine (2 ml), and the organic layer was washed 3 times with distilled water, and further washed once with saturated brine. After drying over anhydrous sodium sulfate and filtering, the concentrate obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography (n-hexane: ethyl acetate = 2: 1 (v / v)), and 2, 6-bis (4-pyridylethynyl) toluene was obtained in 81% yield.

(Physical property value)
White powder
¹ H-NMR (DMSO-d ₆ , 500 MHz, δ ppm); 2.69 (s, 3H), 7.37 (t, J = 7.8 Hz, 1H), 7.57 (d, J6.3 Hz 4H), 7.68 (d, J = 7.8 Hz, 2H), 8.65 (d, J = 5.8 Hz, 4H)
¹³ C-NMR (DMSO-d ₆ , 125 MHz, δ ppm); 18.87 (CH ₃ ), 91.03 (Cq), 91.46 (Cq), 121.99 (Cq), 125.99 (CH) , 126.55 (CH), 129.91 (Cq), 133.22 (CH), 142.20 (Cq), 149.97 (CH)
MS (GC-MS); m / z = 294 (M ^<+> )

(2) 2,6-bis (4-pyridylethynyl) toluene (L) and Pd (NO ₃ ) ₂ (M) to M ₁₂ L ₂₄ spherical complex self-assembly

A reactor was charged with 2,6-bis (4-pyridylethynyl) toluene (5.9 mg, 0.020 mmol), Pd (NO ₃ ) ₂ (2.3 mg, 0.010 mmol), and DMSO (1.0 ml). And stirred at 70 ° C. for 12 hours. Ethyl acetate was added to the reaction solution, and the falling precipitate was centrifuged, and then the supernatant was removed and vacuum-dried to obtain a white powdery solid with a yield of 78%.

(Physical property value)
White powder
¹ H-NMR (DMSO-d ₆ , 500 MHz, δ ppm); 2.67 (s, 3H), 7.39 (br, 1H), 7.68 (br, 2H), 7.90 (br, 4H) , 9.24 (br, 4H)
¹³ C-NMR (DMSO-d ₆ , 125 MHz, δ ppm); 18.73 (CH ₃ ), 89.66 (Cq), 95.88 (Cq), 121.16 (Cq), 126.93 (CH) , 128.59 (CH), 134.12 (CH), 134.40 (Cq), 143.82 (Cq), 151.00 (CH)

CSI-MS is a counter anion _CF 3 SO ₃ ^- was measured after replacing the.
^{_{CSI-MS (CF 3 SO 3}} - salt, CD 3 CN: DMSO = 20: 1); 1553.2 [M-7 (CF 3 SO 3 -)] 7+, 1340.3 [M-8 (CF 3 SO ₃ ⁻ )] ⁸⁺ , 1174.8 [M-9 (CF ₃ SO ₃ ⁻ )] ⁹⁺

(Example 2)
(1) Synthesis of 1,3-dibromo-2- [4- (p-cyanophenyl) -1,4-dioxabutyl] benzene

  Into a reactor purged with argon, 1,3-dibromo-2- [2- (p-toluenesulfonyloxy) ethoxy] benzene (0.90 g, 2.0 mmol), 4-cyanophenol (0.28 g, 3 0.0 mmol) and potassium carbonate (0.83 g, 6.0 mmol) were added, N, N-dimethylformamide (50 ml) was added, and the mixture was stirred at 100 ° C. for 24 hours. The reaction solution was returned to room temperature, extracted with chloroform three times, and the organic layer was washed three times with distilled water and further washed once with saturated brine. After drying over anhydrous sodium sulfate and filtering, the concentrate obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography (chloroform: n-hexane = 1: 1 (v / v)), and 1,3- Dibromo-2- [4- (p-cyanophenyl) -1,4-dioxabutyl] benzene was obtained in a yield of 87%.

(Physical property value)
White powder
¹ H-NMR (CDCl ₃ , 300 MHz, δ ppm); 4.32-4.42 (m, 4H), 6.83 (t, J = 8.1 Hz, 1H), 6.95 (d, J = 9) 0.0 Hz, 2H), 7.45 (d, J = 8.1 Hz, 2H), 7.54 (d, J = 9.0 Hz, 2H)
¹³ C-NMR (CDCl ₃ , 75 MHz, δ ppm); 67.18 (CH ₂ ), 70.92 (CH ₂ ), 104.30 (Cq), 115.35 (CH), 118.26 (Cq), 119.13 (Cq), 126.65 (CH), 132.81 (CH), 133.97 (CH), 152.82 (Cq), 161.86 (Cq)
MS (GC-MS); m / z = 395, 397, 399 (M ⁺ )

(2) Synthesis of 2- [4- (p-cyanophenyl) -1,4-dioxabutyl] -1,3-bis (4-pyridylethynyl) benzene

Into a reactor purged with argon, 1,3-dibromo-2- [4- (p-cyanophenyl) -1,4-dioxabutyl] benzene (1.0 g, 2.5 mmol), 4-ethynylpyridine hydrochloride (1.0 g, 7.2 mmol), Pd (PhCN) ₂ Cl ₂ (76.0 mg, 0.20 mmol), CuI (25.9 mg, 0.14 mmol), and degassed 1,4-dioxane (9 ml) ), Tri-t-butylphosphine (0.120 ml, 0.48 mmol) and degassed diisopropylamine (0.68 ml, 4.8 mmol) were added, and the mixture was stirred at 50 ° C. for 40 hours. Ethyl acetate (20 ml) was added to the reaction solution, suction filtered to remove insoluble matters, the filtrate was washed with ethylenediamine (4 ml), the organic layer was washed 3 times with distilled water, and further washed once with saturated brine. did. After drying over anhydrous sodium sulfate and filtering, the concentrate obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography (chloroform: methanol = 50: 1 (v / v)) and GPC, and 2- [4 -(P-Cyanophenyl) -1,4-dioxabutyl] -1,3-bis (4-pyridylethynyl) benzene was obtained in a yield of 92%.

(Physical property value)
White powder
¹ H-NMR (DMSO-d ₆ , 500 MHz, δ ppm); 4.47-4.49 (m, 2H), 4.71-4.73 (m, 2H), 6.70 (d, J = 9) 0.0 Hz, 1H), 7.29 (t, J = 7.5 Hz, 1H), 7.42 (d, J = 6.0 Hz, 4H), 7.65 (d, J = 8.5 Hz, 1H) 7.70 (d, J = 8.0 Hz, 2H), 8.59 (d, J = 5.5 Hz, 4H)
¹³ C-NMR (DMSO-d ₆ , 125 MHz, δ ppm); 68.24, 72.73, 89.08, 91.25, 102.92, 115.42, 116.03, 118.98, 124.47 , 125.10, 129.77, 134.05, 134.88, 149.84, 161.14, 161.72.
MS (MALDI-TOFMAS); m / z = 442.0 ([M + H] ⁺ )

(3) 2- [4- (p-cyanophenyl) -1,4-dioxabutyl] -1,3-bis (4-pyridylethynyl) benzene (L) and Pd (NO ₃ ) ₂ (M) to M ₁₂ self-assembly of L ₂₄ spherical complex

2- [4- (p-cyanophenyl) -1,4-dioxabutyl] -1,3-bis (4-pyridylethynyl) benzene (8.8 mg, 0.020 mmol), Pd (NO ₃ ) ₂ (2. DMSO (1.0 ml) was added to 3 mg, 0.010 mmol), and the mixture was stirred at 70 ° C. for 12 hours. Ethyl acetate was added to the reaction solution, and the falling precipitate was centrifuged, and then the supernatant was removed and vacuum dried to obtain a white powdery solid in a yield of 87%.

(Physical property value)
White powder
¹ H-NMR (DMSO-d ₆ , 500 MHz, δ ppm); 4.43 (br, 2H), 4.70 (br, 2H), 6.94 (d, J = 8.0 Hz, 1H), 7. 29 (br, 1H), 7.44 (d, J = 8.0 Hz, 1H), 7.68 (br, 2H), 7.75 (br, 4H), 9.23 (br, 4H)
¹³ C-NMR (DMSO-d ₆ , 500 MHz, δ ppm); 69.42, 74.21, 90.94, 94.89, 103.84, 116.21, 116.59, 120.03, 125.77. 129, 47, 134.87, 135.13, 137.12, 151.98, 162.64, 163.33.

CSI-MS is a counteranion _CF 3 SO ₃ ^- was measured after replacing the. ^{_{CSI-MS (CF 3 SO 3}} - salt, CD 3 CN: DMSO = 20: 1); 1781.1 [M-8 (CF 3 SO 3 -)] 8+, 1575.3 [M-9 (CF 3 SO ₃ ⁻ )] ⁹⁺ , 1410.7 [M-10 (CF ₃ SO ₃ ⁻ )] ¹⁰⁺

(Example 3)
(1) Synthesis of 1,3-dibromo-2- (12-tosyloxy-1,4,7,10-tetraoxadodecyl) benzene

  Into a reactor purged with argon, 2,6-dibromophenol (2.6 g, 10.4 mmol), tetraethylene glycol di-p-toluenesulfonate (9.4 g, 18.6 mmol), potassium carbonate (5.6 g, 41.6 mmol) was added, acetone (80 ml) was added, and the mixture was stirred at 55 ° C. for 24 hours. The reaction solution was returned to room temperature, extracted three times with chloroform, and the organic layer was washed three times with distilled water and further washed once with saturated brine. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography (chloroform) to obtain 1,3-dibromo-2- (12-tosyloxy-1,4,7 , 10-tetraoxadodecyl) benzene was obtained in 68% yield.

(Physical property value)
Colorless liquid substance
¹ H-NMR (CDCl ₃ , 500 MHz, δ ppm); 2.44 (s, 3H), 3.58-3.60 (m, 4H), 3.64-3.67 (m, 2H), 3. 68-3.71 (m, 2H), 3.74-3.77 (m, 2H), 3.91-3.94 (m, 2H), 4.16 (m, J = 5.0 Hz, 2H ), 4.19 (t, J = 4.9 Hz, 2H), 6.86 (t, J = 7.9 Hz, 1H), 7.33 (d, J = 8.1 Hz, 2H), 7.50 (D, J = 8.1 Hz, 2H), 7.80 (d, J = 8.2 Hz, 2H)
_{^{13 C-NMR (CDCl 3,}} 75MHz, δppm); 21.62 (CH 3), 68.66 (CH 2), 69.22 (CH 2), 70.10 (CH 2), 70.59 (CH _{2), 70.69 (CH 2)} , 70.75 (CH 2), 70.80 (CH 2), 72.37 (CH 2), 118.38 (Cq), 126.28 (CH), 127 97 (CH), 129.79 (CH), 132.71 (CH), 133.01 (Cq), 144.75 (Cq), 153.27 (Cq)
MS (MALDI-TOFMAS); m / z = 602.9, 604.9, 606.9 ([M + Na] ⁺ ), 618.8, 620.8, 622.8 ([M + K] ⁺ )

(2) Synthesis of 1,3-dibromo-2- (1,4,7,10,13-pentaoxatetradecyl) benzene

  Into a reactor purged with argon, 1,3-dibromo-2- (12-tosyloxy-1,4,7,10-tetraoxadodecyl) benzene (0.80 g, 1.4 mmol), sodium hydroxide (1 0.1 g, 27.0 mmol) was added, acetone (80 ml) was added, and the mixture was stirred at 90 ° C. for 24 hours. The reaction solution was returned to room temperature, extracted with chloroform three times, and the organic layer was washed three times with distilled water and further washed once with saturated brine. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain 1,3-dibromo-2- (1,4,7,10,13-pentaoxatetradecyl) benzene in a yield of 97%.

(Physical property value)
Colorless liquid substance
¹ H-NMR (CDCl ₃ , 500 MHz, δ ppm); 3.38 (s, 3H), 3.54-3.57 (m, 2H), 3.64-3.68 (m, 4H), 3. 68-3.72 (m, 4H), 3.76-3.79 (m, 2H), 3.94 (t, J = 5.1 Hz, 2H), 4.20 (t, J = 5.0 Hz) , 2H), 6.86 (t, J = 8.1 Hz, 1H), 7.50 (d, J = 8.1 Hz, 2H),
_{^{13 C-NMR (CDCl 3,}} 75MHz, δppm); 59.02 (CH 3), 70.08 (CH 2), 70.50 (CH 2), 70.62 (CH 2), 70.65 (CH ₂ ), 70.67 (CH ₂ ), 70.81 (CH ₂ ), 71.93 (CH ₂ ), 72.37 (CH ₂ ), 118.39 (Cq), 126.25 (CH), 132 .69 (CH), 153.29 (Cq)

(3) Synthesis of 2- (1,4,7,10,13-pentaoxatetradecyl) -1,3-bis (4-pyridylethynyl) benzene

Into a reactor purged with argon, 1,3-dibromo-2- (1,4,7,10,13-pentaoxatetradecyl) benzene (0.54 g, 1.2 mmol), 4-ethynylpyridine hydrochloride (0.48 g, 3.4 mmol), Pd (PhCN) ₂ Cl ₂ (28 mg, 0.074 mmol), CuI (9.35 mg, 0.049 mmol), and degassed 1,4-dioxane (2.5 ml) ), Tri-t-butylphosphine (38 μl, 0.15 mmol) and degassed diisopropylamine (1.5 ml, 10.6 mmol) were added, and the mixture was stirred at 50 ° C. for 24 hours. Ethyl acetate (10 ml) was added to the reaction solution and suction filtered to remove insoluble matters. The filtrate was washed with ethylenediamine (2 ml), the organic layer was washed 3 times with distilled water, and once with saturated brine. Washed. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography (chloroform: methanol = 50: 1 (v / v)) and GPC to give 2- (1, 4,7,10,13-pentaoxatetradecyl) -1,3-bis (4-pyridylethynyl) benzene was obtained in a yield of 81%.

(Physical property value)
Colorless liquid substance
¹ H-NMR (CD ₃ CN, 500 MHz, δ ppm); 4.10 (s, 3H), 4.25-4.28 (m, 2H), 4.32-4.37 (m, 8H), 4 .46-4.49 (m, 2H), 4.72-4.75 (m, 2H), 5.31-5.34 (m, 2H), 8.05 (t, J = 7.9 Hz, 1H), 8.33 (d, J = 6.2 Hz, 4H), 8.46 (d, J = 7.6 Hz, 2H), 9.47 (d, J = 5.8 Hz, 4H)
¹³ C-NMR (CD ₃ CN, 125 MHz, δ ppm); 58.71 (CH ₃ ), 70.83 (CH ₂ ), 70.96 (CH ₂ ), 70.97 (CH ₂ ), 71.05 ( _{CH 2), 71.24 (CH 2} ), 71.38 (CH 2), 72.44 (CH 2), 74.72 (CH 2), 89.96 (Cq), 92.00 (Cq), 117.55 (CH), 125.00 (CH), 126.14 (CH), 131.47 (CH), 135.59 (CH), 150.88 (CH), 162.50 (CH)

¹ H-NMR (DMSO-d ₆ , 500 MHz, δ ppm) 3.20 (s, 3H), 3.37-3.40 (m, 2H), 3.43-3.45 (m, 4H), 3 .45-3.48 (m, 4H), 3.57-3.61 (m, 2H), 3.84-3.87 (m, 2H), 4.43-4.46 (m, 2H) 7.26 (t, J = 7.9 Hz, 1H), 7.55 (d, J = 5.8 Hz, 4H), 7.70 (d, J = 7.7 Hz, 2H), 8.66 ( d, J = 6.0 Hz, 4H)
¹³ C-NMR (DMSO-d ₆ , 125 MHz, δ ppm); 57.91 (CH ₃ ), 69.45 (CH ₂ ), 69.64 (CH ₂ ), 69.65 (CH ₂ ), 69.69 _{(CH 2), 69.85 (CH} 2), 69.99 (CH 2), 71.14 (CH 2), 73.58 (CH 2), 89.15 (Cq), 91.13 (Cq) 115.96 (CH), 124.24 (CH), 125.14 (CH), 129.89 (CH), 134.70 (CH), 149.94 (CH), 161.20 (CH)
MS (LC-MS); m / z = 487.0 ([M + H] ⁺ )

(4) From 2- (1,4,7,10,13-pentaoxatetradecyl) -1,3-bis (4-pyridylethynyl) benzene (L) and Pd (CF ₃ SO ₃ ) ₂ (M) Self-assembly of M ₁₂ L ₂₄ spherical complex in CH ₃ CN

The reactor was charged with 2- (1,4,7,10,13-pentaoxatetradecyl) -1,3-bis (4-pyridylethynyl) benzene (9.7 mg, 0.020 mmol), Pd (CF ₃ SO ₃ ) ₂ (4.0 mg, 0.010 mmol) was added, and CH ₃ CN (1 ml) was added thereto, followed by stirring at 50 ° C. for 12 hours. After distilling off the solvent under reduced pressure, the solid was washed with diethyl ether, the precipitate was centrifuged, the supernatant was removed, and vacuum drying was performed to obtain a white powdery solid with a yield of 90%. This transition metal complex is designated as complex (1a).

(Physical property value)
White powder
¹ H-NMR (CD ₃ CN, 500 MHz, δ ppm); 3.94 (s, 3H), 4.07-4.10 (m, 2H), 4.17-4.20 (m, 2H), 4 21-4.24 (m, 2H), 4.27-4.30 (m, 2H), 4.35-4.38 (m, 2H), 4.45-4.48 (m, 2H) , 4.69-4.72 (m, 2H), 5.24-5.27 (m, 2H), 8.04 (t, J = 7.7 Hz, 1H), 8.47 (d, J = 7.8 Hz, 2H), 8.52 (d, J = 6.8 Hz, 4H), 9.87 (d, J = 6.7 Hz, 4H)

¹³ C-NMR (CD ₃ CN, 125 MHz, δ ppm); 58.68 (CH ₃ ), 70.75 (CH ₂ ), 70.92 (CH ₂ ), 70.94 (CH ₂ ), 71.00 ( _{CH 2), 71.21 (CH 2} ), 71.37 (CH 2), 72.34 (CH 2), 75.14 (CH 2), 90.50 (Cq), 95.36 (Cq), 116.63 (Cq), 125.8 (CH), 129.61 (CH), 136.36 (Cq), 137.00 (CH), 151.87 (CH), 163.58 (Cq)

^{_{CSI-MS (CF 3 SO 3}} - salt, CD 3 CN); 1916.8 [M-8 (CF 3 SO 3 -)] 8+, 1687.4 [M-9 (CF 3 SO 3 -)] 9+, _{1503.6 [M-10 (CF 3} SO 3 -)] 10+

(5) 2- (1,4,7,10,13-pentaoxatetradecyl) -1,3-bis (4-pyridylethynyl) benzene (L) and Pd (NO ₃ ) ₂ (M) to M ₁₂ self-assembly in DMSO of L ₂₄ spherical complex

2- (1,4,7,10,13-pentaoxatetradecyl) -1,3-bis (4-pyridylethynyl) benzene (9.7 mg, 0.020 mmol), Pd (NO ₃ ) _{2 was} added to the reactor. (2.3 mg, 0.010 mmol) was added, DMSO (1 ml) was added thereto, and the mixture was stirred at 70 ° C. for 12 hours. Ethyl acetate was added to the reaction solution, and the falling precipitate was centrifuged, and then the supernatant was removed and vacuum dried to obtain a white powdery solid with a yield of 91%.

(Physical property value)
White powder
¹ H-NMR (DMSO-d ₆ , 500 MHz, δ ppm); 3.06 (s, 3H), 3.20-3.24 (m, 2H), 3.29-3.35 (m, 4H), 3.35-3.39 (m, 2H), 3.43-3.47 (m, 2H), 3.54-3.58 (m, 2H), 3.83 (br, 2H), 4. 41 (br, 2H), 7.26 (br, 1H), 7.68 (br, 2H), 7.85 (br, 4H), 9.27 (br, 4H)
¹³ C-NMR (DMSO-d ₆ , 125 MHz, δ ppm); 57.84 (CH ₃ ), 69.41 (CH ₂ ), 69.62 (CH ₂ ), 69.63 (CH ₂ ), 69.67 _{(CH 2), 69.80 (CH} 2), 70.05 (CH 2), 71.08 (CH 2), 73.96 (CH 2), 89.83 (Cq), 93.91 (Cq) 115.15 (Cq), 124.57 (CH), 128.49 (CH), 134.23 (Cq), 136.02 (CH), 151.04 (CH), 162.26 (Cq)

CSI-MS is a counter anion _CF 3 SO ₃ ^- was measured after replacing the. ^{_{CSI-MS (CF 3 SO 3}} - salt, CD 3 CN: DMSO = 20: 1); 1916.6 [M-8 (CF 3 SO 3 -)] 8+, 1687.3 [M-9 (CF 3 SO ₃ ⁻ )] ⁹⁺ , 1503.6 [M-10 (CF ₃ SO ₃ ⁻ )] ¹⁰⁺

(Inclusion behavior of metal ions)
Next, 12 equivalents of various metal ions were added to the acetonitrile solution (0.1 mM) of the spherical transition metal complex (1a) synthesized in (4) of Example 3 above, and ethylene was used using ¹ H-NMR. The interaction between glycol chains and metal ions was investigated. CF ₃ SO ₃ ^— was used as the counter anion of the metal ion.

As a result, when Ca (II) ions and various lanthanoid ions were added, ¹ H of the ethylene glycol chain was observed with a large shift. On the other hand, ¹ H-NMR chemical shifts of the pyridine ring and benzene ring of the skeleton hardly changed. Moreover, although these metal ions were also added to the complex having no ethylene glycol chain, no signal shift was observed.

In acetonitrile spherical transition metal complex (1a), Ca (II) , shown La (III), Sm (III ), the change in the spectrum of ¹ H-NMR in the case of added Eu (III) ions in FIG. 2 .

In FIG. 2, a) is a ¹ H-NMR spectrum diagram of an acetonitrile solution of a spherical transition metal complex (1a), and b) is a spherical transition metal complex (1a) added to an acetonitrile solution of the spherical transition metal complex (1a). 12 is a ¹ H-NMR spectrum diagram after adding 12 equivalents of Ca (CF ₃ SO ₃ ) ₂ to the mixture and stirring for 5 hours, and c) shows a spherical transition to an acetonitrile solution of the spherical transition metal complex (1a). metal complex (1a) relative to the addition of 12 equivalents of _{La (CF 3 SO 3) 3} , a ¹ H-NMR spectrum of after stirring for 5 hours, d) is acetonitrile spherical transition metal complex (1a) solution, spherical transition metal complex (1a) relative to 12 equivalents of _Sm (CF _{3 SO 3)} 3 was added, and the ¹ H-NMR spectrum diagram of after stirring for 5 hours, e) the spherical transition metal complex (1 in acetonitrile a), spherical transition metal complex (1a) relative to the addition of 12 equivalents of _{Eu (CF 3 SO 3) 3} , is a ¹ H-NMR spectrum diagram of After stirring for 5 hours.

From the above, the ¹ H-NMR shift of the ethylene glycol chain strongly suggests that metal ion coordination to the ethylene glycol chain occurs.
Thus, the uptake of metal ions in acetonitrile was confirmed because the coordination of the solvent was not so strong, and ether oxygen, which is a hard donor, preferentially coordinated to the lanthanoid ions. It is thought that.

  Furthermore, in order to estimate the ratio of the spherical transition metal complex (1a) having 24 ethylene glycol chains interacting with the lanthanoid ion, we examined it by job's plot (supervised by Yukito Murakami (supervised) ), Supramolecular chemistry basics and applications, NTS, 1995). As a result, it was found that ethylene glycol chains and guest La (III) ions formed a complex at a ratio of 1: 1. That is, it was shown that 24 La (III) ions accumulate per molecule of the spherical complex.

In this way, by introducing 24 ethylene glycol chains into the inner surface of the M ₁₂ L ₂₄ spherical complex, the environment inside the complex can be changed, and a driving force for taking in metal ions is born. Inclusion is now possible. It was also found that the number of guests included was determined to be 24, which was uniquely determined.

  Next, since it was found that metal ions could be taken into the hollow space of the spherical transition metal complex, an attempt was made to take out the taken-in guest again.

To a sample in which 12 equivalents of La (III) ion and Eu (III) ion are added to 0.6 ml of an acetonitrile solution (0.1 mM) of spherical transition metal complex (1a) and 0.6 ml and stirred for 5 hours, 0.6 ml of DMSO is added. In addition, as shown in FIG. 3, it was observed that each signal returned sharply in ¹ H-NMR.

In FIG. 3, a) shows a case where 12 equivalents of La (CF ₃ SO ₃ ) ₃ is added to the spherical transition metal complex (1a) in an acetonitrile solution of the spherical transition metal complex (1a) and stirred for 5 hours. a ¹ H-NMR spectrum diagram, b) is a ¹ H-NMR spectrum view after the DMSO-d6 was added 0.6ml solution of a), c) are spherical transition metal complex (1a) in acetonitrile solution, spherical transition metal complex (1a) relative to the addition of 12 equivalents of _{Eu (CF 3 SO 3) 3} , a ¹ H-NMR spectrum of after stirring for 5 hours, d) is, c) of it is a ¹ H-NMR spectrum view after the DMSO-d6 was added 0.6ml solution.

  From FIG. 3, since the position of each signal of the spherical transition metal complex (1a) appears at the same position as the case where La (III) ion and Eu (III) ion do not exist, the ethylene glycol chain and the metal ion This indicates that the interaction disappeared.

This was considered to be because DMSO strongly coordinated to metal ions instead of ethylene glycol by adding DMSO having strong coordination ability to metal ions.
By adding DMSO, it can be said that the lanthanoid ions stored inside the complex could be extracted.

  As described above, by constructing the spherical transition metal complex (1a) in acetonitrile, it becomes possible to incorporate Ca (II) ions and various lanthanoid ions into the spherical complex, and the number is uniquely 24. It was found that the number was large. Furthermore, by adding DMSO to this solution, the metal ions included inside were successfully extracted. That is, by introducing a substituent, it became possible to store and release metal ions in a complex molecule whose structure was clearly controlled.

_CF 3 SO ₃ salt of lanthanide ions have been found to act as a catalyst such as an asymmetric Diels-Alder reaction or an aldol reaction (L.Trembleau, J.RebekJr, Chem.Commun., Etc. 2004,58) The inclusion of lanthanoid ions in a space defined by the size and structure of the M ₁₂ L ₂₄ spherical complex is expected to be applied as a catalyst capable of substrate selectivity and stereocontrol.

According to the technique of modifying the inner surface of the spherical complex established by the present invention with a substituent, it is considered that various substituents can be introduced depending on the purpose. Spherical transition metal complexes are very simple because they are spontaneously formed, and their structures are clearly defined, so it is a very useful technique for creating a precisely controlled and unique internal space. I can say that.
In the future, by designing substituents to be introduced into the inner surface of the spherical complex, it is possible to expect new functions due to the cooperative action of substituents to be introduced into the inner surface of the spherical shell structure, similar to biological systems. Such biomolecules can be expected to be included and stabilized, selective recognition of polypeptides and control of secondary structure, and use as a specific reaction field using such a huge space.

It is a figure which shows the three-dimensional structure of the spherical transition metal complex of this invention comprised from 12 transition metal compounds (M) and 24 bidentate ligands (L). In acetonitrile spherical transition metal complex (1a), Ca (II) , La (III), Sm (III), is a diagram illustrating a change in the spectrum of ¹ H-NMR in the case of added Eu (III) ions . The figure which shows the change of the spectrum of ¹ H-NMR when DMSO-d6 is added after adding La (III) and Eu (III) ion to the acetonitrile solution of the spherical transition metal complex (1a) and stirring for 5 hours. is there.

Claims (11)

  A spherical transition metal complex having a hollow shell, wherein the hollow shell has n1 transition metal atoms (n1 represents an integer of 6 to 60) and 2n1 bidentate having a substituent. A spherical transition metal complex formed of an organic ligand and formed so that the substituent is oriented inside the hollow shell.   A spherical transition metal complex having a hollow shell, wherein the hollow shell has n2 (n2 is 6, 12, 24, 30 or 60) transition metal atoms and 2n2 substituents. And a bidentate organic ligand, wherein the substituent is oriented in the hollow shell. From the transition metal compound (M) and the bidentate organic ligand (L) having a substituent, the substituent is formed in a self-organizing manner so that the substituent is oriented inside the hollow shell. The formula: M _n1 L The spherical transition metal complex according to claim 1, which is represented by _2n1 (n1 is an integer of 6 to 60, and _Ms and Ls may be the same or different from each other). From the transition metal compound (M) and the bidentate organic ligand (L) having a substituent, the substituent is formed in a self-organized manner so that the substituent is oriented inside the hollow shell. The formula: M _n2 L The spherical shape according to claim 2, represented by _2n2 (n2 is 6, 12, 24, 30 or 60, and M and L may be the same or different from each other). Transition metal complex.   The spherical transition metal complex according to claim 1, which has a hollow shell having a diameter of 3 to 15 nm.   The transition metal atom constituting the transition metal complex is a kind selected from the group consisting of Ti, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Cd, Os, Ir, and Pt. The spherical transition metal complex according to any one of claims 1 to 5. The bidentate organic ligand is of the formula (I)

{Wherein, R ¹ and R ² each independently represent a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, a cyano group, or a nitro group.
m1 and m2 each independently represents an integer of 0 to 4. m1, m2 is 2 or more, ^{R 1} each other, even ^{R 2} together are each identical or may be different phases.
A represents the following formulas (a-1) to (a-4)

[R ³ represents a substituent.
R ⁴ represents a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, a cyano group or a nitro group.
m3 represents an integer of 0 to 3, and m4 represents an integer of 0 to 2. m3 is 2 or more, when m4 is 2, even a plurality of R ⁴ may be the same or may be different from each other.
Q is, -Nr1-, (r1 represents a hydrogen atom, an alkyl group, an aryl group or an acyl group.) - O -, - C (= O) -, - S-, or -SO ₂ - represents a. ] Is represented. } The spherical transition metal complex according to claim 1, wherein the spherical transition metal complex is a kind of a compound represented by R ³ is an optionally substituted alkyl group, or a formula: — (OCH ₂ CH ₂ ) _s —OR ⁵ wherein R ⁵ is a hydrogen atom, an optionally substituted alkyl group, or a substituted group. An aryl group which may be substituted, a heterocyclic group which may be substituted, and a formula: —CO—C (r2) ═CH ₂ (r2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms). Group represented by the formula: — (CH ₂ ) t—R ⁶ —N═N—R ⁷ (t represents an integer of 0 to 10, R ⁶ represents an optionally substituted arylene group, and R ⁷ represents Represents an optionally substituted aryl group.), And s represents an integer of 0 to 20. The spherical transition metal complex according to claim 7, which is a group represented by the formula: The bidentate organic ligand is represented by the formula (I-1)

{Wherein R ⁸ is an optionally substituted alkyl group, or a formula: — (OCH ₂ CH ₂ ) _s —OR ⁵ [wherein R ⁵ is a hydrogen atom, an optionally substituted alkyl group. , An optionally substituted aryl group, an optionally substituted heterocyclic group, a formula: —CO—C (r ₂ ) ═CH ₂ (r ₂ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ) Group represented by the formula: — (CH ₂ ) t—R ⁶ —N═N—R ⁷ (t represents an integer of 0 to 10, R ⁶ represents an optionally substituted arylene group, R ⁷ represents an optionally substituted aryl group.), And s represents an integer of 0-20. ] Is represented. } The spherical transition metal complex according to claim 1, wherein the spherical transition metal complex is a compound represented by the formula:   The ratio of the transition metal compound (M) and the bidentate organic ligand (L) having a substituent is 1 to 5 moles of the bidentate organic ligand (L) with respect to 1 mole of the transition metal compound (M). The method for producing a spherical transition metal complex according to claim 1, wherein the reaction is performed using The transition metal atom constituting the transition metal compound is a kind selected from the group consisting of Ti, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Cd, Os, Ir, and Pt. The method for producing a spherical transition metal complex according to claim 10.

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