JP2006188560A - High molecular complex - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a high molecular complex having ≥2 species pore groups selectively carrying out uptake and/or release of a specific compound ranging a small gaseous molecule to a large molecule such as a protein, a living body-originated molecule and the like. <P>SOLUTION: The high molecular complex has a three dimensional lattice structure comprising at least an aromatic compound as a ligand and a metal ion as a central metal and ≥2 species pore groups comprising mutually equal pores having proper affinity to a guest component in the three dimensional lattice structure. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polymer complex.

  A specific organic compound can be selectively taken out by passing or contacting a mixture containing many kinds of organic compounds with a material having a pore structure that takes in a guest compound. As such materials, organometallic complexes in which organic ligands are assembled with transition metals, zeolites, and the like are known, and they have many uses such as selective reversible adsorbents and catalyst carriers.

  However, the pore environment (intrapore environment) contained in the structure of zeolite or the like is uniform, and it is difficult to make relatively large pores having different environments coexist in a single zeolite material. Therefore, conventionally, it is difficult to coexist two or more kinds of pores capable of selectively taking in a compound having a relatively large molecular size such as an organic compound in a single material having an action of taking in a guest compound. there were.

  The present invention has been achieved in view of the above circumstances, and its purpose is to selectively take in specific compounds from gaseous small molecules to large molecules such as proteins and other biologically derived molecules and Another object is to provide a polymer complex having two or more kinds of pore groups that can be released.

  The polymer complex provided by the present invention is a polymer complex having a three-dimensional lattice structure composed of at least an aromatic compound as a ligand and a metal ion as a central metal, Further, it is characterized in that it has two or more kinds of pore groups each having the same fine pores having a specific affinity for the guest component.

The pore group formed in the polymer complex of the present invention is composed of a plurality of identical pores having inherent affinity. Therefore, when the polymer complex of the present invention comes into contact with a mixture containing two or more kinds of components, among the plurality of components contained in the contacted mixture, a component having an affinity for the pores constituting the pore group, It is selectively taken into the pores. Since two or more types of pore groups are present in the polymer complex, two or more types of guest components can be incorporated in the polymer complex as a whole. Moreover, two or more guest components incorporated into one polymer complex are present in the polymer complex in a state of being separated in each pore group. It is also possible to selectively release the guest component taken into the pores.
Furthermore, the polymer complex of the present invention can be changed from a gaseous small molecule to a protein or other biological molecule by appropriately adjusting the size of the pores contained in the pore group formed in the polymer complex. Even large molecules can be taken into the pores. That is, it is possible to selectively take in a specific compound for each pore group from a mixture containing two or more kinds of small molecule to large molecule compounds.
Accordingly, the polymer complex of the present invention separates two or more components from the mixture and selectively stores the components stored in the separated state, transported in the separated state, or occluded in the polymer complex. Can be released.

As one form of the polymer complex of the present invention, an aromatic compound as a ligand having two or more coordination sites, a metal ion as a central metal, and a non-coordinating aromatic compound are included. A non-coordinating aromatic compound between the aromatic compound ligands in a three-dimensional network structure formed by coordination of the aromatic compound ligands to the central metal ion. Has a three-dimensional lattice structure including a stacked structure in which 2 is inserted, and in the three-dimensional lattice structure, two pore groups each having the same pore having a specific affinity for a guest component are formed. The thing with more than a seed is mentioned.
The form of the three-dimensional network structure includes a composite three-dimensional network structure formed by combining two or more independent three-dimensional networks. Examples of the composite three-dimensional network structure include an interpenetrating structure in which independent three-dimensional network structures are intertwined in a complicated manner.

The affinity of the pores constituting the pore group with respect to the guest component is the contrast between two pore groups arbitrarily selected from the two or more pore groups, the pore size, the pore shape, And when at least one of the atmospheres in the pores is different, they are different from each other.
For example, in the comparison between two pore groups arbitrarily selected from the two or more pore groups, the occupation ratio between the region where the π plane of the inner wall of the pore is exposed and the region where the hydrogen atom is exposed Are different, the atmosphere in the pores of the pores constituting the pore group is different.

  When the three-dimensional network structure has a sufficient three-dimensional extent and the stacked structure is formed by sufficiently stacking aromatic ligands and non-coordinating aromatic compounds, elongated channel-shaped pores Is formed.

The size of the pores contained in the pore group selected from the two or more kinds of pore groups may be appropriately designed depending on the component to be selectively taken in and / or released. The diameter of the inscribed circle of the pores in a plane parallel to the crystal plane that is closest to the direction perpendicular to the extending direction can be 2 to 70 mm.
Similarly, the inscribed ellipse of the pore in a plane parallel to the crystal plane closest to the direction in which the pores included in the pore group selected from the two or more kinds of pore groups extend. The major axis can be 5 to 70 mm, and the minor axis of the inscribed ellipse can be 2 to 50 mm.

  Specific examples of the aromatic compound ligand include aromatic compounds represented by the following formula (1).

(In the formula, Ar is a structure having an aromatic ring. X is a divalent organic group or a single bond directly connecting Ar and Y. Y is a coordination atom or an atom containing a coordination atom. N represents a number of 3 to 6. A plurality of X contained in one molecule may be different from each other, and a plurality of Y may be different from each other.

  Moreover, a condensed polycyclic aromatic compound is mentioned as a specific example of the said non-coordinating aromatic compound.

  More specifically, the aromatic compound represented by the formula (1) is tris (4-pyridyl) triazine, and the condensed polycyclic aromatic compound is at least one of triphenylene or perylene. A complex. In this form of the polymer complex, the pores in the plane parallel to the crystal plane closest to the perpendicular to the extending direction of the pores contained in the pore group selected from the two or more kinds of pore groups Specifically, the inscribed circle has a diameter of 4.5 to 7.0 mm. In addition, the major axis of the inscribed ellipse of the pore in a plane parallel to the crystal plane closest to the perpendicular to the direction in which the pore included in the pore group selected from the two or more kinds of pore groups extends Is 8.5 to 10.0 mm, and the minor axis of the inscribed ellipse is 6.0 to 8.0 mm. When the pores have a relatively large size as described above, a guest component having a relatively large molecular size such as an organic compound can be incorporated.

  According to the present invention, one or more types, that is, two or more guest components as a whole of the polymer complex can be selectively incorporated into two or more types of pore groups contained in one polymer complex. . Therefore, it is possible to separate two or more specific components from a mixture containing two or more compounds and store them in the polymer complex, or to transport two or more components simultaneously. It is also possible to selectively release the incorporated components. Furthermore, two or more guest components incorporated into the pore group of the polymer complex are usually coexisting when they are sufficiently separated from each other by the rigid main skeleton constituting the three-dimensional lattice structure. Even if it is a combination of two or more components that cannot be performed, such as an acid and a base, an oxidizing agent and a reducing agent, etc., each component can be stored in a stable state in one polymer complex, It can be transported separately.

  The polymer complex of the present invention is a polymer complex having a three-dimensional lattice structure composed of at least an aromatic compound as a ligand and a metal ion as a central metal. It is characterized by having two or more kinds of fine pore groups each having the same fine pores having a specific affinity for the component.

  As one embodiment of the polymer complex of the present invention, an aromatic compound as a ligand having two or more coordination sites, a metal ion as a central metal, and a non-coordinating aromatic compound A non-coordinating aromatic compound between the aromatic compound ligands in a three-dimensional network structure formed by coordination of the aromatic compound ligands to the central metal ion. Has a three-dimensional lattice structure including a stacked structure in which 2 is inserted, and in the three-dimensional lattice structure, two pore groups each having the same pore having a specific affinity for a guest component are formed. A polymer complex having more than one species can be given. Hereinafter, the polymer complex of the present invention will be described using the polymer complex as an example.

  In the polymer complex of the present invention, a three-dimensional network structure is formed by a coordinate bond between an aromatic compound ligand and a central metal ion, and between the aromatic compound ligands forming the three-dimensional network structure. And a three-dimensional lattice structure including a stacked structure in which non-coordinating aromatic compounds that do not contribute to coordination bonds are inserted. In this way, it is formed by the three-dimensional network structure by the coordination bond of the aromatic compound ligand and the central metal ion, and the non-coordinating aromatic compound and the aromatic compound ligand incorporated in the three-dimensional network structure. Depending on the stacked structure, two or more kinds of pores having a specific affinity for the guest component in the polymer complex (that is, having a specific molecular inclusion function) are each provided in a plurality (ie, pores). Group) is thought to be formed.

Two or more kinds of pore groups provided in the polymer complex of the present invention are composed of pores having a specific affinity for the guest component, and different guest components are selected for each pore group based on this specific affinity. Can be captured automatically. That is, in the polymer complex of the present invention, one or more types, that is, two or more guest components as a whole of the polymer complex are selectively contained in two or more types of pore groups contained in one polymer complex. Can be captured. It is also possible to selectively release the guest component taken into the pores. Here, the selective incorporation of guest components into the pores and the selective release from the pores refers to the incorporation of specific components into the pores depending on the atmosphere in the pores, the size and shape of the pores, etc. In addition to the release, the temperature and atmosphere of the guest exchange, and further, the selection of the guest component taken into the pore and / or the guest component released from the pore depending on the time are included.
Furthermore, the polymer complex of the present invention can be changed from a gaseous small molecule to a protein or other biological molecule by appropriately adjusting the size of the pores contained in the pore group formed in the polymer complex. Even large molecules can be taken into the pores. That is, it is possible to selectively take in a specific compound for each pore group from a mixture containing two or more kinds of small molecules and large molecules.

  Thus, for example, two or more specific components can be separated from a mixture containing two or more components and stored in the polymer complex. Further, from the mixture 1 containing one or more components, only a specific component is taken into the pores of the pore group 1, and the components are retained in the pores of the pore group 1, Other specific components can be taken into the pores of a certain pore group 2 from the mixture 2 containing one or more components different from the mixture 1. Alternatively, when the polymer complex of the present invention is used as a material constituting the partition wall, the compound a that is selectively taken into the pore group A between the regions separated by the partition wall passes through the pore group A, The compound b that is selectively taken into the pore group B can also be transported through the pore group B. At this time, if the compound moves according to the concentration distribution and temperature distribution of each compound, the transport direction can be the same as the transport direction of compound a and the transport direction of compound b. It is also possible for the transport direction of the compound and the transport direction of the compound b to face each other.

Also, two or more guest components incorporated for each pore group can be released separately under different conditions. For example, when a polymer complex in which a guest component is incorporated in two or more kinds of pore groups is placed under a predetermined condition, the guest component to be released varies depending on the exposure time under this condition. Specifically, by heating a polymer complex in which different components are incorporated into the pore group 1 and the pore group 2, respectively, first, the components incorporated into the pores contained in the pore group 1 are released. Further, by further heating, the components taken into the pores included in the pore group 2 can be released.
Here, for the convenience of explanation, the action of the polymer complex of the present invention has been described using expressions of the mixture 1, the pore group 1 and the like. However, the expression of the mixture 1 and the like is a specific mixture, the pore group. It does not indicate etc.

  As a three-dimensional network structure in which an aromatic compound ligand is coordinated to the central metal, for example, two or more independent three-dimensional network structures are combined, preferably combined so as to share the same space. There is also a complex three-dimensional network structure. Specifically, an example of a combined three-dimensional network structure is an interpenetrating structure in which two or more independent three-dimensional network structures are intertwined so as to share the same space.

  In the present invention, the aromatic compound is a compound having at least one aromatic ring, may have a substituent, and may contain an intra-ring hetero atom. The aromatic compound ligand used in the present invention is a multidentate aromatic compound having two or more coordination sites. Preferably, it is an aromatic compound in which all coordination sites constituting the aromatic compound ligand exist in substantially the same plane, and more preferably, the aromatic compound ligand as a whole is substantially planar by a π-conjugated system. In shape, that is, at least part of the molecular structure of the aromatic compound ligand is integrated by a π-conjugated system to form a stable substantially planar structure, and all coordination sites are included in the substantially planar structure. Aromatic ligand.

By using an aromatic compound having such a substantially planar structure as a ligand, the three-dimensional network structure formed by coordination bonding of the aromatic compound to the central metal ion has a more regular structure. And have rigidity. By increasing the regularity of the three-dimensional network structure, a stacked structure of aromatic ligands and non-coordinating aromatic compounds is stably formed, and at the same time, pores and finer with higher regularity are formed. A group of holes can be formed. In some cases, a composite three-dimensional network in which two or more independent three-dimensional network structures are combined can be formed.
On the other hand, since the three-dimensional network structure has rigidity, the stability, strength, and the like of the formed three-dimensional lattice structure can be kept high. In addition, since the strength of the polymer complex becomes relatively large due to the rigidity of the three-dimensional network structure, it can be used in applications that require strength, and the technical scope in which the polymer complex of the present invention can be used. Becomes wider.

  From the above viewpoints, the aromatic compound ligand that can be suitably used in the present invention is, for example, centered on one aromatic ring toward the direction in which the plane formed by the π-conjugated system of the aromatic ring widens. However, the present invention is not limited to this.

  Further, the non-coordinating aromatic compound used in the present invention is an aromatic compound that enters between the aromatic compound ligands by a bond or interaction other than a coordination bond and exists in the polymer complex. This means that no coordination bond is formed in the polymer complex of the present invention. Therefore, the non-coordinating aromatic compound referred to here may be one having an ability to form a coordination bond essentially. Preferably, it is an aromatic compound having a stable substantially planar shape in which all aromatic rings included in the molecular structure are integrated by a π-conjugated system. By having a substantially planar shape in this way, in the three-dimensional network structure formed by the aromatic compound ligand, a non-coordinating aromatic compound is easily inserted between the aromatic compound ligands, A stable aromatic compound ligand-non-coordinating aromatic compound-aromatic compound ligand stacked structure can be formed.

At this time, when the aromatic compound ligand also has a substantially planar shape, the plane of the aromatic compound ligand and the plane of the non-coordinating aromatic compound face each other and overlap, A π-π interaction works between the compound ligand, the non-coordinating aromatic compound and the aromatic compound ligand. As a result, the non-coordinating aromatic compound does not have a direct bond with the aromatic compound ligand, but is firmly bound between the aromatic compound ligands. A dimensional grid structure can be formed.
Thus, the non-coordinating aromatic compound tightly bound between the aromatic compound ligands is not extracted even under guest exchange conditions using a general aromatic compound as a guest component. Therefore, the three-dimensional lattice structure having a stacked structure in which the non-coordinating aromatic compound is firmly bound between the aromatic compound ligands is a guest incorporated into the pores in the three-dimensional lattice structure. Before and after exchanging the components with other guest components, the structure can be maintained without change.

  Further, a stacked structure in which a non-coordinating aromatic compound is inserted between aromatic compound ligands is a unit in which the non-coordinating aromatic compound is inserted between aromatic compound ligands. However, it is preferable that the structure in which the aromatic compound ligand and the non-coordinating aromatic compound are alternately stacked continues to some extent. In the polymer complex 3 to be described later, this stacked structure continues indefinitely. However, the number of stacked units sufficient to form two or more kinds of pore groups may be infinite. Good.

  A three-dimensional network structure with sufficient three-dimensional expansion in which aromatic ligands and metal ions are coordinated, and a stacked structure in which aromatic ligands and non-coordinating aromatic compounds are sufficiently stacked Are formed, elongated channel-shaped pores are formed.

  The affinity for the guest component inherently possessed by two or more kinds of pore groups in the polymer complex is the size of the pores in the contrast between two pore groups arbitrarily selected from the two or more kinds of pore groups, If at least one of the pore shape and the atmosphere in the pore is different, they are different from each other. In order to increase the affinity of the pores constituting each pore group to a specific guest component and to allow each pore to take in a specific guest component more selectively, two or more types of pore groups It is preferable that two or more of the pore size, shape, and atmosphere in the pores are different from each other in the contrast between the two pore groups arbitrarily selected from the above. In particular, pore groups in which all three of the pore size, pore shape, and pore atmosphere constituting each pore group are different from each other are preferable because they exhibit higher selectivity for the guest component.

  The elements that make the atmosphere in the pores different among the pore groups are not particularly limited as long as the atmospheres in the pores are different from each other and the affinity for the guest component is different. For example, there are various types depending on the polarity. For example, on the inner surface of a wall forming a pore, a region where the π plane of the aromatic compound (aromatic compound ligand and / or non-coordinating aromatic compound) constituting the wall is exposed, The atmosphere in the pores also varies depending on the occupation ratio of the group compound with the region where the hydrogen atoms are exposed.

  In addition, when the pore sizes differ between the pore groups, the type of guest component incorporated into the pores constituting each pore group and the amount of the guest component incorporated differ depending on the molecular size of the guest component. come. The size of the pore varies depending on the position in the polymer complex even if it is one continuous pore, and the minimum pore size is the minimum molecular size of the guest component that can be incorporated into the pore, and the maximum pore size. Greatly affects the maximum molecular size of guest components that can be incorporated into the pores and the amount of guest components that can be incorporated. Therefore, the pore size range is an important factor that affects the affinity for the guest component.

  The pores formed in the three-dimensional lattice structure of the polymer complex locally meander somewhat, but on the three-dimensional lattice structure, when viewed as a whole, it extends in a certain direction. Has direction. Therefore, in the present invention, an inscribed circle (hereinafter simply referred to as a fine line) in a plane parallel to the crystal plane that is closest to the direction perpendicular to the direction in which the pore extends (hereinafter sometimes referred to as a parallel plane). The diameter of the inscribed circle of the pore) may be used as an index of the pore size. Here, the direction in which the pores extend is the direction of one continuous void that ignores local meandering of the pores.

  The direction in which such pores extend can be determined as follows, for example. First, select a crystal plane X (A plane, B plane, C plane, or a diagonal plane of each) in an appropriate direction crossing the channel whose size is to be measured, and a crystal plane Y shifted by one unit cell from the crystal plane X, A cross-sectional view of the channel at each crystal plane X, Y is drawn. Next, the center of the cross-sectional shape of the channel on each crystal plane is connected by a straight line (dashed line) in the three-dimensional view (see FIG. 8). The direction of the straight line obtained at this time coincides with the direction in which the channel extends. Then, a crystal plane that intersects the obtained straight line at an angle closest to the perpendicular can be selected, and the diameter of the inscribed circle of the pore in the crystal plane can be set as the pore size.

  When considering only the size of the pores as an element that determines the selectivity of the pores with respect to the guest component, a guest component having a molecular size equal to or smaller than the diameter of the inscribed circle will normally be in the pores. Since it can be taken in without difficulty, it is significant to define the pore size by the diameter of the inscribed circle. The pore size between each pore group should just differ from each other, and there is no limitation in the difference.

The size of the pores formed in the polymer complex of the present invention may be appropriately designed depending on the component to be selectively incorporated. Depending on the size, the size of gaseous small molecules, proteins, and other biological molecules can be determined. Such large molecule components can be incorporated into the pores. Specifically, the diameter of the inscribed circle can be 2 to 70 mm, preferably 2 to 20 mm. Alternatively, the major axis of the inscribed ellipse of the pores in the parallel plane (hereinafter sometimes simply referred to as the inscribed ellipse of the pores) is 5 to 70 mm, and the minor axis of the inscribed ellipse of the pores is 2 to 50 mm. can do. When the pore sizes of the respective pore groups are different, the pore sizes of the respective pore groups are preferably different from each other within the above range.
As a comparison element between different pore groups, the diameter of the inscribed circle of the pore, and a measure for defining the deviation of the pore shape from the inscribed circle, the minor axis and the major axis of the inscribed ellipse of the pore Is more preferable.

Here, a method for measuring (calculating) the size of the pores will be described with reference to FIG. FIG. 1 is a projection on the crystal plane (010) of a diagram depicting the main skeleton of the polymer complex 3 described later using the van der Waals radius, and the guest incorporated in the pore C and the pore D Ingredients are omitted.
In the polymer complex 3, the pores C and D are in a direction perpendicular to the crystal plane (010) (not the local direction but the overall direction as described above), that is, on the paper surface of FIG. On the other hand, it extends vertically. That is, since the paper surface of FIG. 1 is the above parallel surface, the diameter of the inscribed circle of the pore shown in FIG. 1 and / or the major axis and minor axis of the inscribed ellipse are measured and converted to an actual scale. The value obtained is the pore size.
The pore size depends on the molecular design, for example, the molecular size of the aromatic compound ligands and non-coordinating aromatic ligands that constitute the three-dimensional lattice structure, the central metal ion and the aromatic compound ligand. It can be adjusted by the coordination force or the like.

  In addition, when the shape of the pore is different between the pore groups, for example, even if the diameter of the inscribed circle and the major axis and minor axis of the inscribed ellipse are substantially the same, The guest components taken into the pores constituting the group are different. The shape of the pores may be different from each other in at least one place between the pore groups, and may not be different in the entire region of the continuous pores.

Hereinafter, the aromatic compound ligand, the non-coordinating aromatic compound, and the metal ion serving as the central metal constituting the polymer complex of the present invention will be specifically described.
As an aromatic compound ligand, the aromatic compound represented by following formula (1) is mentioned, for example.

(In the formula, Ar is a structure having an aromatic ring. X is a divalent organic group or a single bond directly connecting Ar and Y. Y is a coordination atom or an atom containing a coordination atom. N represents a number of 3 to 6. A plurality of X contained in one molecule may be different from each other, and a plurality of Y may be different from each other.

  Here, in Formula (1), Ar has a π plane that forms a substantially planar structure and has a π-π interaction with a non-coordinating aromatic compound. Ar is not particularly limited, and may be appropriately selected in consideration of the fact that the molecular size of the aromatic compound ligand has some influence on the size of the pores formed in the polymer complex. Specifically, 2 to 5 monocyclic aromatic rings, particularly 6-membered aromatic rings, or 2 to 5 condensed polycyclic aromatic rings, particularly 6-membered aromatic rings are condensed. Examples thereof include condensed polycyclic aromatic rings.

In view of ease of synthesis, Ar is preferably a monocyclic aromatic ring such as a 6-membered aromatic ring. Examples of the monocyclic 6-membered aromatic ring include a benzene ring, a triazine ring, a pyridine ring, and a pyrazine ring.
Ar may be a structure having an aromatic ring, and may partially include an alicyclic ring structure or may include an intra-ring hetero atom. Moreover, you may have substituents other than-(XY).

In formula (1), for X intervening between Ar and Y, as the divalent organic group, the chain length and the like are appropriately selected depending on the size required for the pores formed in the polymer complex In order to form pores capable of taking in organic compounds having a relatively large molecular size, for example, a divalent aliphatic group having 2 to 6 carbon atoms or a bivalent monocyclic compound having 6 members is preferable. Examples thereof include condensed polycyclic aromatic rings in which 2 to 4 aromatic rings and 6-membered aromatic rings are condensed.
Here, the aromatic ring may contain a hetero atom in the ring and may have a substituent. Moreover, you may include an alicyclic structure in part. The aliphatic group may have a branched structure, may contain an unsaturated bond, or may contain a hetero atom.

  Specific examples of the divalent organic group include monocyclic aromatic rings such as phenylene group, thiophenylene and furylene, condensed polycyclic aromatic rings condensed with benzene rings such as naphthyl group and anthracene, acetylene group, ethylene Examples thereof include an aliphatic group such as a group, an amide group and an ester group, and a structure in which these groups are connected in an arbitrary number and order. A plurality of X contained in one molecule may be the same or different from each other, but are usually preferably the same from the viewpoint of ease of synthesis.

  Y is a coordination atom or an atomic group containing a coordination atom that can be coordinated to a central metal ion serving as a central metal, and can be coordinated to a central metal ion to form a three-dimensional network structure. There is no particular limitation. For example, group represented by following formula (2) is mentioned.

  Formulas (2b), (2c), and (2d) can donate a lone pair of electrons to the central metal ion by taking a resonance structure. The resonance structure of formula (2c) is shown below as a representative example.

Y may be a coordination atom itself or an atomic group containing a coordination atom. For example, the 4-pyridyl group (2a) is an atomic group containing a coordination atom (N). Of the above formulas, pyridyl groups (2a, 2f) are particularly preferred from the viewpoint that an appropriate coordinating force can be obtained when the lone electron pair of the Y coordination atom has a coordinate bond to the central metal ion.
A plurality of Y contained in one molecule may be the same as or different from each other.

  As described above, the aromatic compound ligand is preferably an aromatic compound in which all coordinating sites constituting the aromatic compound ligand are present in substantially the same plane, and in particular, a π-conjugated system. Therefore, it is preferable that the aromatic compound ligand has a substantially planar shape as a whole. That is, it is preferable that all Y contained in the aromatic compound ligand (1) represented by the above formula (1) exists in substantially the same plane. In particular, it is preferable that together with Ar, a plurality of — (X—Y) bonded to Ar are integrated by a π-conjugated system to form a stable substantially planar structure, and all Ys are present in the substantially planar structure.

  In an aromatic compound ligand in which Ar and a plurality of — (X—Y) are integrated by a π-conjugated system to form a substantially planar structure, — (XY) has a rigid linear structure and is used. In the intended environment, it is preferable that rotation about the axis is limited from the viewpoint of effective π-π interaction with the non-coordinating aromatic compound.

  From such a viewpoint, among those exemplified above, X is a single bond directly connecting Ar and Y, a monocyclic aromatic ring such as a phenylene group, or a condensed polycyclic aromatic ring such as a naphthyl group and anthracene. And an aromatic group such as an acetylene group and an ethylene group, and those having a structure in which these groups are connected in any number and order are preferred. When-(XY) has a structure composed of an aromatic ring, an acetylene group, or an ethylene group or a structure in which these are connected, axial rotation is restricted due to steric hindrance. Furthermore, when a structure composed of an aromatic ring, an acetylene group, and an ethylene group forms a conjugated system in which π electrons are delocalized, axial rotation is also limited by the conformational energy barrier. Therefore, the aromatic compound ligand represented by the above formula (1) can be integrated to form a substantially planar structure, and a stable three-dimensional network structure can be formed.

  In addition, the coordination atom represented by Y or the coordination atom contained in Y has the above-mentioned rigid linear structure in terms of the ease of designing a polymer complex, and the-(XY) axis. It is preferable to have a lone pair of electrons in the extending direction.

The number of — (X—Y) bonded to Ar is usually 3 to 6 although it depends on the structure of Ar. Further,-(X—Y) is preferably bonded to Ar so that the coordination atoms are arranged radially at equal intervals in substantially the same plane centered on Ar.
A fragrance having a structure in which coordination atoms are arranged radially at equal intervals in the direction in which the plane formed by the π-conjugated system of the aromatic ring is centered on one aromatic ring-containing structure Ar as described above. Examples of the group compound ligand (1) include those represented by the following formula (4).

  In the above formula (4), due to the electron-deficient state, the interaction with the non-ligand aromatic compound is strong, and the stacked structure with the non-ligand aromatic compound is more firmly stabilized. In particular, tris (4-pyridyl) triazine (4a) is preferable.

On the other hand, specific examples of non-coordinating aromatic compounds include condensed polycyclic aromatic compounds. This is because, for the reasons already described, it is preferable that all the rings included in the molecular structure are integrated by a π-conjugated system and are an aromatic compound having a stable substantially planar shape.
Examples of the condensed polycyclic aromatic compound include 2 to 7 cyclic compounds. It is preferable that the condensed polycyclic aromatic compound has a planar shape with a certain extent so that the stacked structure with the aromatic compound ligand becomes stable. Examples of such condensed polycyclic aromatic compounds include those represented by the following formula (5).

As the central metal ion coordinated with the aromatic compound ligand, various metal ions may be appropriately selected and used, but a transition metal ion is preferable. In the present invention, the transition metal includes zinc, cadmium, and mercury of Group 12 of the periodic table, and among them, those of Groups 8 to 12 of the periodic table are preferable. Specifically, zinc, copper, nickel, Cobalt, iron, silver and the like are preferable.
In the present invention, the central metal ion is usually present in the three-dimensional lattice structure in the form of a compound such as a metal salt. Examples of the metal compound containing these central metal ions include halogen metal salts, specifically, ZnI ₂ , ZnCl ₂ , ZnBr ₂ , NiI ₂ , NiCl ₂ , NiBr ₂ , CoI ₂ , CoCl ₂ , CoBr _{2 and the} like. Preferably used.

  The aromatic compound ligand is an aromatic compound as shown in the above formula (1), particularly the above formula (4), and the non-coordinating aromatic compound is a condensed polycyclic aromatic compound, particularly the above formula (5). When the aromatic compound as shown in FIG. 1 is used, the size of the pores contained in the pore group selected from two or more kinds of pore groups formed in the polymer complex is the inscribed circle in the parallel plane. The diameter of 3 to 10 mm, particularly 4.5 to 7.0 mm, and the major axis of the inscribed ellipse of the pores in the parallel plane is 5 to 15 mm, particularly 8.5 to 10.0 mm, The minor axis of the inscribed ellipse can be in the range of 3 to 13 mm, particularly 6.0 to 8.0 mm. The polymer complex in which such size pores are formed can take in a relatively large size compound such as an organic compound.

Here, tris (4-pyridyl) triazine (formula 4a) as an aromatic compound ligand, triphenylene (formula 5a) as a non-coordinating aromatic compound, ZnI ₂ as a metal compound containing a metal ion serving as a central atom, The method for producing the polymer complex of the present invention and the structure of the polymer complex will be described more specifically by taking a polymer complex obtained by using as an example.

In the following formula (6), tris (4-pyridyl) triazine (1) is a compound having a substantially planar structure in which a triazine ring and three pyridyl rings are present in substantially the same plane, and three 4-pyridyl nitrogens It can coordinate to a metal ion in an atom. Triphenylene (2) is also a compound having a substantially planar shape. Tris (4-pyridyl) triazine (1) (hereinafter, sometimes simply expressed as (1)), ZnI ₂ , and triphenylene (2) (hereinafter, simply expressed as (2) in the formula) A polymer complex having a three-dimensional lattice structure formed by reacting with ZnI ₂ in the presence of tris (4-pyridyl) triazine (1) and triphenylene (2). (Formula 6).

For example, a polymer complex having a single crystal structure represented by {[(ZnI ₂ ) ₃ (1) ₂ (2)] (nitrobenzene) _3.9 (methanol) _1.8 } _z (hereinafter sometimes referred to as polymer complex 3). ) Can be prepared using a three-layer solution (upper layer: methanol solution of ZnI ₂ , intermediate layer: methanol, lower layer: nitrobenzene-methanol solution of tris (4-pyridyl) triazine and triphenylene). At this time, the methanol layer as an intermediate layer is a buffering agent for preventing ZnI _{2 from} being mixed directly with tris (4-pyridyl) triazine and triphenylene. The three-layer solution is allowed to stand, and ZnI ₂ is gradually mixed with tris (4-pyridyl) triazine and triphenylene, whereby the polymer complex 3 is generated.

  FIG. 2 shows a diagram obtained by X-ray crystal structure analysis of polymer complex 3. FIG. (A) of FIG. 2 has a direction perpendicular to the plane of the paper (crystal 010 plane) as the axis b, and shows a channel C and a channel C, which will be described later, in the three-dimensional lattice structure of the polymer complex 3. It is shown along the direction (axis b) in which D extends. In FIG. 2A, triphenylene and the guest component taken into channel C and channel D are omitted. FIG. 2B shows an aromatic skeleton in which tris (4-pyridyl) triazine (1a) and (1b) and triphenylene (2) are stacked innumerably in the square region marked in FIG. It shows a mutual stacking structure (a view of FIG. 2 (a) seen from the side). FIG. 2 (c) is an enlarged view of FIG. 1 and shows the voids of the channel having two regularities. The polymer complex 3 is seen from the same direction as FIG. 2 (a). It is a figure.

When the polymer complex 3 was analyzed by X-ray crystal structure analysis, as shown in FIG. 2 (a), a tertiary structure in which a plurality of tris (4-pyridyl) triazines and ZnI ₂ were three-dimensionally linked by coordination bonds. It was found that the original network structures 1A and 1B have a composite three-dimensional network structure formed so as to penetrate each other. At this time, the three-dimensional network structure 1A and the three-dimensional network structure 1B do not have indirect or direct coupling such as sharing of ZnI ₂ and are independent of each other so as to share the same space. Is in a state of being intricate with each other.

  Furthermore, by X-ray crystal structure analysis, triphenylene (2) is obtained from the π plane of tris (4-pyridyl) triazine (1a) of the three-dimensional network structure 1A and tris (4-pyridyl) triazine (3D of the three-dimensional network structure 1B). 1b) was firmly inserted (intercalated) between the π plane (see FIG. 2B). At this time, triphenylene (2) is taken in between (1a) and (1b) by π-π interaction between tris (4-pyridyl) triazine (1a) and (1b), and tris (4- It does not have a direct bond with (pyridyl) triazine. However, in this way, the structure (..1a..2..1b..2 ..) in which triphenylene is inserted between the .pi. Planes of two tris (4-pyridyl) triazines has become a polymer. It is considered that the solid structure of the complex 3 is stabilized. Moreover, since triphenylene (2) forming a stacked structure is not extracted in a guest exchange experiment described later, it is considered that it functions as a part of the main skeleton of the polymer complex 3.

This strong restriction of triphenylene (2) is due to the charge transfer (CT) interaction between 1a-2-1b. A broad CT absorption band was observed in the range of 400 to 600 nm in the analysis by ultraviolet / visible spectroscopy. Furthermore, it was derived from calculation that the HOMO (highest occupied molecular orbital) of triphenylene (2) and the LUMO (lowest empty orbital) of tris (4-pyridyl) triazine (1) efficiently overlapped (Fig. 3). The LUMO of tris (4-pyridyl) triazine (1) is obtained by modeling the skeleton of the polymer complex 3 as [(ZnI ₂ ) ₃ (1) ₃ (pyridine) ₃ ].

  (A) of FIG. 3 is a figure which shows (pi) -pi stacking between the tris (4-pyridyl) triazine (1) and triphenylene (2) in the polymer complex 3, (b) of FIG. 3 is HOMO. FIG.

As shown in FIGS. 2A and 2C, the polymer complex 3 has two types of channels (C and D) regularly arranged in the three-dimensional lattice structure. Channels C and D are regularly formed between stacked structures in which tris (4-pyridyl) triazine (1) and triphenylene (2) are alternately stacked. The channel C has a substantially cylindrical shape, and is almost surrounded by hydrogen atoms present on the side edges of the infinite number of stacked tris (4-pyridyl) triazine (1) and triphenylene (2) in the π plane.
On the other hand, the channel D has a substantially triangular prism shape, and two of the three surfaces forming the triangular prism are surrounded by the π plane of tris (4-pyridyl) triazine (1), and the other is It is surrounded by hydrogen atoms present on the side edges of the π plane of the countless tris (4-pyridyl) triazine (1) and triphenylene (2) stacked. The channel C and the channel D have a slender shape meandering slightly.
Further, the channels C and D are different from the diameter of the inscribed circle and the major axis and minor axis of the inscribed ellipse (channel C: inscribed ellipse major axis 8.5 to 10.0 mm, inscribed ellipse minor axis 6.0). ~ 8.0 mm, channel D: inscribed circle diameter 4.5-7.0 mm).

Thus, the channel C formed in the polymer complex 3 having a single crystal structure represented by {[(ZnI ₂ ) ₃ (1) ₂ (2)] (nitrobenzene) _3.9 (methanol) _1.8 } _z Channel D is different in shape, size and atmosphere. The void ratios of the channels C and D were almost the same, and both were about 20%.
In the polymer complex 3, channel C includes methanol and nitrobenzene in random order, and channel D includes only nitrobenzene. These arrangements of methanol and nitrobenzene could not be sufficiently analyzed by X-ray structural analysis because of the disordered structure.

When the polymer complex 3 was immersed in a saturated solution of naphthalene in cyclohexane at room temperature for 2 days, channel C selectively incorporated naphthalene, while channel D selectively incorporated cyclohexane. As a result of this guest exchange, the polymer complex 3 becomes a polymer complex 4 having a single crystal structure represented by {[(ZnI ₂ ) ₃ (1) ₂ (2)] (cyclohexane) _1.3 (naphthalene) _2.3 } _z. Converted to. At this time, the conversion from the polymer complex 3 to the polymer complex 4 proceeded while maintaining a single crystal-single crystal type, that is, a crystalline state.

Although the polymer complex 4 was after guest exchange, high-quality diffraction data could be obtained in the X-ray crystal structure analysis, and the final R ₁ value converged to 0.052. According to this crystal structure analysis, an array of naphthalene was formed in channel C, and an array of cyclohexane was formed in channel D (see FIG. 4). At this time, the presence probability of naphthalene in channel C was 100%, and the presence probability of cyclohexane in channel D was 70%. Here, the existence probability is the ratio of the guest component existing in the actual crystal to 100% of the guest component existing in the single crystal structure that should be composed of unit cells repeatedly arranged, and X It is obtained by line crystal analysis.

In addition, in the conversion from the polymer complex 3 to the polymer complex 4, a large molecule is exchanged in each channel, but intercalated between tris (4-pyridyl) triazines. The main skeleton containing triphenylene hardly changed.
In addition, when a polymer complex is constructed only from tris (4-pyridyl) triazine and ZnI ₂ , the polymer complex 3 has different shapes, sizes and atmospheres, and has different affinity for guest components 2 No seed channel is formed, only a single channel (pore) is formed. In addition, the polymer complex formed without the coexistence of triphenylene and having a network topology different from that of the polymer complex 3 is not converted to the polymer complex 3 under guest exchange conditions in which triphenylene is present. .

Since the polymer complex of the present invention represented by the polymer complex 3 as described above has two or more kinds of pore groups having different affinity for the guest component in one molecule, These two or more guest components are separately included in different pore groups through guest exchange. The guest components taken into these pore groups are separated from each other by a rigid main skeleton constituting a three-dimensional lattice structure. Therefore, the polymer complex of the present invention stores two or more components that cannot coexist, such as an acid and a base, an oxidizing agent and a reducing agent, in a stable state in one polymer complex, It is possible to transport the polymer complex separately. The polymer complex of the present invention can be used for various applications in various fields, for example, a solid high molecular weight compound, by adjusting the affinity for the guest component of two or more kinds of pore groups formed in one polymer complex. It can be used for pore-forming materials used for electrodes of molecular fuel cells, electrolyte membrane electrolytes for polymer electrolyte fuel cells, and technologies for removing impurities from methanol, which is the fuel for direct methanol-added fuel cells. I can expect.
In polymer electrolyte fuel cells, it is known to add a pore former to promote diffusion of fuel gas and oxidant gas, but by adding a pore former, an electrode ( There is a problem in that moisture cannot be retained in the catalyst layer), and the power generation performance is reduced by drying the electrolyte membrane. Since the polymer complex of the present invention has hydrophilic pores and hydrophobic pores, moisture can be retained by the hydrophilic pores even under low humidification conditions. It is considered that the gas diffusivity can be maintained. Further, as an additive for the electrolyte membrane of the polymer electrolyte fuel cell, it is considered that moisture can be maintained in the electrolyte membrane by the hydrophilic portion, and improvement in power generation performance is expected.

  Hereinafter, the present invention will be described in more detail with reference to examples.

[Production of polymer complex 3]
A lower layer consisting of 5 ml of a nitrobenzene-methanol solution (nitrobenzene: methanol = 4: 1 (volume ratio)) containing 0.02 mmol of tris (4-pyridyl) triazine (formula 4a) and 0.1 mmol of triphenylene (formula 5a), A three-layer solution composed of an intermediate layer composed of 0.5 ml of methanol and an upper layer composed of 0.5 ml of a methanol solution containing 0.03 mmol of ZnI ₂ was allowed to stand at about 23-25 ° C. for about one week, { [(ZnI ₂ ) ₃ (1) ₂ (2)] (nitrobenzene) _3.9 (methanol) _1.8 } Polymer complex 3 having the single crystal structure represented by _z (same as polymer complex 3 described above) The composition was determined by elemental analysis). The yield was 54%.

(Analysis of polymer complex 3)
The obtained polymer complex 3 was subjected to elemental analysis and X-ray crystal structure analysis. The results are shown below. Table 1 shows the guest components occluded in channels C and D and their existence probabilities obtained from these results. The crystal structure analysis was performed with a Smart 1000 X-ray diffractometer (manufactured by Bruker, X-ray source: Mo—K _α , temperature: 80 K, output: 55 kV, 30 mA) (hereinafter the same).

<Elemental analysis>
calcd for {[(ZnI ₂ ) ₃ (1) ₂ (2)] ・ 3.9 (nitrobenzene) ・ 1.8 (methanol)} _z (3): C 40.51, H 2.69, N 9.48
found: C 40.89, H 2.60, N 9.49

<X-ray crystal structure analysis>
C _79.33 H _55.56 I ₆ N _15.91 O _9.68 Zn ₃ , M _r = 2344.00, Orthorhombic, space groups, Pbca, a = 27.268 (3), b = 13.6992 (16), c = 45.888 (5) Å, V = 17141 (3) Å ³ , T = 80 K, Z = 8, ρ _calcd = 1.817 g cm ^-3 , 15876 unique reflections out of 21254 with I> 2σ (I), 1025 parameters, 1.72 <θ <28.92 °, final R factors R ₁ = 0.0821 and wR ₂ = 0.1478

[Guest exchange experiment]
The polymer complex 3 obtained above was immersed in each of the mixed solutions shown in Table 1 for 1 day or more at room temperature (about 23 to 25 ° C.) to perform guest exchange.

Elementary analysis and X-ray crystal structure analysis were performed on the polymer complexes 4 to 7 after the guest exchange using the mixed solutions. The results of elemental analysis and X-ray crystal structure analysis of each of the polymer complexes 4 to 7 are as follows.
Table 1 summarizes the compositions of the polymer complexes 4 to 7 obtained by these analyzes, the guest components incorporated in the channels C and D, and their existence probabilities. Furthermore, the arrangement | sequence of the guest component formed in the channels C and D of each polymer complex 3-7 was shown in FIG. Here, in the polymer complex 4 and the polymer complex 7, some disordered guest components are omitted.

(Polymer Complex 4)
<Elemental analysis>
calcd for {[(ZnI ₂ ) ₃ (1) ₂ (2)] ・ 1.3 (cyclohexane) ・ 2.3 (naphtalene)} _z (4): C 45.99, H 3.19, N 7.59
found: C 45.71, H 2.92, N 7.29
<X-ray crystal structure analysis>
C _85.38 H _71.07 I ₆ N ₁₂ Zn ₃ , M _r = 2222.62, Orthorhombic, space groups, Pbca, a = 27.6479 (19), b = 13.7500 (9), c = 45.714 (3) Å, V = 17379 (2 ) Å ³ , T = 80 K, Z = 8, ρ _calcd = 1.854 g cm ^-3 , 15905 unique reflections out of 21663 with I> 2σ (I), 1057 parameters, 1.72 <θ <28.75 °, final R factors R ₁ = 0.0517 and wR ₂ = 0.1174

(Polymer Complex 5)
<Elemental analysis>
calcd for {[(ZnI ₂ ) ₃ (1) ₂ (2)] ・ 1.4 (cyclohexane) ・ 2 (azulene)} _z (5): C 45.30, H 3.17, N 7.69
found: C 45.50, H 2.88, N 7.41
<X-ray crystal structure analysis>
C ₈₆ H ₇₆ I ₆ N ₁₂ Zn ₃ , M _r = 2235.10, Orthorhombic, space groups, Pbca, a = 27.787 (3), b = 13.7247 (12), c = 45.881 (4) Å, V = 17498 (3 ) Å ³ , T = 80 K, Z = 8, ρ _calcd = 1.697 g cm ^-3 , 14824 unique reflections out of 21598 with I> 2σ (I), 904 parameters, 1.71 <θ <28.71 °, final R factors R ₁ = 0.0783 and wR ₂ = 0.1636

(Polymer Complex 6)
<Elemental analysis>
calcd for {[(ZnI ₂ ) ₃ (1) ₂ (2)] ・ 2.4 (nitrobenzene) ・ (naphthalene)} _z (6): C 42.15, H 2.53, N 9.03
found: C 41.85, H 2.67, N 8.94
<X-ray crystal structure analysis>
C ₈₂ H ₅₉ I ₆ N ₁₅ O ₆ Zn ₃ , M _r = 2307.95, Orthorhombic, space groups, Pbca, a = 27.5680 (18), b = 13.7285 (9), c = 45.836 (3) Å, V = 17347 (2) Å ³ , T = 80 K, Z = 8, ρ _calcd = 1.767g cm ^-3 , 14715 unique reflections out of 21416 with I> 2σ (I), 1005 parameters, 1.71 <θ <28.84 °, final R factors R ₁ = 0.0776 and wR ₂ = 0.1678

(Polymer Complex 7)
<Elemental analysis>
calcd for {[(ZnI ₂ ) ₃ (1) ₂ (2)] ・ 2.0 (cyclohexane) ・ 0.4 (nitrobenzene)} _z (7): C 40.51, H 3.08, N 8.56
found: C 40.51, H 3.03, N 8.18.
<X-ray crystal structure analysis>
C _77.13 H _77.65 I ₆ N _12.66 O _1.32 Zn ₃ , M _r = 2307.95, Orthorhombic, space groups, Pbca, a = 27.873 (2), b = 13.7073 (10), c = 45.852 (3) Å, V = 17518 (2) Å ³ , T = 80 K, Z = 8, ρ _calcd = 1.638g cm ^-3 , 15437 unique reflections out of 21619 with I> 2σ (I), 1086 parameters, 1.71 <θ <28.84 °, final R factors R ₁ = 0.0739 and wR ₂ = 0.1323

In order to completely release cyclohexane and nitrobenzene incorporated into the polymer complex 7, the polymer complex 7 was heated at 250 ° C. for 20 minutes under a nitrogen gas (70 ml / min) flow. As a result of determining the composition after heating by elemental analysis, it was found that triphenylene was not exchanged due to guest exchange conditions. The results of elemental analysis were as follows.
<Elemental analysis>
calcd for [(ZnI ₂ ) ₃ (1) ₂ (2)] _z : C 35.82, H 2.00, N 9.28
found: C 36.12, H 2.17, N 9.02

In the polymer complex 3 before guest exchange, nitrobenzene and naphthalene were included in the channel C and nitrobenzene was included in the channel D, but this type of exchange phenomenon is relatively difficult when immersed in the mixed solution shown in Table 1. Guest exchange proceeded promptly, and different guest components were selectively taken into channels C and D (Table 1, FIG. 4).
During the guest exchange, the main skeleton structure of the polymer complex did not change and was maintained.

  From Table 1 and FIG. 4, channel C (substantially cylindrical and surrounded by hydrogen atoms) prefers aromatic compounds such as naphthalene and azulene, and channel D (substantially triangular prism type) It can be seen that among the three surfaces to be formed, two are π planes and the other is surrounded by hydrogen atoms), preferentially taking in cyclohexane.

(Thermogravimetric analysis (TGA))
The polymer complex 4 was subjected to thermogravimetric analysis under the following conditions.
<TGA conditions>
・ Raising rate: 10 ° C / min
・ Atmosphere: Nitrogen gas (70ml / min)

According to the TGA, the polymer complex 4 selectively released guest molecules in three stages. As a result of the TGA measurement, the guest molecules released at each stage, the weight reduction rate (the values in parentheses are values obtained by calculation), and the temperatures thereof are as follows.
First stage: cyclohexane, 4.55% (4.93%), 50-160 ° C
Second stage: naphthalene, 12.87% (13.31%), about 200 ° C
Third stage: Triphenylene, 10.31% (10.31%), about 420 ° C

The TGA result of the polymer complex 4 is consistent with the results of elemental analysis and X-ray crystal structure analysis of the polymer complex 4.
In addition, when triphenylene itself is thermally decomposed under the same conditions as the TGA, the weight decreases at a temperature lower than 420 ° C. (330 ° C. or lower), so that triphenylene intercalated in the polymer complex 4 is It was shown to be tightly bound in the 3D network structure.

[Production of polymer complex 8]
A lower layer consisting of 6 ml of a nitrobenzene-methanol solution (nitrobenzene: methanol = 2: 1 (volume ratio)) containing 0.02 mmol of tris (4-pyridyl) triazine (formula 4a) and 0.02 mmol of perylene (formula 5e), A three-layer solution composed of an intermediate layer composed of 0.5 ml of methanol and an upper layer composed of 0.5 ml of a methanol solution containing 0.03 mmol of ZnI ₂ was allowed to stand at about 23-25 ° C. for about one week, { [(ZnI ₂ ) ₃ (1) ₂ (Perylene)] (Nitrobenzene) ₄ } Polymer complex 8 having a single crystal structure represented by _z (composition determined by elemental analysis) was obtained. The yield was 45%.

<Elemental analysis>
calcd for {[(ZnI ₂ ) ₃ (1) ₂ (perylene)] ・ 4 (nitrobenzene)} _z : C, 41.29; H, 2.66; N, 9.63
found: C, 41.56; H, 2.51; N, 9.35
<X-ray crystal structure analysis>
C _72.38 H _49.63 I ₆ N _14.73 O _5.46 Zn ₃ , M _r = 2170.60, Orthorhombic, space groups, Pbca, a = 28.253 (3), b = 13.8524 (15), c = 44.966 (5) Å, V = 17598 (3) Å ³ , T = 80 K, Z = 8, ρ _lcd = 1.638 g cm ^-3 , 9687 unique reflections out of 12677 with I> 2σ (I), 1012 parameters, 1.87 <θ <23.31 °, final R factors R ₁ = 0.0893 and wR ₂ = 0.2232

When the polymer complex 8 was analyzed by X-ray crystal structure analysis, as in the polymer complex 3, a plurality of tris (4-pyridyl) triazines and ZnI ₂ as shown in FIG. The three-dimensional network structures 1A and 1B that were originally connected to each other had a composite three-dimensional network structure formed so as to penetrate each other.

  Further, by X-ray crystal structure analysis, perylene (hereinafter referred to as perylene (9) or simply (9)) is obtained from the π plane of the tris (4-pyridyl) triazine (1a) of the three-dimensional network structure 1A and the three-dimensional It was firmly inserted (intercalated) by π-π interaction between the π plane of the tris (4-pyridyl) triazine (1b) of the network structure 1B (see FIG. 5). In this way, the polymer complex 8 has a structure in which the stacked structure in which perylene is inserted between the π planes of two tris (4-pyridyl) triazines is innumerable (..1a..9..1b..9 ..). The solid structure is considered to be stabilized. In FIG. 5, in the polymer complex 8, tris (4-pyridyl) triazine (1a) and (1b) and perylene (9) in the square region marked in FIG. It shows a stacked structure of aromatic skeletons.

  This strong restriction of perylene (9) is due to the charge transfer (CT) interaction between 1a-9-1b as in the polymer complex 3. Furthermore, it was derived from calculations that the HOMO (highest occupied molecular orbital) of perylene (9) and the LUMO (lowest empty orbital) of tris (4-pyridyl) triazine (1) efficiently overlapped (Fig. 6). 6A is a diagram showing a π-π stacking between tris (4-pyridyl) triazine (1) and perylene (9) in the polymer complex 8, and FIG. These are figures which show the superposition of HOMO and LUMO.

As shown in FIG. 7, the polymer complex 8 has two types of channels (E and F) regularly arranged in the three-dimensional lattice structure. Channels E and F are regularly formed between stacked structures in which tris (4-pyridyl) triazine (1) and perylene (9) are alternately stacked. The channel E has a substantially cylindrical shape and is substantially surrounded by hydrogen atoms present on the side edges of the infinite number of stacked tris (4-pyridyl) triazine (1) and perylene (9) in the π plane.
On the other hand, the channel F has a substantially triangular prism shape, and two of the three surfaces forming the triangular prism are surrounded by the π plane of tris (4-pyridyl) triazine (1), and the other is It is surrounded by hydrogen atoms present on the side edges of the π plane of the innumerable stacked tris (4-pyridyl) triazine (1) and perylene (9). The channel E and the channel F have a slightly meandering elongated shape.
Further, the channels E and F are different from the diameter of the inscribed circle and the major axis and minor axis of the inscribed ellipse (channel E: inscribed ellipse major axis 8.5 to 10.0 mm, inscribed ellipse minor axis 6.0). ~ 8.0 mm, channel F: inscribed circle diameter 4.5-7.0 mm).

Thus, the channel E and the channel F formed in the polymer complex 8 having a single crystal structure represented by {[(ZnI ₂ ) ₃ (1) ₂ (perylene)] (nitrobenzene) ₄ } _z are The shape, size and atmosphere were all different.

Supplementary data on the crystal structures of polymer complexes 3 to 8 can be found in the Cambridge crystal structure database, CCDC 251671 (polymer complex 3), CCDC 251672 (polymer complex 4), CCDC 251675 (polymer complex 5), CCDC 251673 (polymer complex 6), CCDC 251674 (polymer complex 7), CCDC 258684 (polymer complex 8). These data can be obtained free of charge by contacting the following URL, e-mail address, or the Cambridge Crystallographic Data Center.
・ URL: www.ccdc.cam.ac.uk/data_request/cif
・ E-mail: data_request@ccdc.cam.ac.uk
The Cambridge Crystallographic Data Centre: 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

It is a projection figure of the figure which drew the main frame | skeleton of the polymer complex 3 using the van der Waals radius, and is a figure explaining the method of calculating the pore size of the polymer complex 3. 3 is a diagram showing a crystal structure of a polymer complex 3. FIG. (A) is a figure which shows the (pi) -pi stacking between the tris (4-pyridyl) triazine (1) and triphenylene (2) in the polymer complex 3, (b) is a superposition of HOMO and LUMO. FIG. It is a figure which shows the arrangement | sequence of the guest component in the channel C (left side) and the channel D (right side) of the polymer complexes 3-7. This shows a stacked structure of aromatic skeletons in which tris (4-pyridyl) triazine (1a), (1b) and perylene (9) are stacked innumerably in the polymer complex 8. (A) is a figure which shows (pi) -pi stacking between the tris (4-pyridyl) triazine (1) and perylene (9) in the polymer complex 8, (b) is a superposition of HOMO and LUMO. FIG. It is the projection figure of the figure which drew the main frame | skeleton of the polymer complex 8 using the van der Waals radius. It is a figure explaining the method of determining the direction where a pore extends.

Claims (15)

  A polymer complex having a three-dimensional lattice structure composed of at least an aromatic compound as a ligand and a metal ion as a central metal, and having a unique affinity for a guest component in the three-dimensional lattice structure A polymer complex comprising two or more kinds of pore groups each having the same pores having the above. A polymer complex containing an aromatic compound as a ligand having two or more coordination sites, a metal ion as a central metal, and a non-coordinating aromatic compound,
A stack in which the non-coordinating aromatic compound is inserted between aromatic compound ligands in a three-dimensional network structure formed by coordination of the aromatic compound ligand to the central metal ion. Having a three-dimensional lattice structure including the structure;
2. The polymer complex according to claim 1, wherein the three-dimensional lattice structure has two or more kinds of pore groups each having the same pore having an intrinsic affinity for the guest component.   The polymer complex according to claim 1, wherein the guest component can be selectively incorporated and / or released.   The polymer complex according to claim 2 or 3, wherein the three-dimensional network structure is a composite three-dimensional network structure formed by combining two or more independent three-dimensional network structures.   The polymer complex according to claim 4, wherein the composite three-dimensional network structure is an interpenetrating structure.   The contrast between two pore groups arbitrarily selected from the two or more types of pore groups is different in at least one of pore size, pore shape, and atmosphere in the pores. The polymer complex in any one of.   7. The polymer complex according to claim 6, wherein the atmosphere in the pores is different due to a difference in occupation ratio between the region where the π plane of the pore inner wall is exposed and the region where the hydrogen atom is exposed.   The polymer complex according to any one of claims 1 to 7, wherein the pores contained in the pore group selected from the two or more kinds of pore groups have an elongated channel shape.   The diameter of the inscribed circle of the pores in a plane parallel to the crystal plane closest to the direction perpendicular to the extending direction of the pores included in the pore group selected from the two or more kinds of pore groups is 2 The polymer complex according to any one of claims 1 to 8, which is ˜70Å.   The major axis of the inscribed ellipse of the pores in a plane parallel to the crystal plane closest to the direction perpendicular to the extending direction of the pores included in the pore group selected from the two or more kinds of pore groups is 5 The polymer complex according to any one of claims 1 to 9, wherein the polymer complex has a minor axis of 2 to 50 mm. The polymer complex according to claim 1, wherein the aromatic compound ligand is an aromatic compound represented by the following formula (1).

(In the formula, Ar is a structure having an aromatic ring. X is a divalent organic group or a single bond directly connecting Ar and Y. Y is a coordination atom or an atom containing a coordination atom. N represents a number of 3 to 6. A plurality of X contained in one molecule may be different from each other, and a plurality of Y may be different from each other.   The polymer complex according to claim 2, wherein the non-coordinating aromatic compound is a condensed polycyclic aromatic compound.   The aromatic compound represented by the formula (1) is tris (4-pyridyl) triazine, and the condensed polycyclic aromatic compound is at least one of triphenylene or perylene. Molecular complex.   The diameter of the inscribed circle of the pores in a plane parallel to the crystal plane closest to the direction perpendicular to the extending direction of the pores included in the pore group selected from the two or more kinds of pore groups is 4 The polymer complex according to claim 13, which is 0.5 to 7.0%.   The major axis of the inscribed ellipse of the pore in a plane parallel to the crystal plane closest to the direction in which the pores included in the pore group selected from the two or more pore groups extend is 8 The polymer complex according to claim 13 or 14, wherein the polymer complex has a minor axis of 6.0 to 8.0 mm.

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