Crystal joint and method for manufacturing the same

Abstract

To disclose a novel bonded body composed of two crystals bonded each other.SOLUTION: There is provided a crystal bonded body comprises a first crystal containing a first coordination polymer and a second crystal containing a second coordination polymer. The first crystal and the second crystal are bonded. The first coordination polymer has a main chain including a first rare earth ion and a first linker ligand, and second coordination polymer has a main chain including a second rare earth ion and a second linker ligand. The first linker ligand and the second linker ligand are ligand compounds represented by the following formula (1), wherein X represents a direct bond or a divalent or trivalent linking group, Z represents a group containing a coordinate bonding functional group, a plurality of Z's in the same molecule may be the same or different, and p represents 1 or 2.SELECTED DRAWING: Figure 1

Description

[[Technical Field]]

[0001] The present disclosure relates to a crystal conjugate and a method for producing the same. [[Background Art]]

[0002] Patent Document 1 discloses a binuclear luminescent rare earth complex having 4,4'-bipyridine as a ligand (Patent Document 1). [[Prior Art Documents]] [[Patent Documents]]

[0003] [[Patent Document 1]] Japanese Unexamined Patent Application Publication No. 2020-033268 [[Summary of the Invention]] [[Problem to be Solved by the Invention]]

[0004] The present disclosure relates to a novel conjugate composed of two types of crystals bonded to each other. [[Means for Solving the Problem]]

[0005] One aspect of the present disclosure relates to a crystal conjugate comprising a first crystal containing a first coordination polymer and a second crystal containing a second coordination polymer, wherein the first crystal and the second crystal are bonded to each other. The first coordination polymer has a main chain containing a first rare earth ion and a first linker ligand forming a coordinate bond with the first rare earth ion, and the main chain is formed by alternately linking the first rare earth ions and the first linker ligands. The second coordination polymer has a main chain containing a second rare earth ion and a second linker ligand forming a coordinate bond with the second rare earth ion, and the main chain is formed by alternately linking the second rare earth ions and the second linker ligands. The first rare earth ion and the second rare earth ion may be the same or different. The first linker ligand and the second linker ligand are represented by the following formula (1): [ka] The ligand compound is represented by formula (1). In formula (1), X represents a direct bond or a divalent or trivalent linking group, Z represents a group containing a coordinating functional group, multiple Zs in the same molecule may be the same or different, and p represents 1 or 2. The first linker ligand and the second linker ligand may be the same or different.

[0006] Another aspect of this disclosure relates to a method for producing the above-described crystal joint. The method includes preparing a first crystal comprising a rare earth complex comprising a first rare earth ion and a first linker ligand forming a coordination bond with the first rare earth ion, and a second crystal comprising a rare earth complex comprising a second rare earth ion and a second linker ligand forming a coordination bond with the second rare earth ion; exposing the first crystal and the second crystal in contact with a gas containing a monodentate ligand compound containing a nitrogen atom to introduce the monodentate ligand compound into the first crystal and the second crystal; and forming a first coordination polymer and a second coordination polymer in the first crystal and the second crystal, respectively, by removing the monodentate ligand compound from the first crystal and the second crystal, thereby joining the first crystal and the second crystal. [Effects of the Invention]

[0007] By selecting a first rare earth ion and a second rare earth ion, the crystal junction according to one aspect of this disclosure can form a light-emitting material that emits light in response to various excitation lights with a high degree of freedom. [Brief explanation of the drawing]

[0008] [Figure 1] This is a schematic diagram showing an example of a crystal junction. [Figure 2] This is a schematic diagram showing the three-dimensional structure of the dinuclear rare-earth complex [Tb2(tmh)6(4,4'-bpy)]. [Figure 3]This is a schematic diagram showing the three-dimensional structure of the coordination polymer [Tb(tmh)3(4,4'-bpy)]n. [Figure 4] (I) XRD patterns of [Tb2(tmh)6(4,4'-bpy)], (II) XRD patterns of crystals after exposure to pyridine vapor and before drying, and the XRD pattern of [Tb2(tmh)6(py)2]. [Figure 5] These are the XRD patterns of [Tb(tmh)3(py)1], [Tb(tmh)3(4,4'-bpy)]n, and the crystal after (III) pyridine removal. [Figure 6] These are the XRD patterns of crystals obtained using saturated vapor of 3-bromopyridine (3-Brpy), 3-chloropyridine (3-Clpy), 3-fluoropyridine (3-Fpy), or pyridine (py), and the XRD pattern of the coordination polymer [Tb(tmh)3(4,4'-bpy)]n. [Figure 7] (III) XRD patterns of the crystal [Tb(tmh)3(py)1] and the coordination polymer [Tb(tmh)3(4,4'-bpy)]n after pyridine removal by drying. [Figure 8] (III) XRD patterns of the crystal [Tb(tmh)3(3-Brpy)1] and the coordination polymer [Tb(tmh)3(4,4'-bpy)]n after removal of 3-bromopyridine by drying. [Figure 9] This is a photograph of an example of a crystal junction. [Figure 10] These are the absorption spectra of [Tb(tmh)3(4,4'-bpy)]n and [Dy(tmh)3(4,4'-bpy)]n, and the wavelength profiles of the excitation light. [Figure 11] These are the spatially resolved emission spectra of the crystals before and after the formation of the bond. [Figure 12] These are the spatially resolved emission spectra of the two separated crystals. [Modes for carrying out the invention]

[0009] The present invention is not limited to the following examples.

[0010] Figure 1 is a schematic diagram showing an example of a crystal joint. The crystal joint 5 shown in Figure 1 is composed of a first crystal 1 containing a first coordination polymer and a second crystal 2 containing a second coordination polymer. The first crystal 1 and the second crystal 2 are joined at the joint 10. Here, "the first crystal and the second crystal are joined" means that they are physically bonded together without the use of other materials such as adhesives. For example, if the second crystal moves in accordance with the movement of the first crystal, then the first crystal and the second crystal can be considered to be joined.

[0011] The number of first and second crystals constituting the crystal bond is not particularly limited. For example, multiple first crystals and multiple second crystals may be bonded alternately. Two or more second crystals may be bonded to one first crystal, or two or more first crystals may be bonded to one second crystal. The crystal bond may further have other crystals containing coordination polymers that are different from the first and second crystals. In this case, the other crystals are bonded to at least one of the first or second crystals.

[0012] The first coordination polymer in the first crystal 1 has a main chain containing a first rare earth ion and a first linker ligand that forms a coordination bond with the first rare earth ion. The second coordination polymer in the second crystal 2 has a main chain containing a second rare earth ion and a second linker ligand that forms a coordination bond with the second rare earth ion. The main chains of the first and second coordination polymers are formed by the alternating linkage of the first or second rare earth ion and the first or second linker ligand. In the case of crystal assembly 5 illustrated in Figure 1, the first rare earth ion is dysprosium ion Dy(III), the second rare earth ion is terbium ion Tb(III), and the first and second linker ligands are 4,4'-bipyridine. In the crystal junction 5, Dy(III) in the first crystal 1 is excited by excitation light with a wavelength of 460 nm, causing the first crystal 1 to emit light at a wavelength of 570 nm. Additionally, energy transfer from the first crystal 1 to the second crystal 2 causes the second crystal 2 to emit light at a wavelength of 545 nm. This phenomenon will be described in detail in the examples below.

[0013] At the junction 10, the first linker ligand or the second linker ligand may form a coordination bond with the first rare earth ion and the second rare earth ion. In this case, the first coordination polymer and the second coordination polymer are linked, and long-distance energy transfer between them is particularly efficient.

[0014] The first rare earth ion and the second rare earth ion may be different. If the types of rare earth ions are different, for example, the second crystal may emit strong light by exciting the first rare earth ion with excitation light of a wavelength that does not excite the second rare earth ion. In this case, the strong emission of light from the second crystal is thought to be due to energy transfer from the first crystal 1 containing the excited first rare earth ion to the second crystal 2. If at least one of the first or second rare earth ions is a plurality of types of rare earth ions, some of the first and second rare earth ions may be different from each other.

[0015] The first and second rare earth ions can each be ions of one or more rare earth elements selected from the group consisting of, for example, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Tb, Dy, Ho, Er, Tm, Yb, and Lu. In multiple constituent units of the coordination polymer, the first and second rare earth ions may be the same or different. The rare earth ions are, for example, divalent or trivalent cations. For example, the first rare earth ion may be Dy and the second rare earth ion may be Dy, Tb, Eu, Yb, Gd, Sm, Nd, Ho, Er, or Tm; the first rare earth ion may be Tb and the second rare earth ion may be Tb, Eu, Yb, Gd, Sm, Nd, Ho, Er, or Tm; the first rare earth ion may be Eu and the second rare earth ion may be Eu, Yb, Gd, Sm, Nd, Ho, Er, or Tm; the first rare earth ion may be Yb and the second rare earth ion may be Yb, Gd, Sm, Nd, Ho, Er, or Tm; the first rare earth ion may be The first rare earth ion may be Gd, and the second rare earth ion may be Gd, Sm, Nd, Ho, Er, or Tm; the first rare earth ion may be Sm, and the second rare earth ion may be Sm, Nd, Ho, Er, or Tm; the first rare earth ion may be Nd, and the second rare earth ion may be Nd, Ho, Er, or Tm; the first rare earth ion may be Ho, and the second rare earth ion may be Ho, Er, or Tm; the first rare earth ion may be Er, and the second rare earth ion may be Er or Tm; and the first rare earth ion may be Tm, and the second rare earth ion may be Tm.

[0016] The first linker ligand and the second linker ligand may be the same or different from each other. For example, the first and second linker ligands may be given by the following equation (1): [ka] The ligand compound may be represented by formula (1). In formula (1), X represents a direct bond or a divalent or trivalent linking group, Z represents a group containing a coordinating functional group, and p represents 1 or 2. Multiple Zs in the same molecule may be the same or different.

[0017] X may be a direct bond, an arylene group (e.g., a phenylene group), a C1-C9 alkylene group, an oxy group, a sulfide group, an amino group, an amide group, a sulfonyl group, an aryltriyl group, or a C1-C9 alkanetriyl group. The arylene group and the aryltriyl group may be groups containing two or more aromatic rings linked to each other by single bonds. The linking groups exemplified above may be unsubstituted or substituted. X may also be a direct bond.

[0018] Z may be a nitrogen-containing aromatic group or a phosphine oxide group. When Z is a nitrogen-containing aromatic group, the ligand compound may be, for example, a compound represented by the following formula (11). [ka]

[0019] X and p in equation (11) are the same as X and p in equation (1). A in equation (11) 1 This refers to a group of atoms that form a nitrogen-containing aromatic group, which may have substituents, together with a nitrogen atom. Multiple A atoms in the same molecule 1 They may be the same or different. A 1 The nitrogen-containing aromatic group formed by the nitrogen atom may be a heteroaryl group or a monovalent group having two or more aromatic rings linked to each other by single bonds. This nitrogen-containing aromatic group may be substituted with any substituent such as an alkyl group, a halogen atom, or a hydroxyl group.

[0020] Specific examples of ligand compounds (bidentate ligands) of formula (11) when p is 1 and X is a direct bond include the following compounds. These compounds may have substituents such as aryl groups and aliphatic hydrocarbon groups. [ka]

[0021] Specific examples of ligand compounds (bidentate ligands) of formula (11) when p is 1 and X is a divalent linking group include the following compounds. In the formula, Ar represents an aryl group. These compounds may have substituents such as aryl groups and aliphatic hydrocarbon groups. [ka]

[0022] Specific examples of ligand compounds (tridentate ligands) represented by formula (11) when p is 2 and X is a trivalent linking group include the following compounds. These compounds may have substituents such as aryl groups and aliphatic hydrocarbon groups. [ka]

[0023] A in equation (11) 1 The nitrogen-containing aromatic group formed by nitrogen atoms may contain two or more nitrogen atoms that form a coordinate bond with rare earth ions. p is 1, X is a direct bond, and A 1 Specific examples of ligand compounds (tridentate ligands) represented by formula (11) when the nitrogen-containing aromatic group formed by nitrogen atoms contains two nitrogen atoms include the following compounds. These compounds may have substituents such as aryl groups and aliphatic hydrocarbon groups. [ka]

[0024] The first and second coordination polymers may contain a non-linker ligand that forms a coordination bond with one first or second rare earth ion. The non-linker ligand may be optically active. An example of a non-linker ligand is a diketone ligand represented by the following formula (12). An example of an optically active non-linker ligand is (aR)-a-methyl-4-pyridinemethanol. [ka]

[0025] In formula (12), R 1 and R 2 each independently represent an optionally substituted aliphatic hydrocarbon group having 3 to 20 carbon atoms, or an optionally substituted aromatic group, and R 3 represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aromatic group. R 3 may be bonded to R 1 or R 2 to form an optionally substituted cyclic aliphatic hydrocarbon group or an optionally substituted aromatic group. When R 1 and R 2 are relatively bulky groups, the structure of the linker ligand is easily twisted. Twisting of the ligand structure facilitates the formation of an eight-coordinate complex structure. Since π-electron resonance is restricted by the twisting of the linker ligand structure, it is possible to increase the excited state of the linker ligand. Thereby, the luminescence quantum efficiency and photosensitized energy transfer efficiency can be improved. The substituent that may be possessed by the aliphatic hydrocarbon group or aromatic group as R 1 , R 2 , or R 3 may be a halogen atom (for example, a fluorine atom or a chlorine atom), an aryl group, a hydroxyl group, a nitro group, an amino group, a sulfonyl group, a cyano group, a silyl group, a phosphonic acid group, a diazo group, or a mercapto group. R 3 may be a deuterium atom.

[0026] R 1 , R 2 , or R 3Examples of aliphatic hydrocarbon groups that may have substituents as include linear or branched alkyl groups, linear or branched perfluoroalkyl groups, linear or branched perchloroalkyl groups, linear or branched alkenyl groups (e.g., allyl and butenyl groups), linear or branched perfluoroalkenyl groups (e.g., perfluoroallyl and perfluorobutenyl groups), linear or branched perchloroalkenyl groups, cycloalkyl groups, perfluorocycloalkyl groups, perchloroalkyl groups, cycloalkenyl groups (e.g., cyclopentyl and cyclohexyl groups), perfluorocycloalkenyl groups, aralkyl groups (e.g., benzyl and phenethyl groups), perfluoroaralkyl groups (e.g., perfluorobenzyl groups), and linear or branched alkynyl groups. 1 and R 2 This may be a t-butyl group.

[0027] R 1 or R 2 The aromatic group may be an aryl group, a heteroaryl group, or a group having two or more aromatic rings, which may be substituted, and which are linked to each other by a single bond. These aromatic groups may be substituted. Examples of substituted aryl groups include phenyl, perfluorophenyl, perchlorophenyl, naphthyl, perfluoronaphthyl, and perchloronaphthyl groups. Examples of substituted heteroaryl groups include pyridyl and perfluoropyridyl groups. Examples of groups having two or more aromatic rings, which may be substituted, and which are linked to each other by a single bond include biphenyl, perfluorobiphenyl, and perchlorobiphenyl groups.

[0028] The first coordination polymer and the second coordination polymer may contain a constituent unit that includes an eight-coordinate complex structure containing the first or second rare earth ion. For example, if the first and second coordination polymers contain a ligand compound represented by formula (1) (linker ligand) and a diketone ligand represented by formula (12) (non-linker ligand), the first coordination polymer may contain a constituent unit represented by the following formula (I), and the second coordination polymer may contain a constituent unit represented by the following formula (II). The constituent unit represented by formula (I) or (II) includes an eight-coordinate complex structure. [ka] [ka]

[0029] In equations (I) and (II), X, Z, R 1 , R 2 , R 3 , and p are synonymous with the above. Ln 1 This represents the first rare earth ion, Ln 2 This represents a second rare earth ion. In the constituent units represented by multiple formulas (I) in the first crystal, Ln 1 X, Z, R 1 , R 2 , R 3 , and p may be the same or different. In the constituent units represented by multiple formulas (II) in the second crystal, Ln 2 X, Z, R 1 , R 2 , R 3 , and p may be the same or different.

[0030] A method for producing the crystal joint described above includes, for example, preparing a first crystal containing a rare earth complex containing a first rare earth ion and a first linker ligand, and a second crystal containing a rare earth complex containing a second rare earth ion and a second linker ligand; exposing the first and second crystals to a gas containing a monodentate ligand compound containing a nitrogen atom while they are in contact, thereby introducing the monodentate ligand compound into the first and second crystals; and removing the monodentate ligand compound from the first and second crystals to form a first coordination polymer and a second coordination polymer in the first and second crystals, respectively, thereby joining the first and second crystals.

[0031] The rare earth complexes contained in the first and second crystals before exposure to a gas containing a monodentate ligand compound (hereinafter sometimes referred to as the "treatment gas") may contain a hepta-coordinate complex structure containing the first or second rare earth ion. The hepta-coordinate complex structure can be easily transformed into an octa-coordinate complex structure by introducing the monodentate ligand compound. As a result, it is thought that a coordination polymer having an octa-coordinate complex structure can be easily formed when the monodentate ligand compound is removed. The first and second crystals before exposure to the treatment gas may also be single crystals of the rare earth complex.

[0032] If the boiling point of the monodentate ligand compound is low, it is easier to remove the monodentate ligand compound introduced into the crystal in order to remove the coordination polymer. Therefore, the boiling point of the monodentate ligand compound at 1 atmosphere may be 200°C or lower. The boiling point of the monodentate ligand at 1 atmosphere may be 60°C or higher.

[0033] The monodentate ligand compound may be a nitrogen-containing aromatic compound. The nitrogen-containing aromatic compound may be, for example, pyridine or a pyridine derivative. The pyridine derivative has a pyridine ring and a substituent bonded to the pyridine ring. The substituent may be, for example, a halogen group, an alkyl group (e.g., a methyl group), or a nitro group. The monodentate ligand compound may be, for example, at least one selected from the group consisting of pyridine, 3-bromopyridine, 3-chloropyridine, 3-fluoropyridine, 3-iodopyridine, 2-fluoropyridine, 2-chloropyridine, 2-fluoropyridine, 2-iodopyridine, pentafluoropyridine, 4-methylpyridine, 2,4,6-trimethylpyridine, and 3-nitropyridine. The monodentate ligand compound may be at least one selected from the group consisting of pyridine, 3-bromopyridine, 3-chloropyridine, and 3-fluoropyridine.

[0034] The first and second crystals are exposed to a processing gas, thereby introducing a monodentate ligand compound into them. The temperature of the processing gas to which the first and second crystals are exposed may be, for example, between -50°C and 250°C. The processing gas may be a saturated vapor gas of the monodentate ligand compound. The exposure time of the first and second crystals to the processing gas may be between 1 second and 72 hours.

[0035] By removing the monodentate ligand compound from the first and second crystals, the first and second coordination polymers are formed in the first and second crystals, respectively. It is not necessary for all of the monodentate ligand compound introduced into the first and second crystals to be removed; some of the introduced monodentate ligand compound may remain in the first or second crystal.

[0036] For example, by placing the first and second crystals under a reduced pressure atmosphere, the monodentate ligand compound can be easily removed from the first and second crystals. The pressure of the reduced pressure atmosphere may be, for example, between 0.0001 hPa and 1000 hPa. While the monodentate ligand compound is being removed, the temperature of the first and second crystals may be, for example, between -50°C and 250°C. The time for the process of removing the monodentate ligand compound may be, for example, between 1 second and 72 hours. [Examples]

[0037] The present invention is not limited to the following embodiments.

[0038] 1. Dinuclear rare earth complexes Tb2(tmh)6 and Dy2(tmh)6 Tb2(tmh)6 and Dy2(tmh)6 were prepared as precursors for synthesizing rare earth complexes. Tb2(tmh)6 and Dy2(tmh)6 are rare earth complexes composed of two terbium ions Tb(III) or dysprosium ions Du(III) and six 2,2,6,6-tetramethylheptane-3,5-dione (tmh) atoms.

[0039] Dinuclear rare-earth complexes [Tb2(tmh)6(4,4'-bpy)] and [Dy2(tmh)6(4,4'-bpy)] [ka] Tb2(tmh)6 or Dy2(tmh)6 (0.15 mmol) and 4,4'-bipyridine (4,4'-bpy) (0.10 mmol) were dissolved in methanol. The molar ratio of Tb2(tmh)6 or Dy2(tmh)6 to 4,4'-bpy was 3:2. The solution was stirred at room temperature for 24 hours. The solvent was then removed from the solution by distillation, and the residue was purified by recrystallization in methanol to obtain single crystals of the seven-coordinate dinuclear rare-earth complexes [Tb2(tmh)6(4,4'-bpy)] and [Dy2(tmh)6(4,4'-bpy)]. The XRD of the obtained single crystals was measured. It was confirmed that [Tb2(tmh)6(4,4'-bpy)] forms a seven-coordinate dinuclear rare-earth complex. Figure 2 is a schematic diagram showing the three-dimensional structure of [Tb2(tmh)6(4,4'-bpy)], created based on the XRD measurement results. In the bipyridine skeleton (4,4'-bpy) of [Tb2(tmh)6(4,4'-bpy)], the two pyridine rings were located in approximately the same plane. [Tb2(tmh)6(4,4'-bpy)] Yield: 0.190 g (92%) IR (ATR) ν= 2836-3002 (m, CH), 1589 (m, CN), 1569 cm -1 (s, C=O) elemental analysis (%): calcd. for C 76 H 122 N2O 12 Tb2:C, 58.01; H, 7.81; N, 1.78; found: C, 57.38; H, 7.95; N, 1.32 [Dy2(tmh)6(4,4'-bpy)] Yield: 0.150 g (71%) IR (ATR) ν= 2836-3002 (m, CH), 1589 (m, CN),1569 cm -1 (s, C=O) elemental analysis (%): calcd. for C 76 H 122 N2O 12Dy2+ 3 CH3OH: C, 56.58; H, 8.05; N, 1.67; found: C, 56.78; H,7.77; N, 1.51

[0040] 2. Coordination polymer [Tb(tmh)3(4,4'-bpy)] n Solution synthesis [ka] Tb2(tmh)6 and 4,4'-bipyridine (4,4'-bpy) were dissolved in methanol. The molar ratio of Tb2(tmh)6 to 4,4'-bpy was 1:2. The solution was stirred at room temperature for 2 hours. The solution was allowed to stand, and the precipitated coordination polymer [Tb(tmh)3(4,4'-bpy)] was obtained. n A single crystal was recovered. IR (ATR) = 2836-3002 (m, CH), 1587 (m, CN), 1574 cm -1 (s,C=O) ESI-MS (m / z): calcd. for C 32 H 46 N2O4Tb[M- tmh] + : 681.27, found: 681.27 Elemental analysis (%): calcd. for C 43 H 65 N2O6Tb:C,59.71; H, 7.58; N, 3.24; found: C, 59.35; H, 7.61; N, 3.18

[0041] The obtained single crystal was subjected to XRD analysis. [Tb(tmh)3(4,4'-bpy)] n It was confirmed that it forms a coordination polymer containing the structure of an eight-coordinate rare-earth complex. Figure 3 was created based on the XRD measurement results, [Tb(tmh)3(4,4'-bpy)] n This is a schematic diagram showing the three-dimensional structure of [Tb(tmh)3(4,4'-bpy)]. nIt was confirmed that the two pyridine rings in the bipyridine skeleton (4,4'-bpy) are in a twisted arrangement relative to each other. [Tb(tmh)3(4,4'-bpy)] n The angle between the two pyridine rings in the compound was approximately 47 degrees.

[0042] 3. Solid-phase synthesis of coordination polymers 3-1.[Tb2(tmh)6(4,4'-bpy)] / pyridine A single crystal of [Tb2(tmh)6(4,4'-bpy)] was placed in a reaction vessel. The single crystal was exposed to saturated pyridine vapor by flowing pyridine vapor into the reaction vessel at room temperature. Subsequently, the crystal was dried under a reduced pressure atmosphere and then dried in air for 1 hour to remove the pyridine, resulting in the eight-coordinate type coordination polymer [Tb(tmh)3(4,4'-bpy)]. n We obtained crystals containing [the substance]. [Tb(tmh)3(4,4'-bpy)] n IR (ATR) ν= 2836-3002 (m, CH), 1589 (m, CN),1571 cm -1 (s, C=O) elemental analysis (%): calcd. for C 43 H 65 N2O6Tb1([Tb(tmh)3(4,4'-bpy)] n ) + C 114 H 186 N3O 18 Tb3(3[Tb(tmh)3(py)1]): C, 58.41; H, 7.84; N, 2.17; found: C,58.02; H, 7.84; N, 2.10

[0043] Figure 4 shows the XRD pattern of (I) a single crystal of [Tb2(tmh)6(4,4'-bpy)], (II) the XRD pattern of the crystal after exposure to pyridine vapor and before drying, and the XRD pattern of [Tb2(tmh)6(py)2] (an eight-coordinate complex with a pyridine ligand). The XRD pattern of [Tb2(tmh)6(py)2] was created based on the XRD pattern of a separately prepared single crystal of [Tb(tmh)3(py)2]. Comparison of the XRD patterns suggests that exposure to pyridine vapor caused the pyridine introduced into the crystal to form a coordination bond with terbium instead of bipyridine, thereby changing the structure of the complex to an eight-coordinate type.

[0044] Figure 5 shows the XRD pattern of [Tb(tmh)3(py)1] (a seven-coordinate terbium complex with a pyridine ligand), and the coordination polymer [Tb(tmh)3(4,4'-bpy)]. n These are the XRD patterns of the crystals [Tb(tmh)3(py)1] and [Tb(tmh)3(4,4'-bpy)]. n The XRD patterns were created from the XRD measurement results of each single crystal. From the comparison of the XRD patterns, the obtained crystals were [Tb(tmh)3(py)1] and [Tb(tmh)3(4,4'-bpy)]. n It was suggested that it included [something].

[0045] 3-2. [Tb2(tmh)6(4,4'-bpy)] / 3-fluoropyridine, 3-chloropyridine, or 3-bromopyridine Except for exposing a single crystal of [Tb2(tmh)6(4,4'-bpy)] to saturated vapor of 3-fluoropyridine, 3-chloropyridine, or 3-bromopyridine instead of saturated vapor of pyridine, the eight-coordinate type coordination polymer [Tb2(tmh)6(4,4'-bpy)] was obtained in the same manner as in 3-1. nCrystals containing [Tb(tmh)3(4,4'-bpy)] were obtained. Figure 6 shows the XRD patterns of crystals obtained using saturated vapor of 3-bromopyridine (3-Brpy), 3-chloropyridine (3-Clpy), 3-fluoropyridine (3-Fpy), or pyridine (py), and the coordination polymer [Tb(tmh)3(4,4'-bpy)]. n The XRD pattern of the single crystal is shown. In all cases using pyridine derivatives, [Tb(tmh)3(4,4'-bpy)] is present in the crystal. n It was suggested that it was generated by

[0046] 3-3.[Dy2(tmh)6(4,4'-bpy)] / pyridine The procedure was the same as in 3-1, except that the single crystal of [Dy2(tmh)6(4,4'-bpy)] was replaced with the single crystal of [Tb2(tmh)6(4,4'-bpy)], resulting in the eight-coordinate type coordination polymer [Dy2(tmh)6(4,4'-bpy)]. n Crystals containing the following were obtained. Figure 7 shows the XRD pattern of the crystal after pyridine removal by drying (III), the XRD pattern of [Tb(tmh)3(py)1] (a seven-coordinate terbium complex containing a pyridine ligand), and the coordination polymer [Tb(tmh)3(4,4'-bpy)]. n The XRD patterns are shown. From a comparison of the XRD patterns, the obtained crystals are [Dy(tmh)3(py)1] and the coordination polymer [Dy(tmh)3(4,4'-bpy)]. n It was suggested that it included [something]. IR (ATR) ν= 2836-3002 (m, CH), 1591 (m, CN),1570 cm -1 (s, C=O) elemental analysis (%): calcd. for C 43 H 65 N2O6Dy1([Dy(tmh)3(4,4'-bpy)] n ) + C 114 H 186 N3O 18 Dy3(3[Dy(tmh)3(py)1]): C, 58.15; H, 7.80; N, 2.16; found: C, 57.80; H, 7.68; N, 2.19

[0047] 3-4.[Dy2(tmh)6(4,4'-bpy)] / 3-bromopyridine Except for exposing a single crystal of [Dy2(tmh)6(4,4'-bpy)] to saturated vapor of 3-bromopyridine instead of saturated vapor of pyridine, the eight-coordinate type coordination polymer [Dy2(tmh)6(4,4'-bpy)] was obtained in the same manner as in 3-3. n Crystals containing [Tb(tmh)3(3-Brpy)1] were obtained. Figure 8 shows the XRD pattern of the crystal after (III) removal of 3-bromopyridine by drying, the XRD pattern of [Tb(tmh)3(4,4'-bpy)], and the coordination polymer [Tb(tmh)3(4,4'-bpy)]. n The XRD patterns are shown. From a comparison of the XRD patterns, the obtained crystals are [Dy(tmh)3(3-Brpy)1] and the coordination polymer [Dy(tmh)3(4,4'-bpy)]. n It was suggested that it included [something].

[0048] 4. Optical properties Table 1 shows the optical properties of the single crystals of the prepared dinuclear rare-earth complexes and coordination polymers.

[0049] [Table 1]

[0050] 5. Crystal joint 5-1. Formation of crystalline bonds A first single crystal containing [Dy2(tmh)6(4,4'-bpy)] and a second single crystal containing [Tb2(tmh)6(4,4'-bpy)] were placed in contact with each other on a quartz plate. In this state, the two crystals were exposed to pyridine vapor at room temperature for 10 minutes. After that, the pyridine was evaporated in dry air for 30 minutes, at which point the first and second crystals joined together. Figure 9 is a photograph of the crystal joint formed by the two crystals.

[0051] 4-2. Analysis of crystalline structures In Figure 9, the excitation area, indicated by the dashed line, was irradiated with excitation light at a wavelength of 460 nm ± 10 nm, and the spatially resolved emission spectra at positions (1), (2), (3), or (4) were measured. The spatially resolved emission spectra were similarly measured for the two crystals before they were joined.

[0052] Figure 10 is [Tb(tmh)3(4,4'-bpy)] n and [Dy(tmh)3(4,4'-bpy)] n The absorption spectrum and excitation light wavelength profile are shown. The excitation light effectively excites only Dy(III) in the first crystal. Figure 11 shows the spatially resolved emission spectrum of the crystal. In Figure 11, (a) is the spatially resolved emission spectrum of the two crystals before joining, and (b) is the spatially resolved emission spectrum of the crystal joint. In the case of the two crystals before joining (a), emission based on Dy(III) was clearly observed at position (1) in the first crystal around 570 nm. On the other hand, at positions (2), (3), and (4) in the second crystal, almost no emission based on Tb(III) was observed around 550 nm. A weak emission based on Dy(III) was observed around 570 nm, which is thought to be due to the emission from the first crystal being observed as noise at positions (2), (3), and (4). In the case of the crystal joint (b), [Tb(tmh)3(4,4'-bpy)] n Strong emission based on Tb(III) was observed at positions (3) and (4) in the second crystal containing at a wavelength of around 550 nm. Considering that only Dy(III) in the first crystal is excited by the excitation light, the observed strong emission suggests energy transfer from Dy(III) in the first crystal to Tb(III) in the second crystal. The distance between the edge of the first crystal and position (4) in the second crystal is approximately 150 μm. Energy transfer over such a long distance suggests that coordination polymers were linked together at the junction of the two crystals.

[0053] For comparison, the first and second crystals were placed approximately 100 μm apart, and coordination polymers were formed in each of the two separated crystals by a method including exposure to pyridine vapor. Figure 12 shows the spatially resolved emission spectra of the crystals. In Figure 12, (a) is the spatially resolved emission spectrum of the two crystals before coordination polymer formation, and (b) is the spatially resolved emission spectrum of the two crystals containing the coordination polymer. (1) is the position in the first crystal, and (2), (3), and (4) are the positions in the second crystal. As shown in Figure 12, the emission spectra remained almost unchanged before and after the formation of the coordination polymer, suggesting that the two crystals did not interfere with each other and did not transfer energy. Emission bands based on Tb(III) were observed around 550 nm at positions (2), (3), and (4) in the second crystal, but their intensity was very weak, indicating emission based on direct transitions due to excitation light at 460 nm, and not suggesting energy transfer from Dy(III). [Industrial applicability]

[0054] Crystal junctions can be applied as novel optical materials, such as nanocrystalline pn semiconductors, lasers, and fibers. [Explanation of Symbols]

[0055] 1...First crystal, 2...Second crystal, 5...Crystal junction, 10...Joint.

Claims

1. A first crystal containing the first coordination polymer, A second crystal containing a second coordination polymer, Equipped with, The first crystal and the second crystal are both single crystals. The first crystal and the second crystal are joined together in such a way that they are physically bonded without the need for any other material. The first coordination polymer has a main chain comprising a first rare earth ion and a first linker ligand that forms a coordination bond with the first rare earth ion, wherein the main chain is formed by the alternating linkage of the first rare earth ion and the first linker ligand. The second coordination polymer has a main chain comprising a second rare earth ion and a second linker ligand that forms a coordination bond with the second rare earth ion, wherein the main chain is formed by the alternating linkage of the second rare earth ion and the second linker ligand. The first rare earth ion and the second rare earth ion are different, The first linker ligand and the second linker ligand are given by the following formula (1): 【Chemistry 1】 The ligand compound is represented by the formula, where X is a direct bond, an arylene group, a C1-C9 alkylene group, an oxy group, a sulfide group, an amino group, an amide group, a sulfonyl group, an aryltriyl group, or a C1-C9 alkanetriyl group, the amino group is -NH- or -N<, the arylene group and the aryltriyl group may be groups containing two or more aromatic rings bonded to each other by single bonds, Z represents a nitrogen-containing aromatic group, multiple Zs in the same molecule may be the same or different, p represents 1 or 2, and the first linker ligand and the second linker ligand may be the same or different. The first coordination polymer and the second coordination polymer each contain an octaucoordinate complex structure comprising the first rare earth ion or the second rare earth ion. Crystal junction.

2. The crystal junction according to claim 1, wherein when the first rare earth ion is excited, the second crystal emits light due to energy transfer from the first crystal to the second crystal.

3. The first crystal is a single crystal containing a rare earth complex, which includes a first rare earth ion and a first linker ligand forming a coordinate bond with the first rare earth ion; and the second crystal is a single crystal containing a rare earth complex, which includes a second rare earth ion and a second linker ligand forming a coordinate bond with the second rare earth ion. With the first crystal and the second crystal in contact, the first crystal and the second crystal are exposed to a gas containing a monodentate ligand compound containing nitrogen atoms, thereby introducing the monodentate ligand compound into the first crystal and the second crystal. By removing the monodentate ligand compound from the first crystal and the second crystal, a first coordination polymer and a second coordination polymer are formed in the first crystal and the second crystal, respectively, thereby joining the first crystal and the second crystal so as to be physically bonded together without the use of other materials. Includes, The first coordination polymer has a main chain comprising the first rare earth ion and the first linker ligand that forms a coordination bond with the first rare earth ion, wherein the main chain is formed by the alternating linkage of the first rare earth ion and the first linker ligand. The second coordination polymer has a main chain comprising the second rare earth ion and the second linker ligand that forms a coordination bond with the second rare earth ion, wherein the main chain is formed by the alternating linkage of the second rare earth ion and the second linker ligand. The first rare earth ion and the second rare earth ion are different, The first linker ligand and the second linker ligand are given by the following formula (1): 【Chemistry 2】 The ligand compound is represented by , where X is a direct bond, an arylene group, a C1-C9 alkylene group, an oxy group, a sulfide group, an amino group, an amide group, a sulfonyl group, an aryltriyl group, or a C1-C9 alkanetriyl group, the amino group is -NH- or -N<, the arylene group and the aryltriyl group may be groups containing two or more aromatic rings bonded to each other by single bonds, Z represents a nitrogen-containing aromatic group, multiple Zs in the same molecule may be the same or different, p represents 1 or 2, and the first linker ligand and the second linker ligand are different. The rare earth complex comprises a seven-coordinate complex structure containing the first rare earth ion or the second rare earth ion. The first coordination polymer and the second coordination polymer each contain an eight-coordinate complex structure comprising the first rare earth ion or the second rare earth ion. the monodentate ligand compound is a nitrogen-containing aromatic compound, A method for manufacturing a crystal junction.

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