CN110903309A - Dinuclear dysprosium complex based on pyridine ligand and preparation method and application thereof - Google Patents
Dinuclear dysprosium complex based on pyridine ligand and preparation method and application thereof Download PDFInfo
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- 229910052692 Dysprosium Inorganic materials 0.000 title claims abstract description 20
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 18
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Abstract
The invention discloses a dinuclear dysprosium complex based on a pyridine ligand and a preparation method and application thereof. The chemical formula of the complex is [ Dy2(L)2(NO3)4]L is 2-amino-1, 2-di-pyridine-ethanol with one negative charge after hydroxyl hydrogen atom is removed; the complex belongs to a monoclinic system, I2/a space group. The preparation method of the binuclear dysprosium complex comprises the following steps: putting dysprosium nitrate hexahydrate and 2- (aminomethyl) -pyridine into a mixed solvent, heating for reaction in the presence of 4-methoxy-3-hydroxybenzaldehyde, cooling a reactant, separating out crystals, and collecting the crystals to obtain the dysprosium nitrate-N-oxide. The binuclear dysprosium complex of the invention is used for organic solventsHas good luminous response, particularly good luminous response to acetic acid and acetonitrile, can be used for detecting or identifying different organic solvents, and can be used as a sensitizer.
Description
Technical Field
The invention relates to a rare earth complex, in particular to a dinuclear dysprosium complex based on a pyridine ligand and a preparation method and application thereof.
Background
Coordination chemistry plays a crucial role in the design of photoluminescent probes for metal ions. Coordination of the metal to the organic dye causes a different optical reaction, indicating that there is energy transfer between them. d6、d8And d10The configured luminescent lanthanide and transition metal complexes often exhibit unique luminescent properties different from organic dyes, such as high quantum yield, large combustion volume, long emission wavelength and emission lifetime, and can be used as probes for exploring luminescent metal ions, anions and neutral substances due to low sensitivity to microenvironment. In the literature, the design principles and coordination chemistry-related studies of metal problems based on the pct, esprit, fit and exiter formation mechanisms are discussed in detail. Based on Ln3+And d6、d8And d10The fluorescent probe design of metal complexes has also been investigated by discussing certain factors that affect the fluorescence of these metal complexes. The research on the photoluminescence probe for identifying the essential metal cations of human body or the toxic metal cations in environment is rapidly developed, and the emphasis is to introduce the design principle and sensing behavior. In addition, there are also some that combine metal coordination related sensing behavior and design approaches, such as metal complex based photoluminescent probes that discuss biologically relevant particles ppi, neutral biomolecules adenosine triphosphate, nitric oxide, and hydrogen sulfide. .
Pyridine-based ligands, such as 2,2' -bipyridine and 1,10-phenanthroline, have attracted considerable interest in the field of supramolecular chemistry as well as in material science. Over the past decades, polymers containing phosphorescence have been weighted d6Transition metal ion complexes have attracted much attention, particularly because of the utility of these metal complexes, such as ru (ii), ir (iii), os (ii) and re (i) ions for important applications in material science. By embedding the metal complex into the polymer structure, the photophysical and electrochemical properties of the obtained material can regulate the properties of the metal complex and the polymer through the properties: such as processability and film-forming ability. Meanwhile, metal polymers are receiving a wide attention from various scientific research fields: supramolecular chemistry, basic electron and energy transfer, metalsIon sensors and electronic devices. Some groups have also extensively studied photovoltaic and optical power limiting applications for metal polymers containing transition metal elements. d6Preparing metal ions [ namely Ru (II), Ir (III), Os (II) and Re (I)]Are selected transition metal ions, and have photosensitivity and a broad absorption wavelength in the visible light region due to their characteristic spectral properties. Their unique coherence of chemical stability, redox properties, luminescence, excited state lifetime and excited state reactivity is a trigger for the synthesis of numerous derivatives. Late d with Metal-ligand Charge transfer (MLCT) feature6The relatively long-lived excited states of metal complexes have prompted comprehensive photophysical and photochemical research.
Photoluminescence technology has high sensitivity and selectivity and high time and space resolution, and is considered to be one of effective means for detecting various analysis material components. The fine instrumentation capabilities, commercial availability, lower detection limits, in situ and in vivo detection capabilities make this technique extremely attractive. The sensing and imaging of photosites of biological and environmental interest for chemical species has become an important and rapidly evolving area stimulated to a large extent by improvements in confocal microscopy and optical imaging techniques. Over the last decade, a large number of photoluminescence phenomena with various properties have been reported. They can be used to detect or image specific molecules, microenvironments, biological processes and events.
In photoluminescence sensing and detection, metal coordination induced changes in photophysical, electrophysical or biological properties are indispensable relevant applications. Most metal ion fluorescent probes are developed based on metal coordination-induced changes in emission intensity, lifetime, or wavelength of organic dyes. The fluorescent radiation of the metal complex comes from the radiative immobilization of the pi-pi x excited state of the organic dye. Based on d6、d8And d10Photoluminescent probes of configuration lanthanide Ln and transition metal cations differ from organic dyes, which luminesce with emission from thermal relaxation of the metal center (MC, by LMCT process) or MLCT excited state.
By reacting an organic fluorophore with a specific chelating agentBulk) in combination as a fluorescent signal transmitter is a common method of designing metal ion fluorescent probes. In this case, coordination of the metal to the receptor is critical. The presence of metal cations is detected by varying the fluorescence intensity, lifetime or excitation/emission maximum. The intramolecular interaction between the fluorophore and the receptor is crucial for the design of these fluorescent probes[9]. Conventional PET mechanisms such as photoinduced electron transfer fluorescence resonance energy transfer of Photoinduced Charge Transfer (PCT). FRET and the formation of photo-induced exciton/exciton clusters are common methods for the construction of probe molecules. On the other hand, new theories such as proton transfer (ESIPT) and aggregation induction in metal ion coordination inhibition excited state molecules are widely applied, and emission (AIE) is also used for designing probes.
The emission metal complex has the characteristics of high quantum yield, large combustion displacement, long emission wavelength, long service life, good water solubility and the like. Their emission is generally ph independent, less sensitive to the microenvironment, and has important advantages over organic fluorophores. These metal complexes are potential fluorescent reporters for designing photoluminescent probes. The most interesting examples reported to date are lanthanide complexes (Ln ═ Sm) based on luminescence3+，Eu3+，Tb3+，Dy3+，Yb3+) Or has d6，d8And d10Configurational transition metal complexes. Their emission is commonly referred to as phosphorescence according to their mechanism associated with intersystem crossing (Wisc).
Phosphorescence of lanthanide compounds (Ln ═ Sm)3+，Eu3+，Tb3+，Dy3+，Yb3+) F-f transition from excitation induction, f and f14The complex of the configured lanthanide centers is non-luminescent. Ln for half f filling3+Its structure will lead to a large energy gap between its ground and excited states, which makes it difficult for them to display luminescence in the visible window. Because Ln3+The f-f transition of the ions is forbidden, and the low molar extinction coefficient is not sufficient to excite these metal centers directly. This problem can be solved by combining electrons in some cases, which can also be regarded as Waco-Gilligan into Ln3+And (c) a complex. When an electron is excited from the ground state to its singlet excited state, it is in the triplet state. Then, the energy in the molecule is transferred from the triplet state of the electron to Ln3+Then the luminescent f-f transitions to the ground state of Ln, emitting in the visible range. Due to the light emitting mechanism, the Ln complexes have emission lifetimes between milliseconds and microseconds, the emission phenomenon also known as phosphorescence or fluorescence.
Long-lived Ln ions are advantageous for the detection of analytes in complex microenvironments such as cells, tissues, etc. by time-gating to minimize interference of light scattering or autofluorescence, compared to the short emission lifetimes of most organic dyes (on the nanosecond scale). Ln3+The emission spectra of the complexes are usually well separated. E.g. Tb3+Main of (f)5、d4And f4-d4The emission peaks do not overlap with any EUT emission peaks. Furthermore, Ln3+The inner shell rails of (a) are hardly affected by other factors. Thus, Ln3+The emission bands of the complexes are typically narrow (-20 nm), providing additional advantages for these complexes. In multicolor imaging. The anti-stokes effect is converted from antenna absorption to LNT emission, and the tunable quantum yield is an additional optical characteristic of the Ln complex, thereby providing a suitable platform for designing the luminescent probe. Eu (Eu)3+And Tb3+Are most frequent because of their lower sensitivity of the excimer to vibration quenching effects caused by energy transfer to the O-H, N-H or C-H oscillator, which are often present in solution and imaging microenvironments.
There are several major factors in the quantum yield of rare earth complexes. The energy level of the electronic triplet should be at least 1700cm higher than the excited state of Ln, and too high or too low an energy level will only result in the disappearance of the fluorescence of the antenna. If the energy level of the antenna triplet is too close to Ln3+D excited state of (2), from Ln occurs3+Reverse energy transfer to the antenna, resulting in Ln3+Reduction of luminescence[23]. On the other hand, the antenna and Ln3+The center distance is advantageous to achieve antenna-to-LNT energy transfer. Furthermore, Ln3+The central coordination environment is also connected withThe luminous efficiency and lifetime are closely related. Due to Ln3+Centers tend to have a high coordination number (>6) And show high affinity for hard ligands, a number of Ln3+The complex is subjected to coordination exchange with solvents such as water, so that a non-emission scattering process is triggered, and the quantum yield is remarkably reduced. Thus, the careful design of the antenna ligands and other co-ligands is of great significance for implementing LNT-based luminescent materials for specific analytes. At present, no relevant report on the construction and fluorescence properties of a metal dysprosium complex based on a pyridine ligand exists.
Disclosure of Invention
The invention aims to solve the technical problem of providing a dinuclear dysprosium complex based on a pyridine ligand, which has a novel structure and good luminescence response to acetic acid and acetonitrile, and a preparation method and application thereof.
The dinuclear dysprosium complex based on the pyridine ligand has the chemical formula as follows: [ Dy ]2(L)2(NO3)4]Wherein, L is 2-amino-1, 2-di-pyridine-ethanol with one unit negative charge after hydroxyl hydrogen atom is removed; the complex belongs to a monoclinic system, I2/a space group and has the unit cell parameter of
α＝90.00°，β＝110.003(3)°，γ＝90.00°。
The invention also provides a preparation method of the dinuclear dysprosium complex based on the pyridine ligand, which comprises the following steps: putting dysprosium nitrate hexahydrate and 2- (aminomethyl) -pyridine into a mixed solvent, heating to react in the presence of 4-methoxy-3-hydroxybenzaldehyde, cooling a reactant, separating out crystals, and collecting the crystals to obtain a target complex; wherein the mixed solvent is a composition of methanol and acetonitrile.
In the preparation method, the molar ratio of the dysprosium nitrate hexahydrate and the 2- (aminomethyl) -pyridine is a stoichiometric ratio, and the amount of the dysprosium nitrate hexahydrate can be relatively excessive in the actual operation process. In the composition of the mixed solvent, the volume ratio of methanol to acetonitrile is 2: 1-1: 2. the amount of the mixed solvent may be determined as required, and it is usually preferable that the raw materials for the reaction are dissolved. Specifically, the total amount of the mixed solvent used for all the raw materials is usually 6 to 15mL based on 1mmol of 2- (aminomethyl) -pyridine. In the specific dissolving step, the raw materials can be respectively dissolved by using a certain component in the mixed solvent and then mixed together for reaction; or mixing all the raw materials together and adding the mixed solvent for dissolving.
In the above-mentioned preparation method, the presence of 4-methoxy-3-hydroxybenzaldehyde does not participate in coordination, but when it is not present, the objective complex of the present invention cannot be obtained, and therefore, the present applicant speculates that it functions as a catalyst. The 4-methoxy-3-hydroxybenzaldehyde is used in an amount of usually 0.1 times or more the amount of the 2- (aminomethyl) -pyridine substance, and preferably in an amount corresponding to the amount of the 2- (aminomethyl) -pyridine substance.
In the above production method, the reaction is preferably carried out at not less than 50 ℃ and more preferably at 60 to 120 ℃. When the reaction is carried out at 60-120 ℃, the reaction time is usually controlled to be 30-60 h.
The applicant researches and discovers that the dinuclear dysprosium complex based on the pyridine ligand has different luminous intensities in different organic solvents, and can be used for detecting or identifying different organic solvents. Therefore, the invention also comprises the application of the dinuclear dysprosium complex based on the pyridine ligand in the preparation of a sensitizer.
Compared with the prior art, the invention provides the dinuclear dysprosium complex based on the pyridine ligand and the preparation method thereof, and the applicant finds in experiments that the dinuclear dysprosium complex has good luminescent response to organic solvents, particularly good luminescent response to acetic acid and acetonitrile, can be used for detecting or identifying different organic solvents, and therefore, can be used as a sensitizer.
Drawings
FIG. 1 is a photograph of the cooled inner liner tube and the reactants therein after the reaction in example 1 of the present invention; wherein, (a) is a picture of the inner lining tube and the reactant therein after cooling after completion of the reaction, and (b) is an enlarged picture of the crystal at the bottom of the inner lining tube.
FIG. 2 is an IR spectrum of the final product obtained in example 1 of the present invention.
FIG. 3 is a powder diffraction pattern of the final product obtained in example 1 of the present invention.
FIG. 4 is a thermogravimetric plot of the final product made in example 1 of the present invention.
FIG. 5 is a crystal structure diagram of the final product obtained in example 1 of the present invention.
FIG. 6 is a photograph of the cooled liner tube and the reactants therein after reaction for 48h under the same conditions as in example 1 for three control experiments; wherein (a) represents HL2+ Dy (NO)3)3·6H2O, (b) represents HL1+ Dy (NO)3)3·6H2O, (c) represents HL1+ HL 2).
FIG. 7 is a UV spectrum of the complex of the present invention in different solvents.
FIG. 8 is a fluorescence spectrum of the complex of the present invention in different solvents.
FIG. 9 shows the complex of the present invention, HL1, HL2 and Dy (NO)3)3·6H2The fluorescence spectrum of O in ethanol shows that complex represents the complex of the invention.
FIG. 10 shows the complex of the present invention, HL1, HL2 and Dy (NO)3)3·6H2The fluorescence spectrum of O in acetonitrile shows that complex represents the complex of the invention.
Detailed Description
The present invention will be better understood from the following detailed description of specific examples, which should not be construed as limiting the scope of the present invention.
Example 1: complex [ Dy2(L)2(NO3)4](hereinafter also referred to simply as complex)
0.5mmol of 4-methoxy-3-hydroxybenzaldehyde (hereinafter also abbreviated as HL1) (76mg) was weighed out into a reaction vessel equipped with a polytetrafluoroethylene-lined tube, and 10mL of a solution prepared from methanol and acetonitrile in a weight ratio of 1: 1 in the mixed solvent, stirring for 5min and dissolving; then 0.5mmol Dy (NO) was weighed3)3·6H2Placing O (228mg) in the reaction kettle, and continuously stirring for 5min to dissolve; taking 0.5mmol of 2- (aminomethyl) -pyridine (hereinafter also referred to as HL2 or ligand HL2) (61 mu L), fully stirring for 5min, uniformly mixing the whole reaction system, and sealing; and then, placing the reaction kettle at the temperature of 80 ℃ for reaction for 48h, taking out, cooling, observing that dark green strip crystals are separated out from the lining tube (as shown in figure 1), collecting the crystals, and drying. Yield 35% (based on HL 2).
The product obtained in this example was characterized:
1) the spectrum of the infrared spectrum analysis is shown in figure 2.
The infrared spectrogram shows that: the complex is 3400--1Two peaks appear between, which are 3273cm respectively-1、3340cm-1We know the telescopic shock absorption peaks of primary amine and secondary amine, and the two primary amines are 3200--1In between, secondary amine is one, tertiary amine is absent, it is clear that these two peaks correspond to the N-H stretching vibration on primary amine; 3070-3020cm-1,1600-1510cm-1，900-700cm-1Is the characteristic absorption peak of pyridine, which can be seen in 1595cm-1、1042cm-1、786cm-1Is the characteristic absorption peak of pyridine; 1600cm-1The absorption peaks in the vicinity indicate a structure of-C ═ N.
2) Powder diffraction analysis, the spectrum is shown in figure 3.
As can be seen from FIG. 3, the experimental spectrum and the theoretical spectrum obtained by fitting the crystal data are basically consistent, and the complex is proved to be pure phase, so that the reliability of the data obtained by characterization is ensured.
3) Thermogravimetric analysis, the curve of which is shown in FIG. 4.
Thermogravimetric analysis shows that [ Dy ] of complex of the invention2(L)2(NO3)4]Thermal analysis curve ofIn N2Under protection, the temperature range is from 30 ℃ to 1000 ℃, and the collection is carried out at the temperature rising speed of 5 ℃/min. Complex [ Dy2(L)2(NO3)4]The quality is relatively stable before the temperature is 260 ℃, and the weight loss is rapidly realized after the continuous heating. The higher temperature frame undergoes thermal decomposition with weight loss. As can be seen from the TG diagram, the complex [ Dy2(L)2(NO3)4]In the absence of a guest molecule. The absence of guest molecules indicates close intermolecular packing, which also corresponds to the packing pattern shown in the packing diagram.
4) And (3) analyzing a crystal structure:
determining the blackish green elongated crystals with perfect surface structures by X-ray diffraction to determine the crystal structures, wherein the obtained crystal structure data are shown in the following table 1, part of bond length data are shown in the following table 2, part of bond angle data are shown in the following table 3, the crystal structures of the obtained blackish green elongated crystals are shown in the figure 5, and the obtained blackish green elongated crystals are determined to be the dinuclear dysprosium complex [ Dy ] based on pyridine ligands according to the invention2(L)2(NO3)4]Wherein, L is 2-amino-1, 2-di-pyridine-ethanol with one unit negative charge after hydroxyl hydrogen atom is removed.
Table 1: crystal structure data sheet of the complexes of the invention
Table 2: partial bond length table of the complexes of the invention
| Dy(1)-O(1) | 2.556(10) | Dy(1)-O(6) | 2.493(10) | Dy(1)-N(3) | 2.324(7) |
| Dy(1)-O(3) | 2.438(9) | Dy(1)-N(1) | 2.501(10) | Dy(1)-N(3)#1 | 2.324(7) |
| Dy(1)-O(4) | 2.468(10) | Dy(1)-N(2) | 2.545(10) | Dy(1)-N(4) | 2.539(10) |
Table 3: partial bond angle meter for the complexes of the invention
The X-ray single crystal diffraction shows that the complex belongs to a monoclinic system I2/a space group, and the unit cell parameter is
α ═ 90.00 °, β ═ 110.003(3 °), γ ═ 90.00 °, and the asymmetric unit is composed of a ligand HL2 and two NO' s3 -And a Dy (III). The metal center isNine coordination, consisting of 5N atoms from the ligand and 4O atoms from the nitrate, two dysprosium ions are bridged by the nitrogen atom on the ligand generated in situ to form a binuclear structure.
Since HL1 did not participate in coordination in the structure analyzed from the single crystal, the applicant immediately performed three control experiments (specifically, (a) HL2+ Dy (NO)3)3·6H2O，(b)HL1+Dy(NO3)3·6H2O, (c) HL1+ HL2) were allowed to react for 48h under the same experimental conditions, and the results showed that the three control experiments were clear solutions and no precipitation or other phenomena occurred, and the photographs of the cooled liner and the reactants therein are shown in fig. 6. Therefore, the applicant speculates that HL1 may play a catalytic role in the reaction system although not participating in coordination.
Example 2
Example 1 was repeated, except that the volume ratio of methanol and acetonitrile was changed to 1: 2.
the result was a greenish black elongated crystal. Yield 28% (based on HL 2).
The product obtained in the embodiment is analyzed by single crystal diffraction, and the obtained blackish green strip crystal is determined to be the target complex of the invention.
Example 3
Example 1 was repeated, except that the volume ratio of methanol and acetonitrile was changed to 2: 1, the reaction is carried out at 120 ℃ for 30 h.
The result was a greenish black elongated crystal. Yield 14% (based on HL 2).
The product obtained in the embodiment is analyzed by single crystal diffraction, and the obtained blackish green strip crystal is determined to be the target complex of the invention.
Example 4
Example 1 was repeated, except that the reaction was carried out at 50 ℃ for 60 hours.
The result was a greenish black elongated crystal. Yield 19% (based on HL 2).
The product obtained in the embodiment is analyzed by single crystal diffraction, and the obtained blackish green strip crystal is determined to be the target complex of the invention.
Example 5: ultraviolet and fluorescence measurement of the complex of the invention
Dissolving the complex in different solvents respectively to obtain a concentration of 1 × 10-5A methanol solution of mol/mL (10mL) was subjected to UV and fluorescence measurements. The ultraviolet absorption peak is shown in FIG. 7, and the result shows that the maximum absorption peak of the used solvent has slight red shift or blue shift around 290nm, and the applicant uses the absorption peak to measure the emission, and the fluorescence test condition is that the slit width is set to 5nm, the sweep rate is 240nm/min, the room temperature is 26 ℃, and the scanning voltage is 490eV, and the spectrogram is shown in FIG. 8.
As can be seen from fig. 8: the emission peaks of the complex in the used solvent are about 386nm, 413nm, 441nm and 560nm and have slight red shift and blue shift, and the complex has good fluorescence effect and high fluorescence intensity in the solution of ethanol and acetonitrile. To determine whether the ligand emits light, the Applicant configured the complexes of the invention, HL1, HL2 and Dy (NO) in equal volumes and concentrations, respectively3)3·6H2As a result of fluorescence measurement using ethanol and acetonitrile solution of O, the slit width was set to 5nm, the scanning speed was 240nm/min, the room temperature was 26 ℃ and the scanning voltage was 490eV as shown in FIGS. 9 and 10.
The results show that: HL1, HL2 and Dy (NO)3)3·6H2None of O was fluorescent, from which it can be seen that: we speculate that the luminescence of the compound belongs to a mode of a metal-ligand compound, and the luminescence mechanism is attributed to fluorescence emission (LMCT) caused by ligand-to-metal charge transfer, and the applicant speculates from the figure that the complex has potential value in the industrial detection of ethanol and acetonitrile.
Claims (6)
1. The dinuclear dysprosium complex based on the pyridine ligand is characterized in that:
the chemical formula of the complex is as follows: [ Dy ]2(L)2(NO3)4]Wherein, L is 2-amino-1, 2-di-pyridine-ethanol with one unit negative charge after hydroxyl hydrogen atom is removed;
the complex belongs to a monoclinic system, I2/a space group and has the unit cell parameter of
α＝90.00°，β＝110.003(3)°，γ＝90.00°。
2. The method for preparing a dinuclear dysprosium complex based on a pyridine ligand as claimed in claim 1, wherein: putting dysprosium nitrate hexahydrate and 2- (aminomethyl) -pyridine into a mixed solvent, heating to react in the presence of 4-methoxy-3-hydroxybenzaldehyde, cooling a reactant, separating out crystals, and collecting the crystals to obtain a target complex; wherein the mixed solvent is a composition of methanol and acetonitrile.
3. The method of claim 2, wherein: in the composition of the mixed solvent, the volume ratio of methanol to acetonitrile is 2: 1-1: 2.
4. the method of claim 2, wherein: the reaction is carried out at a temperature of more than or equal to 50 ℃.
5. The method of claim 2, wherein: the reaction is carried out at 60-120 ℃.
6. Use of a dinuclear dysprosium complex based on a pyridine ligand according to claim 1 for the preparation of a sensitizer.
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| HUI-FENG WANG等: "Multifunctional Binuclear Ln(III) Complexes Obtained viaIn Situ Tandem Reactions: Multiple Photoresponses to Volatile Organic Solvents and Anticounterfeiting and Magnetic Properties", 《INORG. CHEM.》 * |
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