CN101899038A - Near-infrared light emitting ionic complex and preparation method thereof - Google Patents
Near-infrared light emitting ionic complex and preparation method thereof Download PDFInfo
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- CN101899038A CN101899038A CN 200910085765 CN200910085765A CN101899038A CN 101899038 A CN101899038 A CN 101899038A CN 200910085765 CN200910085765 CN 200910085765 CN 200910085765 A CN200910085765 A CN 200910085765A CN 101899038 A CN101899038 A CN 101899038A
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Abstract
The invention discloses a near-infrared light emitting ionic complex and a preparation method thereof. The molecular formula of the near-infrared light emitting lanthanide series ionic complex provided by the invention is [Ln (L0) 3L], and the structure is shown in formula I, wherein Ln is Nd, Er or Yb; R1 and R2 are alkyl of which the number of carbon atoms is 1-4; R3 and R4 are methyl or H; R5, R6, R7 and R8 are H or alkyl of which the number of carbon atoms is 1-3; n is 0 or 1; and L0 (namely XYC3O2H-diketone anion) is anion with a structure shown in formula IA. The novel near-infrared light emitting lanthanide series ionic complex provided by the invention has a wide excitation window in a visible light region and/or a near-infrared light region, simultaneously has excellent photoactivated lanthanide light emitting performance, can be used for preparing a bioluminescence probe with excellent performance, and has important application value and wide prospects in the aspects of biosensing, imaging, fluorescence immunoassay, and the like.
Description
Technical field
The present invention relates to a class and have ionic complex of the near-infrared luminous performance of long wave sensitization and preparation method thereof.
Background technology
The distinct electrical minor structure of lanthanide ion, particularly its 5S
25P
6The shielding effect of electron pair 4f track makes it have many special spectral qualities.They have significant application value at aspects such as luminescent device (electricity-saving lamp, photodiode, indicating meter), optical fiber, optical amplifier, laser, bio-sensing, bio-imaging and fluoroimmunoassays.Lanthanide ion can reduce the fluorescence interference that biomaterial itself produces in the sharp line emission and the long luminous attitude life-span (ms level) of visible or near-infrared region, with this type of title complex is that the bioprobe of luminescent material can make bioanalysis have highly sensitive and high-level efficiency, has avoided a series of problems of using radioelement to bring simultaneously.
Because the f-f transition of lanthanide ion is subjected to eelctric dipole to select the restriction of rate, the light absorpting ability of lanthanide ion itself is very weak, molar extinction coefficient is very little, therefore to obtain luminescent properties preferably, need carry out sensitization to lanthanide ion, promptly absorb exciting light, and transfer the energy to the luminous attitude of lanthanide ion to realize the efficiently luminous of lanthanide ion by sensitive ligand.In the good title complex of the luminescent properties of having reported at present, be the VISIBLE LIGHT EMISSION lanthanide ion title complex of uv photosensitization mostly.For example WO patent WO2003076938-A report with N, N, N ', N '-[(4 '-(5 " '-amino-2 " '-thienyl)-2,2 ': 6 ', 2 " terpyridyls-6,6 ", two bases) two (methylene radical itrile groups)] acetate is as the Eu of sensitive ligand
3+The peak value of the excitation spectrum of title complex appears at the 336nm place, excites the window afterbody to extend to 410nm, and fluorescence quantum yield is 0.15.Yet not only penetration depth is little as exciting light with UV-light, and can cause damage to organism and tissue thereof, and can produce serious background interference; On the other hand, organism and tissue thereof will reduce detection signal strength to the radiative sorption that is positioned at the visible region, make that investigation depth reduces, the detection sensitivity reduction.If the window that excites of lanthanide ion title complex is widened visible light or even near infrared light zone to long wave, not only can increase the investigation depth of detection, also can reduce exciting light to the damage of organism and the interference of scattered light; In addition,, then can make fluoroimmunoassay or bio-imaging have highly sensitive, big investigation depth concurrently, and realize detecting in the organism body of non-invasi if can utilize longwave optical sensitization lanthanide ion emission near infrared light.Therefore, the lanthanide ion title complex with the near-infrared luminous performance of good long wave sensitization has significant application value.
Yet, lanthanide ion title complex sensitive ligand is can sensitization efficient all multifactor relevant with the molecular structure of part, level structure, the ion coordination environment and the level structure of lanthanide ion etc. on every side to the biography of lanthanide ion, so far, still do not have complete, reliable theory and can be used to instruct synthetic design and synthetic work with near infrared emission lanthanide ion title complex of higher sensitized luminescence efficient.Many efficiently sensitization Eu, Tb plasma send the sensitive ligand of visible light, and sensitization Nd, Er, Ho or Yb plasma send the near infrared light of feature effectively.At present, have lanthanide ion title complex still very limited (Werts, M.H.V.et al., Chem.Phys.Lett.1997,276, the 196-201 that good longwave optical excites the near infrared emitting performance; Hebbink, G.A.et al., ChemPhysChem.2002,3,1014-1018; Aita, K.et al., Luminescence 2007,22,455-461; Shavaleev, N.M.et al., Eur.J.Inorg.Chem.2008,1523-1529.).Creating novel near-infrared luminous lanthanide ion title complex, make it to excite to descend to have higher sensitized luminescence efficient at long wave visible light or even near infrared light, is challenging research topic.
Summary of the invention
The invention provides a class and have broad in visible region and/or near-infrared region and excite window, have lanthanide ion title complex of good near infrared light emitting performance and preparation method thereof.
The general structure of near-infrared luminous lanthanide ion title complex provided by the invention is suc as formula shown in the I, and molecular formula is [Ln (L
0)
3L].Wherein, Ln is Nd, Er or Yb; L
0(be XYC
3O
2H
-The diketone negative ion) is selected from shown in the formula IA numbering and is respectively in hfa, pom, dbm, dnm, tta, hft, fod, bta, nta and the nha negative ion any one;
Among the described formula I, preferred R
1, R
2Be ethyl; R
3, R
4Be H; R
5=R
6=R
7=R
8=H or CH
3-; N is 0 or 1; L
0Be tta and the fod in the negative ion shown in the formula IA; Ln is Nd, Er or Yb (structure is suc as formula shown in the II).
The preparation method of lanthanide ion title complex provided by the invention is to make compound shown in the formula III structural formula and Ln (L
0)
3Reaction, reaction product obtains the novel Photostimulable luminescence lanthanide ion title complex shown in the formula I after operations such as precipitation, washing.Wherein, R in the formula III
1, R
2Be that carbonatoms is the alkyl of 1-4; R
3, R
4Be methyl or H; R
5, R
6, R
7, R
8For H or carbonatoms are the alkyl of 1-3; N is 0 or 1.Ln is Nd, Er or Yb among the formula IV; L
0For structure suc as formula the negative ion shown in the IA.
Comprise also in the described method that the lanthanide ion title complex that described reaction is obtained carries out purifying, described purification process makes the title complex precipitation for add poor solvent in complex solution; Described poor solvent is selected from one or more in sherwood oil, normal hexane, the hexanaphthene.
Among the above-mentioned lanthanide ion title complex preparation method, described reaction can be carried out in many organic solvents, for example tetrahydrofuran (THF), ether, benzene, toluene, chloroform, methylene dichloride equal solvent.
The lanthanide ion title complex that has near-infrared luminous ability shown in the formula I provided by the present invention excites the following good photosensitization lanthanide ion luminescent properties that has at visible region or near infrared light.For example, R in formula I
1, R
2Be ethyl; R
3, R
4Be H; R
5=R
6=R
7=R
8=CH
3-; N=0; Ln=Nd; L
0During for the tta in the negative ion shown in the formula IA, structure has wide excited by visible light window suc as formula the neodymium title complex shown in the IV, and the maximum excitation peak position of its excitation spectrum (Fig. 1) in toluene solution is in the 402nm place; Concentration is 1.0 * 10
-5During M, excite window to may extend to the 441nm place.Figure 2 shows that title complex IV is the emmission spectrum under the optical excitation of 402nm at wavelength, its emission peak is positioned at the near-infrared region.In addition, title complex shown in the formula I of the present invention has good Near-infrared Double photon excitation luminescent properties, and for example title complex IV can send the feature near-infrared radiation (see figure 3) of neodymium ion under 808nm laser two-photon excitation.R in formula I
1, R
2Be ethyl; R
3, R
4Be H; R
5=R
6=R
7=R
8=CH
3-; N=1; Ln=Nd; L
0During for the tta in the negative ion shown in the formula IA, structure suc as formula the maximum excitation peak position of the excitation spectrum (Fig. 4) of the neodymium title complex shown in the V in toluene solution in about 436nm; When concentration is 1.0 * 10
-5During M, excite window to may extend to the 495nm place.Figure 5 shows that the emmission spectrum of title complex V under the optical excitation of 436nm wavelength.Title complex V can send the feature near-infrared radiation of neodymium ion under 880nm laser two-photon excitation.
As previously mentioned, the sensitized luminescence of rare earth ion is subjected to influence of various factors, and the isoionic f orbitals energy level spacing of Nd, Er, Ho or Yb is little, nonradiative transition probability height, thereby make its sensitized luminescence more difficult." antenna " part (structure is shown in formula III) in Nd provided by the invention, Er, the Yb title complex excites down at visible and/or near infrared light can effectively send out the near infrared light that ground sensitization Nd, Er and Yb ion send feature, and this has only by experiment and could determine.
The near-infrared luminous lanthanide ion title complex of a class provided by the invention can be used for preparing biological fluorescent labeling, has significant application value and bright prospects at aspects such as bio-sensing, imaging and fluoroimmunoassays.
Description of drawings
Fig. 1 is the exciting light spectrogram of neodymium title complex of the present invention (structure is suc as formula IV) in toluene solution, and the detection wavelength is 1064nm;
Fig. 2 is the emmission spectrum of neodymium title complex of the present invention (structure is suc as formula IV) in toluene solution, and excitation wavelength is 402nm;
Fig. 3 is the two-photon excitation emission spectrum of neodymium title complex of the present invention (structure is suc as formula IV) in toluene solution, and excitation wavelength is 808nm;
Fig. 4 is the exciting light spectrogram of neodymium title complex of the present invention (structure is suc as formula V) in toluene solution, and the detection wavelength is 1064nm;
Fig. 5 is the emmission spectrum of neodymium title complex of the present invention (structure is suc as formula V) in toluene solution, and excitation wavelength is 436nm.
Fig. 6 is the emmission spectrum of erbium title complex of the present invention (structure is suc as formula VIII) in toluene solution, and excitation wavelength is 402nm;
Fig. 7 is the emmission spectrum of ytterbium title complex of the present invention (structure is suc as formula IX) in toluene solution, and excitation wavelength is 402nm;
Fig. 8 is the exciting light spectrogram of ytterbium title complex of the present invention (structure is suc as formula XI) in toluene solution, and the detection wavelength is 980nm;
Fig. 9 is the exciting light spectrogram of ytterbium title complex of the present invention (structure is suc as formula XV) in toluene solution, and the detection wavelength is 980nm;
Embodiment
In order to be described more specifically the present invention, now provide some embodiment.But content involved in the present invention is not limited only to these examples.Method among the following embodiment if no special instructions, is ordinary method.Used raw material all can be commercially available in reaction.
The preparation method of near-infrared luminous lanthanide ion title complex of the present invention, its reaction process is shown below:
In formula I and the formula III, R
1, R
2Be that carbonatoms is the alkyl of 1-4; R
3, R
4Be methyl or H; R
5, R
6, R
7, R
8For H or carbonatoms are the alkyl of 1-3; N is 0 or 1.Formula I and molecular formula Ln (L
0)
3In, Ln is Nd, Er or Yb; L
0(be XYC
3O
2H
-The diketone negative ion) be that structure is suc as formula the negative ion shown in the IA.
Embodiment 1, synthetic compound (IV), (IV)=[Nd (tta)
3(VI)], NdC
47H
40N
8F
9O
6S
3
Under argon shield, with 10mL Nd (tta)
32H
2The tetrahydrofuran solution of O (24.9mmol) is added drop-wise in 10mL compound (VI) tetrahydrofuran solution (24.9mmol), and normal temperature stirs 30min down.Remove and desolvate, use a small amount of ether dissolution, filter, separate out solid also washing, drying as precipitation agent, obtain [Nd (tta) with normal hexane
3(VI)] yellow powder 31mg.Wherein, compound shown in the formula VI is to prepare according to the method that embodiment 1 in the following Chinese patent application file provides: 200710118979.2.
Mass spectrum (ESI-MS) characterizes and records [M+Na]
+=1247; Ultimate analysis (quality percentage composition): C, 46.02% (46.11%); H, 3.49% (3.29%); N, 9.41% (9.15%), in the bracket theoretical value; Nuclear magnetic resonance spectrum proof product is (IV).
Structure has wide excited by visible light window suc as formula the neodymium title complex shown in the IV, and the maximum excitation peak position of its excitation spectrum (Fig. 1) in toluene solution is in the 402nm place; When concentration is 1.0 * 10
-5During M, excite window to may extend to about 441nm.Fig. 2 is the emmission spectrum of structure suc as formula the neodymium title complex shown in the IV, and excitation wavelength is 402nm; This title complex can send the characteristic radiation (Fig. 3) of neodymium ion under 808nm laser two-photon excitation.
Embodiment 2, synthetic compound (V), (V)=[Nd (tta)
3(VII)], NdC
53H
44N
8F
9O
6S
3
Under argon shield, with 10mL Nd (tta)
32H
2The tetrahydrofuran solution of O (24.9mmol) is added drop-wise to 2-shown in the 10mL formula VII (4-N, N-diethyl-p-diaminodiphenyl-4 '-yl)-4,6-two (3-1-yl)-1,3,5-triazines compound (C
29H
32N
8) in (24.9mmol) the tetrahydrofuran solution, normal temperature stirs 30min down.Remove and desolvate, use a small amount of ether dissolution, filter, separate out solid also washing, drying as precipitation agent, obtain [Nd (tta) with normal hexane
3(VII)] orange powder 28mg.
Mass spectrum (ESI-MS) characterizes and records [M+Na]
+=1323; Ultimate analysis (quality percentage composition): C, 48.79% (48.95%); H, 3.55% (3.41%); N, 8.46% (8.62%), in the bracket theoretical value; Nuclear magnetic resonance spectrum proof product is (V).
Structure has wide excited by visible light window suc as formula the neodymium title complex shown in the V, and the maximum excitation peak position of its excitation spectrum (Fig. 4) in toluene solution is in about 436nm; When concentration is 1.0 * 10
-5During M, excite window to may extend to the 495nm place.Fig. 5 be structure suc as formula the emmission spectrum of title complex shown in the V, excitation wavelength is 436nm.This title complex can send the feature near-infrared radiation of neodymium ion under 880nm laser two-photon excitation.
In addition, the formula VII compound as reactant is prepared as follows:
Under argon shield, the potassium metal 1.25mmol that newly cuts is added in the anhydrous tetrahydro furan; Add 3 1.75mmol, reflux 3h generates the 3 negative ion; Reaction mixture is placed ice bath, to wherein adding 2-(4-N, N-diethyl biphenyl-4 '-yl)-4,6-two chloro-1,3,5-triazines 0.5mmol, stirring at room 1h, back flow reaction 8-9h in 80-85 ℃ oil bath then.Cooling, concentrated is made eluent with the mixed solution (volume ratio of methylene dichloride and ethyl acetate is 1: 3) of methylene dichloride and ethyl acetate, separates by silica gel column chromatography.The gained crude product is with mixed solution (volume ratio of sherwood oil and methylene dichloride is 1: the 1) recrystallization of sherwood oil and methylene dichloride, synthetic 2-(4-N, the N-diethyl-p-diaminodiphenyl-4 '-yl)-4 of obtaining, 6-two (3,5-dimethyl pyrazole-1-yl)-1,3,5-triazines compound 40mg.
Mass spectrum (EI MS) analysis records the compound molecule quasi-molecular ions M/Z=492 of gained; Ultimate analysis (quality percentage composition): C, 70.57% (70.71%); H, 6.49% (6.55%); N, 22.60% (22.75%), in the bracket theoretical value; Nuclear magnetic resonance spectrum proves that the product structure of above-mentioned preparation is suc as formula shown in the VII.
Embodiment 3, synthetic compound (VIII), (VIII)=[Er (nta)
3(VI)], ErC
65H
52N
8F
9O
6
Under argon shield, with 10mL Er (nta)
32H
2The tetrahydrofuran solution of O (24.9mmol) is added drop-wise in 10mL compound (VI) tetrahydrofuran solution (24.9mmol), and normal temperature stirs 30min down.Remove and desolvate, use a small amount of ether dissolution, filter, separate out solid also washing, drying as precipitation agent, obtain [Er (nta) with normal hexane
3(VI)] yellow powder 32mg.
Mass spectrum (ESI-MS) characterizes and records [M+Na]
+=1402; Ultimate analysis (quality percentage composition): C, 56.45% (56.60%); H, 3.70% (3.80%); N, 8.24% (8.12%), in the bracket theoretical value; Nuclear magnetic resonance spectrum proof product is (VIII).This title complex is to send Er ionic feature near infrared emission (Fig. 6) under the optical excitation of 402nm at wavelength.
Embodiment 4, synthetic compound (IX), (IX)=[Yb (hft)
3(VI)], YbC
53H
40N
8F
21O
6S
3
Under argon shield, with 10mL Yb (hft)
32H
2The tetrahydrofuran solution of O (24.9mmol) is added drop-wise in 10mL compound (VI) tetrahydrofuran solution (24.9mmol), and normal temperature stirs 30min down.Remove and desolvate, use a small amount of ether dissolution, filter, separate out solid also washing, drying as precipitation agent, obtain [Yb (hft) with normal hexane
3(VI)] yellow powder 22mg.
Mass spectrum (ESI-MS) characterizes and records [M+Na]
+=1576; Ultimate analysis (quality percentage composition): C, 41.05% (40.99%); H, 2.43% (2.60%); N, 7.14% (7.21%), in the bracket theoretical value; Nuclear magnetic resonance spectrum proof product is (IX).This title complex is to send Yb ionic feature near infrared emission (Fig. 7) under the optical excitation of 402nm at wavelength.
Embodiment 5, synthetic compound (X), (X)=[Er (nha)
3(VII)], ErC
77H
56N
8F
21O
6
Under argon shield, with 10mL Er (nha)
32H
2The tetrahydrofuran solution of O (24.9mmol) is added drop-wise in 10mL compound (VII) tetrahydrofuran solution (24.9mmol), and normal temperature stirs 30min down.Remove and desolvate, use a small amount of ether dissolution, filter, separate out solid also washing, drying as precipitation agent, obtain [Er (nha) with normal hexane
3(VII)] orange powder 20mg.
Mass spectrum (ESI-MS) characterizes and records [M+Na]
+=1779; Ultimate analysis (quality percentage composition): C, 52.79% (52.68%); H, 3.15% (3.22%); N, 6.49% (6.38%), in the bracket theoretical value; Nuclear magnetic resonance spectrum proof product is (X).Structure can be sent the emission of Er ionic feature near infrared suc as formula the erbium title complex shown in the X under excited by visible light.
Embodiment 6, synthetic compound (XI), (XI)=[Yb (tta)
3(VII)], YbC
53H
44N
8F
9O
6S
3
Under argon shield, with 10mL Yb (tta)
32H
2The tetrahydrofuran solution of O (24.9mmol) is added drop-wise in 10mL compound (VII) tetrahydrofuran solution (24.9mmol), and normal temperature stirs 30min down.Remove and desolvate, use a small amount of ether dissolution, filter, separate out solid also washing, drying as precipitation agent, obtain [Yb (tta) with normal hexane
3(VII)] orange powder 25mg.
Mass spectrum (ESI-MS) characterizes and records [M+Na]
+=1352; Ultimate analysis (quality percentage composition): C, 48.03% (47.89%); H, 3.25% (3.34%); N, 8.45% (8.43%), in the bracket theoretical value; Nuclear magnetic resonance spectrum proof product is (XI).
This title complex is to send the emission of Yb ionic feature near infrared under the optical excitation of 436nm at wavelength.Title complex has wide excited by visible light window, and the maximum excitation peak position of its excitation spectrum (Fig. 8) in toluene solution is in about 436nm; When concentration is 1.0 * 10
-5During M, excite window to may extend to the 495nm place.
Embodiment 7, synthetic compound (XII), (XII)=[Nd (tta)
3(XIII)], NdC
43H
32N
8F
9O
6S
3
Under argon shield, with 10mL Nd (tta)
32H
2The tetrahydrofuran solution of O (24.9mmol) is added drop-wise in 10mL compound (XIII) tetrahydrofuran solution (24.9mmol), and normal temperature stirs 30min down.Remove and desolvate, use a small amount of ether dissolution, filter, separate out solid also washing, drying as precipitation agent, obtain [Nd (tta) with normal hexane
3(XIII)] yellow powder 22mg.Wherein, compound shown in the formula XIII is to prepare according to the method that embodiment 7 in the following Chinese patent application file provides: 200710118977.3.
Mass spectrum (ESI-MS) characterizes and records [M+Na]
+=1191; Ultimate analysis (quality percentage composition): C, 44.45% (44.21%); H, 2.66% (2.76%); N, 9.81% (9.59%), in the bracket theoretical value; Nuclear magnetic resonance spectrum proof product is (XII).This title complex is to send the emission of Nd ionic feature near infrared under the optical excitation of 410nm at wavelength.
Embodiment 8, synthetic compound (XIV), (XIV)=[Er (dnm)
3(XIII)], ErC
88H
65N
8O
6
Under argon shield, with 10mL Er (dnm)
32H
2The tetrahydrofuran solution of O (24.9mmol) is added drop-wise in 10mL compound (XIII) tetrahydrofuran solution (24.9mmol), and normal temperature stirs 30min down.Remove and desolvate, use a small amount of ether dissolution, filter, separate out solid also washing, drying as precipitation agent, obtain [Er (dnm) with normal hexane
3(XIII)] yellow powder 22mg.
Mass spectrum (ESI-MS) characterizes and records [M+Na]
+=1521; Ultimate analysis (quality percentage composition): C, 70.68% (70.57%); H, 4.49% (4.37%); N, 7.51% (7.48%), in the bracket theoretical value; Nuclear magnetic resonance spectrum proof product is (XIV).This title complex is to send the emission of Er ionic feature near infrared under the optical excitation of 410nm at wavelength.
Embodiment 9, synthetic compound (XV), (XV)=[Yb (tta)
3(XIII)], YbC
43H
32N
8F
9O
6S
3
Under argon shield, with 10mL Yb (tta)
32H
2The tetrahydrofuran solution of O (24.9mmol) is added drop-wise in 10mL compound (XIII) tetrahydrofuran solution (24.9mmol), and normal temperature stirs 30min down.Remove and desolvate, use a small amount of ether dissolution, filter, separate out solid also washing, drying as precipitation agent, obtain [Yb (tta) with normal hexane
3(XIII)] yellow powder 32mg.
Mass spectrum (ESI-MS) characterizes and records [M+Na]
+=1220; Ultimate analysis (quality percentage composition): C, 43.29% (43.15%); H, 2.79% (2.69%); N, 9.41% (9.36%), in the bracket theoretical value; Nuclear magnetic resonance spectrum proof product is (XV).
Structure can be sent the emission of Yb ionic feature near infrared suc as formula the ytterbium title complex shown in the XV under excited by visible light.Title complex has wide excited by visible light window, and the maximum excitation peak position of its excitation spectrum (Fig. 9) in toluene solution is in about 410nm; When concentration is 1.0 * 10
-5During M, excite window to may extend to the 445nm place.This title complex can send the feature near-infrared radiation of ytterbium ion under 820nm laser two-photon excitation.
Embodiment 10, synthetic compound (XVI), (XVI)=[Nd (pom)
3(XVII)], NdC
72H
27N
8F
90O
6
Under argon shield, with 10mL Nd (pom)
32H
2The tetrahydrofuran solution of O (24.9mmol) is added drop-wise in 10mL compound (XVII) tetrahydrofuran solution (24.9mmol), and normal temperature stirs 30min down.Remove and desolvate, use a small amount of ether dissolution, filter, separate out solid also washing, drying as precipitation agent, obtain [Nd (pom) with normal hexane
3(XVII)] yellow powder 31mg.Wherein, compound shown in the formula XVII is to prepare according to the method that embodiment 2 in the following Chinese patent application file provides: 200710118979.2.
Mass spectrum (ESI-MS) characterizes and records [M+Na]
+=2977; Ultimate analysis (quality percentage composition): C, 29.02% (29.27%); H, 1.02% (0.92%); N, 3.90% (3.79%), in the bracket theoretical value; Nuclear magnetic resonance spectrum proof product is (XVI).This title complex is to send the emission of Nd ionic feature near infrared under the optical excitation of 400nm at wavelength.
Embodiment 11, synthetic compound (XVIII), (XVIII)=[Nd (dbm)
3(XIX)], NdC
72H
69N
8O
18
Under argon shield, with 10mL Nd (dbm)
32H
2The tetrahydrofuran solution of O (24.9mmol) is added drop-wise in 10mL compound (XIX) tetrahydrofuran solution (24.9mmol), and normal temperature stirs 30min down.Remove and desolvate, use a small amount of ether dissolution, filter, separate out solid also washing, drying as precipitation agent, obtain [Nd (dbm) with normal hexane
3(XIX)] yellow powder 44mg.Wherein, compound shown in the formula XIX is to prepare according to the method that embodiment 3 in the following Chinese patent application file provides: 200710118979.2.
Mass spectrum (ESI-MS) characterizes and records [M+Na]
+=1502; Ultimate analysis (quality percentage composition): C, 58.80% (58.49%); H, 4.69% (4.70%); N, 7.87% (7.58%), in the bracket theoretical value; Nuclear magnetic resonance spectrum proof product is (XVIII).This title complex is to send the emission of Nd ionic feature near infrared under the optical excitation of 400nm at wavelength.
Embodiment 12, synthetic compound (XX), (XX)=[Nd (hfa)
3(XXI)], NdC
40H
35N
8F
18O
6
Under argon shield, with 10mL Nd (hfa)
32H
2The tetrahydrofuran solution of O (24.9mmol) is added drop-wise in 10mL compound (XXI) tetrahydrofuran solution (24.9mmol), and normal temperature stirs 30min down.Remove and desolvate, use a small amount of ether dissolution, filter, separate out solid also washing, drying as precipitation agent, obtain [Nd (hfa) with normal hexane
3(XXI)] yellow powder 42mg.Wherein, compound shown in the formula XXI is to prepare according to the method that embodiment 1 in the following Chinese patent application file provides: 200710118978.8.
Mass spectrum (ESI-MS) characterizes and records [M+Na]
+=1233; Ultimate analysis (quality percentage composition): C, 39.77% (39.71%); H, 2.61% (2.92%); N, 9.03% (9.26%), in the bracket theoretical value; Nuclear magnetic resonance spectrum proof product is (XX).This title complex is to send the emission of Nd ionic feature near infrared under the optical excitation of 408nm at wavelength.
Embodiment 13, synthetic compound (XXII), (XXII)=[Nd (fod)
3(VI)], NdC
53H
58N
8F
21O
6
Under argon shield, with 10mL Nd (fod)
32H
2The tetrahydrofuran solution of O (24.9mmol) is added drop-wise in 10mL compound (VI) tetrahydrofuran solution (24.9mmol), and normal temperature stirs 30min down.Remove and desolvate, use a small amount of ether dissolution, filter, separate out solid also washing, drying as precipitation agent, obtain [Nd (fod) with normal hexane
3(VI)] yellow powder 40mg.
Mass spectrum (ESI-MS) characterizes and records [M+Na]
+=1469; Ultimate analysis (quality percentage composition): C, 44.21% (44.01%); H, 3.99% (4.04%); N, 7.97% (7.75%), in the bracket theoretical value; Nuclear magnetic resonance spectrum proof product is (XXII).This title complex is to send the emission of Nd ionic feature near infrared under the optical excitation of 402nm at wavelength.
Embodiment 14, synthetic compound (XXIV), (XXIV)=[Nd (bta)
3(VII)], NdC
59H
50N
8F
9O
6
Under argon shield, with 10mL Nd (bta)
32H
2The tetrahydrofuran solution of O (24.9mmol) is added drop-wise in 10mL compound (VII) tetrahydrofuran solution (24.9mmol), and normal temperature stirs 30min down.Remove and desolvate, use a small amount of ether dissolution, filter, separate out solid also washing, drying as precipitation agent, obtain [Nd (bta) with normal hexane
3(VII)] yellow powder 12mg.
Mass spectrum (ESI-MS) characterizes and records [M+Na]
+=1305; Ultimate analysis (quality percentage composition): C, 55.41% (55.26%); H, 3.99% (3.93%); N, 8.69% (8.74%), in the bracket theoretical value; Nuclear magnetic resonance spectrum proof product is (XXIV).This title complex is to send the emission of Nd ionic feature near infrared under the optical excitation of 436nm at wavelength.
Embodiment 15, synthetic compound (XXVI), (XXVI)=[Er (fod)
3(VI)], ErC
53H
58N
8F
21O
6
Under argon shield, with 10mL Er (fod)
32H
2The tetrahydrofuran solution of O (24.9mmol) is added drop-wise in 10mL compound (VI) tetrahydrofuran solution (24.9mmol), and normal temperature stirs 30min down.Remove and desolvate, use a small amount of ether dissolution, filter, separate out solid also washing, drying as precipitation agent, obtain [Er (fod) with normal hexane
3(VI)] yellow powder 22mg.
Mass spectrum (ESI-MS) characterizes and records [M+Na]
+=1492; Ultimate analysis (quality percentage composition): C, 43.52% (43.32%); H, 3.96% (3.98%); N, 7.81% (7.63%), in the bracket theoretical value; Nuclear magnetic resonance spectrum proof product is (XXVI).This title complex is to send the emission of Er ionic feature near infrared under the optical excitation of 402nm at wavelength.
Embodiment 16, synthetic compound (XXVIII), (XXVIII)=[Yb (bta)
3(VII)], YbC
59H
50N
8F
9O
6
Under argon shield, with 10mLYb (bta)
32H
2The tetrahydrofuran solution of O (24.9mmol) is added drop-wise in 10mL compound (VII) tetrahydrofuran solution (24.9mmol), and normal temperature stirs 30min down.Remove and desolvate, use a small amount of ether dissolution, filter, separate out solid also washing, drying as precipitation agent, obtain [Yb (bta) with normal hexane
3(VII)] yellow powder 42mg.
Mass spectrum (ESI-MS) characterizes and records [M+Na]
+=1334; Ultimate analysis (quality percentage composition): C, 54.12% (54.05%); H, 3.98% (3.84%); N, 8.43% (8.55%), in the bracket theoretical value; Nuclear magnetic resonance spectrum proof product is (XXVIII).This title complex is to send the emission of Yb ionic feature near infrared under the optical excitation of 436nm at wavelength.
Claims (26)
1. near-infrared light emitting ionic complex comprises part shown in the formula III and metal center ion;
In the described formula III general structure, R
1, R
2Be that carbonatoms is the alkyl of 1-4; R
3, R
4Be methyl or H; R
5, R
6, R
7And R
8Be selected from the alkyl that H or carbonatoms are 1-3 any one; N is 0 or 1;
Described metal center ion is Nd, Er or Yb.
2. title complex according to claim 1 is characterized in that: the general structure of described title complex is suc as formula shown in the I; In the described formula I general structure, Ln is Nd, Er or Yb; R
1And R
2Be that carbonatoms is the alkyl of 1-4; R
3And R
4Be methyl or H; R
5, R
6, R
7And R
8Be selected from the alkyl that H and carbonatoms are 1-3 any one; N is 0 or 1;
Group is selected from shown in the formula IA numbering and is respectively in hfa, pom, dbm, dnm, tta, hft, fod, bta, nta and the nha negative ion any one;
4. title complex according to claim 3 is characterized in that: among the described formula XXX, and n=0,
Group is selected from the negative ion that is numbered tta shown in the formula IA, and the structural formula of described title complex is suc as formula shown in the XXXIII;
9. title complex according to claim 2 is characterized in that: in the described formula I general structure, and Ln=Er, the structural formula of described title complex is suc as formula shown in the XXXI;
10. title complex according to claim 9 is characterized in that: among the described formula XXXI, and R
1, R
2Be ethyl, R
3, R
4Be H; R
5=R
6=R
7=R
8=CH
3-; N=0;
Group is selected from the negative ion that is numbered tta shown in the formula IA, and the structural formula of described title complex is suc as formula shown in the XXXV;
11. title complex according to claim 9 is characterized in that: among the described formula XXXI, R
1, R
2Be ethyl, R
3, R
4Be H; R
5=R
6=R
7=R
8=H; N=0;
Group is selected from the negative ion that is numbered tta shown in the formula IA, and the structural formula of described title complex is suc as formula shown in the XXXVI;
12. title complex according to claim 9 is characterized in that: among the described formula XXXI, R
1, R
2Be ethyl, R
3, R
4Be H; R
5=R
6=R
7=R
8=CH
3-; N=1;
Group is selected from the negative ion that is numbered tta shown in the formula IA, and the structural formula of described title complex is suc as formula shown in the XXXVII;
13. title complex according to claim 2 is characterized in that: Ln=Yb among the described formula I, described complex structure formula is suc as formula shown in the XXXII;
14. title complex according to claim 13 is characterized in that: among the described formula XXXII, R
1, R
2Be ethyl, R
3, R
4Be H; R
5=R
6=R
7=R
8=CH
3-; N=0;
Group is selected from the negative ion that is numbered tta shown in the formula IA, and the structural formula of described title complex is suc as formula shown in the XXXVIII;
15. title complex according to claim 13 is characterized in that: among the described formula XXXII, R
1, R
2Be ethyl, R
3, R
4Be H; R
5=R
6=R
7=R
8=H; N=0;
Group is selected from the negative ion that is numbered tta shown in the formula IA, and described complex structure formula is suc as formula shown in the XV;
16. title complex according to claim 13 is characterized in that: among the described formula XXXII, R
1, R
2Be ethyl, R
3, R
4Be H; R
5=R
6=R
7=R
8=CH
3-; N=1;
Group is selected from the negative ion that is numbered tta shown in the formula IA, and described complex structure formula is suc as formula shown in the XI;
23. a method for preparing the described near-infrared luminous lanthanide ion title complex of claim 2 comprises the steps:
With compound shown in the formula III structural formula and Ln (L
0)
3React, obtain described near-infrared luminous lanthanide ion title complex;
In the described formula III general structure, R
1, R
2Be that carbonatoms is the alkyl of 1-4; R
3, R
4Be methyl or H; R
5, R
6, R
7And R
8Be selected from the alkyl that H and carbonatoms are 1-3 any one; N is 0 or 1;
Molecular formula Ln (L
0)
3In, Ln is Nd, Er or Yb; L
0Be selected from shown in the formula IA numbering and be respectively in hfa, pom, dbm, dnm, tta, hft, fod, bta, nta and the nha negative ion any one;
24. method according to claim 23 is characterized in that: the reaction medium of described reaction is selected from least a in tetrahydrofuran (THF), ether, benzene, toluene, chloroform and the methylene dichloride.
25., it is characterized in that: also comprise in the described method: after reaction finishes, described near-infrared luminous lanthanide ion title complex is carried out the step of purifying according to claim 23 or 24 described methods;
Described purification step is the poor solvent that adds described near-infrared luminous lanthanide ion title complex in reaction system, and the precipitation of washing generation;
Described poor solvent is selected from least a in sherwood oil, normal hexane and the hexanaphthene.
26. a photosensitization Nd, Er or Yb ion send the method for feature near infrared light, comprise the steps: with the described near-infrared light emitting ionic complex of optical excitation claim 1, sensitive ligand in the described near-infrared light emitting ionic complex absorbs energy sensitization Nd, Er or Yb ion, sends the feature near infrared light;
The structural formula of the sensitive ligand in the described near-infrared luminous lanthanide ion title complex is shown in formula III; Wherein, R
1, R
2Be that carbonatoms is the alkyl of 1-4; R
3, R
4Be methyl or H; R
5, R
6, R
7And R
8Be selected from the alkyl that H or carbonatoms are 1-3 any one; N is 0 or 1;
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WO2011088744A1 (en) * | 2010-01-22 | 2011-07-28 | 北京大学 | Photoluminescent nanoparticle, preparation, and application thereof |
CN105973472A (en) * | 2015-03-12 | 2016-09-28 | 北京大学 | Near infrared fluorescence temperature sensing method and material |
CN108676555A (en) * | 2018-05-28 | 2018-10-19 | 青岛农业大学 | One kind red light material of liquid containing europium ion and preparation method and application |
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CN101066975B (en) * | 2007-06-15 | 2010-06-02 | 北京大学 | Europium complex with visible light sensitized light emitting performance and its synthesis process |
CN100532378C (en) * | 2007-06-15 | 2009-08-26 | 北京大学 | Light-sensitive luminous europium complex and light-sensitive ligand molecule and their synthesizing method |
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WO2011088744A1 (en) * | 2010-01-22 | 2011-07-28 | 北京大学 | Photoluminescent nanoparticle, preparation, and application thereof |
CN105973472A (en) * | 2015-03-12 | 2016-09-28 | 北京大学 | Near infrared fluorescence temperature sensing method and material |
CN108676555A (en) * | 2018-05-28 | 2018-10-19 | 青岛农业大学 | One kind red light material of liquid containing europium ion and preparation method and application |
CN108676555B (en) * | 2018-05-28 | 2020-11-20 | 青岛农业大学 | Europium-containing ionic liquid red light material, and preparation method and application thereof |
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