3,4-bis-(4'-carboxyl phenyl) phenylformic acid cadmium complex and preparation method thereof
Technical field
The present invention relates to d
10metal complex fluorescent Material Field, a kind of 3,4-bis-(4'-carboxyl phenyl) phenylformic acid cadmium complex and preparation method thereof, the crystal of described title complex is three-dimensional net structure, the three-dimensional net structure of this title complex can be simplified as one (4,10)-connection (3.4
5) (3
4.4
9.5
12.6
17.7
2.8) topology network architecture, can be used as fluorescent material by further Application and Development.
Background technology
The research of ligand polymer association area combines traditional inorganic chemistry, organic chemistry and physical chemistry, and merges with the subject crossing such as supramolecular chemistry, materials chemistry, biological chemistry and environmental chemistry, has formed thus many novel frontier branches of science.Ligand polymer not only has interesting and various molecular structure and topological framework, the more important thing is that it shows tempting application prospect in field of new such as fluorescence, absorption, catalysis, magnetic, thereby become in recent years the advanced subject that integrates fundamental research and applied research.(as: Mal, P.; Schultz, D.; Beyeh, K.; Rissanen, K.; Nitschke J. R.
angew. Chem., Int. Ed. 2008,
47, 8297 – 8301; Wang, J.; Lin, Z.; Ou, Y.-C.; Yang, N.-L.; Zhang, Y.-H.; Tong, M.-L.
inorg. Chem. 2008,
47, 190 – 199; Liu, W.-T.; Ou, Y.-C.; Xie, Y.-L.; Lin, Z.; Tong, M.-L.
eur. J. Inorg. Chem. 2009, 4213 – 4218; Fang, S.-M.; Zhang, Q.; Hu, M.; Carolina Sa udo, E.; Du, M.; Liu, C.-S.
inorg. Chem. 2010,
49, 9617 – 9626; Xu, X.; Zhang, X.; Liu, X.; Sun, T.; Wang, E.
cryst. Growth Des. 2010,
10, 2272 – 2277; Liu, C.-S.; Carolina Sa udo, E.; Hu, M.; Zhou, L.-M.; Guo, L.-Q.; Ma, S.-T.; Gao, L.-J.; Fang, S.-M
. CrystEngComm,
2010,
12, 853 – 865; Fang, S.-M.; Hu, M.; Zhang, Q.; Du M.; Liu, C.-S.
dalton Trans.
2011,
40,4527 – 4541).Aromatic ring multi-carboxylic acid organic molecule is the important bridgingligand of a class, reacts and constructs some molecular based coordination polymer materials of obtaining by extensive synthetic report, and show good Potential performance with this class part with metal ion.The aromatic ring organic ligand containing single phenyl ring (Benzene) and naphthalene nucleus (Naphthalene) in the past often using in metalcomplex sythesis is compared, the large volume aromatic ring frame poly carboxylic acid part that contains a plurality of aromatic rings generally has larger conjugated pi system, and large skeleton also can affect to some extent on the coordination situation of part.(as: Lei, H.; Zhang, J.-P.; Chen, X.-M.
cryst.Growth Des. 2009,
9, 2415 – 2419; Dinc ǎ, M.; Dailly, A.; Tsay, C.; Long, J. R.
inorg. Chem. 2008,
47, 6825 – 6828; Ma, S.; Wang, X.-S.; Yuan, D.; Zhou, H.-C.
angew. Chem., Int. Ed. 2008,
47, 4130 – 4133; Hsu, Y.-F.; Lin, C.-H.; Chen, J.-D.; Wang, J.-C.
cryst. Growth Des. 2008,
8, 1094 – 1096; Ma, S.; Sun, D.; Ambrogio, M.; Fillinger, J. A.; Parkin, S.; Zhou, H.-C.
j. Am. Chem. Soc. 2007,
129, 1858 – 1859; Zeng, M.-H.; Zhang, W.-X.; Sun, X.-Z.; Chen, X.-M.
angew. Chem., Int. Ed. 2005,
44, 3079 – 3082; Chae, H. K.; Williams, C. A.; Blake, A. J.; Hubberstey, P.; Schro ¨ der, M.
chem.Commun. 2005, 5435 – 5437; Siberio-Pe ' rez, D. Y.; Kim, J.; Go, Y.; Eddaoudi, M.; Matzger, A. J.; O ' Keeffe, M.; Yaghi, O. M.
nature (London) 2004,
427, 523 – 527).
3,4-bis-(4'-carboxyl phenyl) phenylformic acid is a kind of large volume aromatic ring frame poly carboxylic acid part that contains a plurality of aromatic rings, its d
10so far also nobody reports in the research of metal complexes.The advantages such as the invention discloses a kind of benzoic cadmium complex of 3,4-bis-(4'-carboxyl phenyl) that contains, its synthetic method is simple, easy to operate, and has good stability, and productive rate height and reproducibility are good.
Summary of the invention
The object of the invention is to disclose a kind of 3,4-bis-(4'-carboxyl phenyl) phenylformic acid cadmium complex and preparation method thereof and application.
For achieving the above object, the technical solution used in the present invention is as follows:
Of the present invention 3,4-bis-(4'-carboxyl phenyl) phenylformic acid cadmium complex, title complex is the title complex of following chemical formula: [Cd
4 l 2(OH)
2(H
2o)
3]
∞, wherein
l=3,4-bis-(4'-carboxyl phenyl) phenylformic acid anion ligand; Its skeleton symbol is as follows:
Described complex crystal belongs to rhombic system, and spacer is
pnma, unit cell parameters is
a=14.4403 (4),
b=27.2329 (6),
c=9.8291 (3), α=90
o,
β=90
o, γ=90
o,
v=3865.31 (18)
3.
The basic structure of described title complex is a three-dimensional net structure, has four kinds of different Cd
iIcoordination environment, the octahedral coordination environment that wherein Cd1 is distortion, respectively with 4
l 2 –part and 2 m
3the coordination of-hydroxyl; Cd2 and Cd3 respectively with 4
l 2 –part, 2 m
3-hydroxyl and 1 coordinated water coordination; And the sterie configuration of Cd4 is the tetragonal pyramid of distortion, respectively with 3
l 2 –part and 2 m
3the coordination of-hydroxyl.M
3-O connects Cd atom and forms one-dimensional chain structure, by
lbridge linking effect in spatial spread, be complicated three-dimensional net structure.For the three-dimensional net structure of title complex is described clearly, can be abstracted into topological framework: if by the four [Cd of vouching unit
4(m
3-OH)
2] regard a node of network as, it connects two four identical core cell nodes by two pairs of O5 – C3 – O6 carboxyls, also connects in addition 8
lpart, thereby can be reduced to the node that 10-connects.And
lpart connects four four core cell nodes can be reduced to 4-connected node.The three-dimensional net structure of whole like this complexity just can be reduced to (3.4 of (4,10)-connection
5) (3
4.4
9.5
12.6
17.7
2.8) topology.
Under the condition of solvent thermal, by 3,4-bis-(4'-carboxyl phenyl) phenylformic acid part and metal cadmium salt are dissolved in the solution of making soluble in water and enclose in the reactor of 25 mL, with the speed of 10 ℃ per hour, be heated at certain temperature, maintain this temperature 3 days, be then naturally down to room temperature, can obtain colourless rhabdolith, this monocrystalline is separated, through washing, drying treatment, obtained target product successively.
Described is 0.005 ~ 0.01 mol L in 3,4-bis-(4'-carboxyl phenyl) the phenylformic acid part strength of solution of making soluble in water
– 1.
Described metal cadmium salt is cadmium acetate, and the strength of solution of making soluble in water is 0.01 ~ 0.02 mol L
-1.
Reaction mixture is heated to 160 ~ 180 ℃ with 10 ℃ per hour.
The advantages such as synthetic method provided by the invention obtains title complex, has good stability, synthetic simple, easy to operate, and productive rate height and reproducibility are good.The fluorescence data of crystal prototype shows that this type of title complex has stable fluorescence property, can be used as fluorescent material and is applied at material science.The thermogravimetric analysis of title complex characterize show its skeleton approach 250 ℃ of left and right still can stable existence, there is certain thermostability, for its further Application and Development as sorbing material provides assurance.
Accompanying drawing explanation
Fig. 13, Cd in 4-bis-(4'-carboxyl phenyl) phenylformic acid cadmium complex
iIcoordination environment figure;
Fig. 23, the three-dimensional net structure figure of 4-bis-(4'-carboxyl phenyl) phenylformic acid cadmium complex;
Fig. 33, the topological network of 4-bis-(4'-carboxyl phenyl) phenylformic acid cadmium complex;
Fig. 43, the solid state fluorescence spectrogram of 4-bis-(4'-carboxyl phenyl) phenylformic acid cadmium complex;
Fig. 53, the test of the powdery diffractometry (XPRD) of 4-bis-(4'-carboxyl phenyl) phenylformic acid cadmium complex and theoretical contrast figure;
Fig. 63, the thermogravimetric curve figure of 4-bis-(4'-carboxyl phenyl) phenylformic acid cadmium complex.
Embodiment
Complex crystal of the present invention is characterized in that described complex crystal belongs to rhombic system, and spacer is
pnma, unit cell parameters is
a=14.4403 (4),
b=27.2329 (6),
c=9.8291 (3), α=90
o,
β=90
o, γ=90
o,
v=3865.31 (18)
3.Basic structure is a novel three-dimensional net structure, has four kinds of different Cd
iIcoordination environment, the octahedral coordination environment that wherein Cd1 is distortion, respectively with 4
l 2 –part and 2 m
3the coordination of-hydroxyl; Cd2 and Cd3 respectively with 4
l 2 –part, 2 m
3-hydroxyl and 1 coordinated water coordination; And the sterie configuration of Cd4 is the tetragonal pyramid of distortion, respectively with 3
l 2 –part and 2 m
3the coordination of-hydroxyl.M
3-O connects Cd atom and forms one-dimensional chain structure, by
lbridge linking effect in spatial spread, be complicated three-dimensional net structure.For the three-dimensional net structure of title complex is described clearly, can be abstracted into topological framework: if by the four [Cd of vouching unit
4(m
3-OH)
2] regard a node of network as, it connects two four identical core cell nodes by two pairs of O5 – C3 – O6 carboxyls, also connects in addition 8
lpart, thereby can be reduced to the node that 10-connects.And
lpart connects four four core cell nodes can be reduced to 4-connected node.The three-dimensional net structure of whole like this complexity just can be reduced to (3.4 of (4,10)-connection
5) (3
4.4
9.5
12.6
17.7
2.8) topology.
In the preparation method of title complex of the present invention, 3,4-bis-(4'-carboxyl phenyl) the phenylformic acid part strength of solution of making soluble in water is 0.005 ~ 0.01 mol L
– 1, the acetic acid cadmium salt strength of solution of making soluble in water is 0.01 ~ 0.02 mol L
-1; Reaction conditions is that constant temperature drops to room temperature for three days afterwards naturally under 160 ~ 180 ° of C.
Embodiment 1
3,4-bis-(4'-carboxyl phenyl) phenylformic acid (0.05 mmol, 18.0 mg) and cadmium acetate (0.15 mmol, 39.97 mg) are dissolved in to stirring in water (8 mL) to be enclosed in the hydrothermal reaction kettle of 25ml after 5 minutes.Reaction mixture is heated at 160 ℃ with 10 ℃ per hour again, maintains this temperature 3 days, be then down to room temperature, can obtain colourless bulk crystals, this monocrystalline is separated, through washing, drying treatment, obtain target product successively, productive rate is about 45%.Main infrared absorption peak is: 3393m, 1590s, 1534w, 1383vs, 1179w, 1134w, 1102w, 1038w, 1016w, 919w, 861w, 786m, 719m, 678w, 659w, 465w, 425w.
Embodiment 2
3,4-bis-(4'-carboxyl phenyl) phenylformic acid (0.1 mmol, 36.0 mg) and cadmium acetate (0.15 mmol, 39.97 mg) are dissolved in to stirring in water (10 mL) to be enclosed in the hydrothermal reaction kettle of 25ml after 5 minutes.Reaction mixture is heated at 160 ℃ with 10 ℃ per hour again, maintains this temperature 3 days, be then down to room temperature, can obtain colourless bulk crystals, this monocrystalline is separated, through washing, drying treatment, obtain target product successively, productive rate is about 55%.Main infrared absorption peak is: 3393m, 1590s, 1534w, 1383vs, 1179w, 1134w, 1102w, 1038w, 1016w, 919w, 861w, 786m, 719m, 678w, 659w, 465w, 425w.
Embodiment 3
3,4-bis-(4'-carboxyl phenyl) phenylformic acid (0.05 mmol, 18.0 mg) and cadmium acetate (0.15 mmol, 39.97 mg) are dissolved in to stirring in water (8 mL) to be enclosed in the hydrothermal reaction kettle of 25ml after 5 minutes.Reaction mixture is heated at 180 ℃ with 10 ℃ per hour again, maintains this temperature 3 days, be then down to room temperature, can obtain colourless bulk crystals, this monocrystalline is separated, through washing, drying treatment, obtain target product successively, productive rate is about 65%.Main infrared absorption peak is: 3393m, 1590s, 1534w, 1383vs, 1179w, 1134w, 1102w, 1038w, 1016w, 919w, 861w, 786m, 719m, 678w, 659w, 465w, 425w.
Embodiment 4
3,4-bis-(4'-carboxyl phenyl) phenylformic acid (0.1 mmol, 36.0 mg) and cadmium acetate (0.15 mmol, 39.97 mg) are dissolved in to stirring in water (10 mL) to be enclosed in the hydrothermal reaction kettle of 25ml after 5 minutes.Reaction mixture is heated at 180 ℃ with 10 ℃ per hour again, maintains this temperature 3 days, be then down to room temperature, can obtain colourless bulk crystals, this monocrystalline is separated, through washing, drying treatment, obtain target product successively, productive rate is about 60%.Main infrared absorption peak is: 3393m, 1590s, 1534w, 1383vs, 1179w, 1134w, 1102w, 1038w, 1016w, 919w, 861w, 786m, 719m, 678w, 659w, 465w, 425w.
Get embodiment 1 gained 3,4-bis-(4'-carboxyl phenyl) phenylformic acid cadmium complex further characterizes, and its process is as follows:
(1) crystal structure determination of title complex
The monocrystalline of choosing under the microscope suitable size at room temperature carries out the experiment of X – ray diffraction.At Xcalibur, Eos, on Gemini diffractometer, uses the K through the Mo of graphite monochromator monochromatization –
aray (
l=0.71073), Yi φ – ω mode is collected diffraction data.With CrysAlisPro, Agilent Technologies, Version 1.171.35.15 program is carried out reduction of data.The diffraction data of part-structure carries out absorption correction by SADABS program.Crystalline structure is solved in conjunction with difference Fourier is synthetic by direct method.All non-hydrogen atom coordinate and anisotropic parameters carry out complete matrix least-squares refinement, and hydrogen atom position is determined by theoretical mode computation.Hydrogen atom on partial solvent water and methyl alcohol is processed by the method for difference Fourier peak-seeking.Detailed axonometry data are in Table 1; Important bond distance and bond angle data are in Table 2.Crystalline structure is shown in Fig. 1 and Fig. 2, and Fig. 3 is shown in by the topological network of title complex.
(2) the solid fluorescence performance study of title complex
Complex crystal sample after enrichment is processed, through further milled processed, carries out the test of solid fluorescence: title complex excites at 333 nm places, at 398 nm places, obtains an emission peak, sees Fig. 4.(instrument model: HITACHI/F – 7000).
(3) the XPRD phase purity of title complex characterizes
The XPRD of title complex characterizes and shows that it has reliable phase purity, for its application as fluorescent material provides assurance, sees Fig. 5.(instrument model: Bruker/D8 Advance).
(4) thermal stability of title complex characterizes
The thermogravimetric analysis of title complex characterize show its skeleton approach 250 ℃ of left and right still can stable existence, there is certain thermostability, for its further Application and Development as sorbing material provides assurance, see Fig. 6.(instrument model: Perkin – Elmin Diamond TG/DTA).
By above-mentioned characterization result, can be seen, complex crystal of the present invention belongs to rhombic system, and spacer is
pnma, unit cell parameters is
a=14.4403 (4),
b=27.2329 (6),
c=9.8291 (3), α=90
o,
β=90
o, γ=90
o,
v=3865.31 (18)
3.Basic structure is a novel three-dimensional net structure, has four kinds of different Cd
iIcoordination environment, the octahedral coordination environment that wherein Cd1 is distortion, respectively with 4
l 2 –part and 2 m
3the coordination of-hydroxyl; Cd2 and Cd3 respectively with 4
l 2 –part, 2 m
3-hydroxyl and 1 coordinated water coordination; And the sterie configuration of Cd4 is the tetragonal pyramid of distortion, respectively with 3
l 2 –part and 2 m
3the coordination of-hydroxyl.M
3-O connects Cd atom and forms one-dimensional chain structure, by
lbridge linking effect in spatial spread, be complicated three-dimensional net structure.For the three-dimensional net structure of title complex is described clearly, can be abstracted into topological framework: if by the four [Cd of vouching unit
4(m
3-OH)
2] regard a node of network as, it connects two four identical core cell nodes by two pairs of O5 – C3 – O6 carboxyls, also connects in addition 8
lpart, thereby can be reduced to the node that 10-connects.And
lpart connects four four core cell nodes can be reduced to 4-connected node.The three-dimensional net structure of whole like this complexity just can be reduced to (3.4 of (4,10)-connection
5) (3
4.4
9.5
12.6
17.7
2.8) topology.
Above embodiment is only for illustrating content of the present invention, and in addition, the present invention also has other embodiment.But all employings are equal to replaces or technical scheme that equivalent deformation mode forms all drops in protection scope of the present invention.
table 1the main crystallographic data of title complex
Empirical formula C
42H
30O
17Cd
4
Formula weight 1256.26
Crystal system Orthorhombic
Space group
Pnma
a / 14.4403(4)
b / 27.2329(6)
c / 9.8291(3)
α/
o90
b/
o 90
γ/
o 90
Volume /
3 3865.31(18)
Z 4
D / g cm
-3 2.159
m /mm
–1 18.106
F (000) 2440
R int 0.0469
T / K 293(2)
Goodness-of-fit on
F 2 1.109
R 1 a /
wR 2 b [
I >2
σ(
I)] 0.0630 / 0.1528
R 1 a /
wR 2 b (All data) 0.0706 / 0.1578
r max / r min (e
–3) 1.737 /
- 2.024
a R 1 = S(||
F o|
-|
F c||)/S|
F o|;
b wR 2 = [S
w(|
F o|
2 -|
F c|
2)
2/S
w(
F o 2)
2]
1/2