CN104230995B - A kind of have mixed ligand containing manganese one dimensional polymers and its preparation method - Google Patents
A kind of have mixed ligand containing manganese one dimensional polymers and its preparation method Download PDFInfo
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Abstract
The present invention relates to coordination polymer material field, in particular to a kind of have mixed ligand containing manganese one dimensional polymers and its preparation method. What have mixed ligand contains manganese one dimensional polymers, and chemical formula is C20H26N4O10Mn, described polymkeric substance is oblique system,<i>P21/ n</i>spacer, unit cell parameters is<i>a</i>=13.7358 (2)?,<i>b</i>=12.0317 (8)?,<i>c</i>=13.9217 (3)?,<i>��=</i>90.00o,<i>��=</i>110.578 (3) o,<i>��=</i>90.00o, V=2257.38 (12)?3. The present invention is easy to preparation, good stability containing manganese one dimensional polymers, and the fault in material being synthesized is few, degree of crystallinity height. This dimensional polymers has extraordinary potential application prospect in fields such as molecular magnet, sensing, molecular recognition, molecular luminescences.
Description
Technical field
The present invention relates to polymer materials field, in particular to a kind of have mixed ligand containing manganese one dimensional polymers and its preparation method.
Background technology
The coordination chemistry of polydentate ligand is one of hot fields of coordination chemistry research all the time. Conventional polydentate ligand has many teeth Carboxylic acid ligand and many teeth containing n-donor ligand. The ligand polymer utilizing many teeth Carboxylic acid ligand or many teeth containing n-donor ligand to construct has good stability, easily preparation and tool and has been widely used, and is widely used in molecular magnet, gas adsorption, catalysis, fluorescence and biological activity etc. including as functional materials. Ligand polymer containing many teeth Carboxylic acid ligand has following characteristics and advantages: (1) has abundant coordination mode, has and comprises monodentate ligand, Bidentate State and bridge connection coordination mode. (2) Atomic coordinate ability is strong, it is possible to various metals coordination, and can form bunch base title complex or bunch unit with metal ion, thus the topology network architecture that construction structure is more novel, character is unique. (3) the degree difference of the carboxyl deprotonation of many teeth carboxylic acid can form different structures. Carboxyl can deprotonation in whole or in part, it is possible to as acceptor or the donor of hydrogen bond, and the collaborative effect such as coordinate bond and metallic bond participates in the self-assembly of supramolecule. The superiority of Carboxylic acid ligand facilitates the development of carboxylic acid ligand polymer to a great extent. Many teeth containing n-donor ligand also has above-mentioned similar effect.
Summary of the invention
Technical problem to be solved by this invention be to provide a kind of have mixed ligand containing manganese one dimensional polymers.
Another object of the present invention is to provide the preparation method of above-mentioned polymkeric substance.
Technical problem to be solved by this invention is achieved by the following technical programs:
What have mixed ligand contains manganese one dimensional polymers, and chemical formula is C20H26N4O10Mn, described polymkeric substance is oblique system, P21/ n spacer, unit cell parameters is a=13.7358 (2), b=12.0317 (8), c=13.9217 (3), ��=90.00o, ��=110.578 (3) o, ��=90.00o, V=2257.38 (12)3��
A kind of preparation method containing manganese one dimensional polymers with mixed ligand: be added in the middle of methanol solution by organic ligand terephthalic acid, 1,4-bis--(3-pyridyl)-2,3-two nitrogen-1,3-divinyl, at room temperature stirs and forms mixed liquor A; Then soluble manganese salt is dissolved in the middle of distilled water, at room temperature stirs and form solution B, leave standstill volatilization in room temperature after finally solution B being slowly added in mixed liquor A and within more than 5 days, obtain a described dimensional polymers.
Described 1,4-bis--(3-pyridyl)-2,3-two nitrogen-1,3-divinyl English 1,4-bis-(3-pyridyl)-2,3-diaza-1,3-butadiene by name, its chemical structural formula is as follows:
Further, the mol ratio of described terephthalic acid, 1,4-bis--(3-pyridyl)-2,3-two nitrogen-1,3-divinyl and soluble manganese salt is 0.8 ~ 1.2:0.8 ~ 1.2:1 ~ 1.2.
Preferred further, the mol ratio of described terephthalic acid, 1,4-bis--(3-pyridyl)-2,3-two nitrogen-1,3-divinyl and soluble manganese salt is preferably 1:1:1.
Further, the volume ratio of described methyl alcohol and distilled water is 1.5 ~ 3:1.
Further, described soluble manganese salt is at least one in manganous nitrate, Manganous chloride tetrahydrate.
In the process of synthetic polymer, it has been found that 1,4-bis--(3-pyridyl)-2,3-bis-nitrogen-1,3-divinyl part has abundant coordination mode and bridge linking effect, and the Sauerstoffatom on terephthalic acid can form hydrogen bond action with water molecules, it is to increase the stability of whole polymkeric substance.
The present invention has following useful effect:
The present invention is easy to preparation, good stability containing manganese one dimensional polymers, and the fault in material being synthesized is few, degree of crystallinity height. This dimensional polymers has extraordinary potential application prospect in fields such as molecular magnet, sensing, molecular recognition, molecular luminescences.
Accompanying drawing explanation
Fig. 1 be the present invention have mixed ligand containing manganese one dimensional polymers C20H26N4O10Mn is with the coordination environment figure of metal center Mn.
Fig. 2 be the present invention have mixed ligand containing manganese one dimensional polymers C20H26N4O10The one-dimentional structure figure of Mn.
Embodiment
Below in conjunction with embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention, is not limitation of the invention.
Embodiment 1
Organic ligand 0.5mmol terephthalic acid, 0.5mmol1,4-bis--(3-pyridyl)-2,3-two nitrogen-1,3-divinyl are added in the middle of 8mL methanol solution, at room temperature stir and form mixed liquor A; Then 0.5mmol manganous nitrate is dissolved in the middle of 4mL distilled water, at room temperature stirs and form solution B, leave standstill volatilization in room temperature after finally solution B being slowly added in mixed liquor A and within 7 days, obtain described containing manganese one dimensional polymers C20H26N4O10Mn, product rate is 63.7% (based on Mn).
Then above-mentioned manganese one dimensional polymers that contains with mixed ligand is carried out structural characterization.
This has the X ray diffracting data containing manganese one dimensional polymers of mixed ligand is visit on diffractometer in BrukerSmartApexCCD face, uses MoK��Radiation (��=0.71073), collects with �� scan mode and carries out Lp factor correction, and absorption correction uses SADABS program. Use direct method solution structure, then obtain whole non-hydrogen atom coordinate by difference fourier method, and obtain hydrogen atom position (C H1.083) with theoretical hydrogenation method, by method of least squares, structure is revised. Evaluation work completes with SHELXTL routine package on PC. This polymer crystals parameter is in table 1. Structure is shown in Fig. 1, Fig. 2.
The crystallographic parameter of table 1. polymkeric substance and structure elucidation
From crystalline structure, this polymkeric substance belongs to oblique system, P21/ n spacer. Each structure cell unit comprises two independent Mn atoms, terephthaldehyde's acid molecule of a monodentate ligand, 1,4-bis--(3-pyridyl)-2,3-two nitrogen-1,3-butadiene molecule and six water moleculess (as shown in Figure 1). Wherein, Mn1 is 2.0723(3 with the O(Mn1-O bond distance on two terephthalic acids respectively) ~ 2.1189(11)), two 1,4-bis--(3-pyridyl)-2, N(Mn1-N bond distance on 3-bis-nitrogen-1,3-divinyl is 2.1625(4) and two water molecule coordination. N(Mn2-N bond distance on Mn2 difference two 1,4-bis--(3-pyridyl)-2,3-two nitrogen-1,3-divinyl is 2.165(6) and four water molecules (Mn2-O bond distance is 2.175(3) ~ 2.088(21))) coordination. In this structure, two kinds of Mn atoms all adopt the octahedral coordination of distortion, coordinated water molecule and terephthalic acid do not have the O atom of coordination to define interaction of hydrogen bond, the hydrogen bond of this kind of unique types may make remaining O atom on terephthalic acid be difficult to coordination, thus have employed the pattern of monodentate ligand. Finally, atoms metal, 1,4-bis--(3-pyridyl)-2,3-two nitrogen-1,3-divinyl part and water molecules define the one-dimentional structure (as shown in Figure 2) of a kind of uniqueness under the interaction and intermolecular ��-�� interaction of hydrogen bond.
Embodiment 2
Organic ligand 0.5mmol terephthalic acid, 0.4mmol1,4-bis--(3-pyridyl)-2,3-two nitrogen-1,3-divinyl are added in the middle of 6mL methanol solution, at room temperature stir and form mixed liquor A; Then 0.5mmol Manganous chloride tetrahydrate is dissolved in the middle of 4mL distilled water, at room temperature stirs and form solution B, leave standstill volatilization in room temperature after finally solution B being slowly added in mixed liquor A and within 6 days, obtain described containing manganese one dimensional polymers C20H26N4O10Mn, product rate is 57.3% (based on Mn).
Embodiment 3
Organic ligand 0.4mmol terephthalic acid, 0.6mmol1,4-bis--(3-pyridyl)-2,3-two nitrogen-1,3-divinyl are added in the middle of 10mL methanol solution, at room temperature stir and form mixed liquor A; Then 0.5mmol Manganous chloride tetrahydrate is dissolved in the middle of 4mL distilled water, at room temperature stirs and form solution B, leave standstill volatilization in room temperature after finally solution B being slowly added in mixed liquor A and within 10 days, obtain described containing manganese one dimensional polymers C20H26N4O10Mn, product rate is 47.6% (based on Mn).
Embodiment 4
Organic ligand 0.6mmol terephthalic acid, 0.5mmol1,4-bis--(3-pyridyl)-2,3-two nitrogen-1,3-divinyl are added in the middle of 6mL methanol solution, at room temperature stir and form mixed liquor A; Then 0.6mmol manganous nitrate manganese is dissolved in the middle of 4mL distilled water, at room temperature stirs and form solution B, leave standstill volatilization in room temperature after finally solution B being slowly added in mixed liquor A and within 8 days, obtain described containing manganese one dimensional polymers C20H26N4O10Mn, product rate is 51.8% (based on Mn).
The above embodiment only have expressed embodiments of the present invention; it describes comparatively concrete and detailed; but therefore can not be interpreted as the restriction to patent scope of the present invention; in every case the technical scheme adopting the form of equivalent replacement or equivalent transformation to obtain, all should drop within protection scope of the present invention.
Claims (5)
1. one kind has the preparation method containing manganese one dimensional polymers of mixed ligand, it is characterized in that: by organic ligand terephthalic acid, 1,4-bis--(3-pyridyl)-2,3-two nitrogen-1,3-divinyl is added in the middle of methanol solution, at room temperature stirs and forms mixed liquor A; Then soluble manganese salt is dissolved in the middle of distilled water, at room temperature stirs and form solution B, leave standstill volatilization in room temperature after finally solution B being slowly added in mixed liquor A and within more than 5 days, obtain a described dimensional polymers;
Described is C containing manganese one dimensional polymers chemical formula20H26N4O10Mn, oblique system, P21/ n spacer, unit cell parameters is a=13.7358 (2), b=12.0317 (8), c=13.9217 (3), ��=90.00o, ��=110.578 (3) o, ��=90.00o, V=2257.38 (12)3, its chemical structural formula is as follows:
��
2. a kind of preparation method containing manganese one dimensional polymers with mixed ligand according to claim 1, it is characterized in that: described terephthalic acid, 1,4-bis--(3-pyridyl)-2, the mol ratio of 3-bis-nitrogen-1,3-divinyl and soluble manganese salt is 0.8 ~ 1.2:0.8 ~ 1.2:1 ~ 1.2.
3. a kind of preparation method containing manganese one dimensional polymers with mixed ligand according to claim 2, it is characterized in that: described terephthalic acid, 1, the mol ratio of 4-bis--(3-pyridyl)-2,3-two nitrogen-1,3-divinyl and soluble manganese salt is preferably 1:1:1.
4. a kind of preparation method containing manganese one dimensional polymers with mixed ligand according to claim 1, it is characterised in that: the volume ratio of described methyl alcohol and distilled water is 1.5 ~ 3:1.
5. a kind of preparation method containing manganese one dimensional polymers with mixed ligand according to claim 1, it is characterised in that: described soluble manganese salt is at least one in manganous nitrate, Manganous chloride tetrahydrate.
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