CN104447819B - Chiral zinc nitrogen complexes of double naphthyl oxalic acid and preparation method thereof - Google Patents

Chiral zinc nitrogen complexes of double naphthyl oxalic acid and preparation method thereof Download PDF

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CN104447819B
CN104447819B CN201410634223.3A CN201410634223A CN104447819B CN 104447819 B CN104447819 B CN 104447819B CN 201410634223 A CN201410634223 A CN 201410634223A CN 104447819 B CN104447819 B CN 104447819B
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oxalic acid
naphthyl
nitrogen complexes
preparation
chiral zinc
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CN104447819A (en
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刘莹莹
杨进
李萌
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Northeast Normal University
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/40—Unsaturated compounds
    • C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
    • C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
    • C07C59/66—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups

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Abstract

Chiral zinc nitrogen complexes of a kind of pair of naphthyl oxalic acid and preparation method thereof, belongs to technical field of chemistry, and coordination compound is following chemical formula: [Zn3(L)3(H2O)3]·H2O, wherein L is (S) () 1 of two protons, 1 ' double naphthyl 2,2 ' oxalic acid aniones.Coordination compound uses solvent thermal process to prepare.The fluorescence data of coordination compound shows that this material can launch stable purple fluorescence, can be applied at material science as fluorescent material.

Description

Chiral zinc nitrogen complexes of double naphthyl oxalic acid and preparation method thereof
Technical field
The invention belongs to technical field of chemistry, relate to a kind of transient metal complex and preparation method thereof.
Background technology
Chirality coordination polymer is due to the potential application at aspects such as molecular recognition, catalysis, optical material and biomimetic chemistries Be worth and be widely studied (U. Knof, A. von Zelewsky,Angew. Chem. Int. Ed. 1999,38,302； A. L ü tzen, M. Hapke, J. Griep-Raming, D. Haase, W. Saak, Angew. Chem. Int. Ed. 2002, 41, 2086).But compared with tradition coordination compound, report the most less (G. Yuan, the C. of chiral coordination compound Zhu, Y. Liu, W. Xuan, Y. Cui,J. Am. Chem. Soc.2009, 131, 10452).
1,1 '-bis--beta naphthal is due to conformational stability, and there is optical activity, it is widely used in asymmetric synthesis and hands In property identification (M. Canlica, T. Nyokong,Dalton Trans. 2011,40, 1497；R. Wang, L. Xu, X. Li, Y. Li, Q. Shi, Z. Zhou, M. Hong, A. S. C. Chan,Eur. J. Inorg. Chem.2004,1595). W. teacher Lin (Y. Cui, S. J. Lee, Y. W. Lin,J. Am. Chem. Soc. 2003,125, 6014；Y. Cui, H. L. Ngo, P. S. White, W. Lin,Inorg. Chem. 2003,42,652；Y. Cui, H. L. Ngo, P. S. White, W. Lin, Chem. Commun.2003,994；H. L. Ngo, W. Lin,J. Am. Chem. Soc. 2002, 124, 14298；Y. Cui, H.L. Ngo, P. S. White, W. Lin,Chem. Commun.2002,1666；Y. Cui, O. R. Evans, H. L. Ngo, P. S.White, W. Lin,Angew. Chem. Int. Ed. 2002,41,1159) and teacher Hong Maochun (R. Wang, L. Xu, X. Li, Y. Li, Q. Shi, Z. Zhou, M. Hong, A. S. C. Chan, Eur. J. Inorg. Chem.2004,1595) this type of part was carried out Research work, they with 1,1 '-bis--beta naphthal connects two pyridine units, has synthesized multiple chirality supermolecule metal combination Thing.But, never reported based on the metal complex synthesized by 1,1 '-bis--beta naphthal oxalic acid part.
Summary of the invention
It is an object of the invention to disclose the chiral zinc nitrogen complexes of a kind of pair of naphthyl oxalic acid.
The present invention also discloses the preparation method of this chiral zinc nitrogen complexes.
The chiral zinc nitrogen complexes of double naphthyl oxalic acid has following chemical formula, it may be assumed that [Zn3(L)3(H2O)3]·H2O, wherein L For go (S) of two protons-(-)-1,1 '-bis-naphthyls-2,2 '-oxalic acid anion ligand.
H2L part
Complex crystal belongs to monoclinic system, and space group is P21, cell parameter is a=18.3740 (5), b= 8.2230 (6), c=21.3210 (4), α=90 °, β=103.573 (2) °, γ=90 °, V=3131.4 (3) Å3, basic structure is one-dimensional catenary structure.
The preparation method of the chiral zinc nitrogen complexes of described double naphthyl oxalic acid, comprises the steps:
Take equimolar Zinc diacetate dihydrate and H2L puts in politef reactor, the water with volume ratio as 7:1 and Ethanol is mixed solvent, places in an oven, is heated to 120 DEG C of constant temperature 72 hours, is then slowly decreased to room temperature and prepares.
The fluorescence data of crystal prototype shows that this coordination compound has stable fluorescence property, can be as fluorescent material It is applied at material science.
Chiral zinc nitrogen complexes of the present invention is obtained by simple solvent-thermal process, have that preparation method is simple, repeatability is strong, The features such as properties of product are stable.
Accompanying drawing explanation
Fig. 1 is to cooperate with the coordination environment figure of metal in thing；
Fig. 2 is one-dimensional catenary structure figure；
Fig. 3 is to cooperate with the fluorescence emission spectrogram of thing；
Fig. 4 is to cooperate with the fluorescent quenching curve chart of thing；
Fig. 5 is to cooperate with the powder diagram of thing.
Detailed description of the invention
The synthesis of the chiral zinc nitrogen complexes of double naphthyl oxalic acid: take Zinc diacetate dihydrate 0.05 mmol, H2L 0.05 Mmol puts in 15 mL politef reactors, with 7 mL water and 1 mL ethanol as mixed solvent, places in an oven, adds Heat to 120 DEG C constant temperature 72 hours, is then slowly decreased to room temperature, available colourless bulk crystals, productivity 38%.
Main infrared absorption peak is: 3445 (w), 3051 (w), 1593 (m), 1507 (w), 1427 (w), 1363 (w), 1269 (m), 1220 (m), 1148 (s), 1075 (w), 1054 (w), 933 (w), 810 (w), 745 (w), 705 (w), 593 (w) 438(w)。
The relevant characterization of coordination compound
(1) crystal structure determination of coordination compound
The diffraction data of coordination compound is to collect on Oxford Diffraction Gemini R Ultra diffractometer, Mo KαRay (λ=0.71069), 293 K.The scanning of use technology is corrected.Crystal structure is by SHELEXL-97 journey Sequence solves with direct method, uses SHELEXL-97 to carry out refine with complete matrix method of least square.The temperature factor of non-hydrogen atom is used Anisotropy is modified.Detailed axonometry data are shown in Table 1；Important bond distance and bond angle data are shown in Table 2；Crystal structure is shown in Fig. 1 and Fig. 2.
The coordination compound of invention is characterized in that described complex crystal belongs to monoclinic system, and space group is C2/c, and structure cell is joined Number is a=18.3740 (5), b=8.2230 (6), c=21.3210 (4), α=90 °, β=103.573 (2) °, γ=90 °, V=3131.4 (3)3.Three independent Zn (II) ions of existence in unit cell, three L aniones, three Water of coordination molecule and a free hydrone.Zn1 and Zn3 ion is the distorted octahedra configuration of hexa-coordinate, and Zn2 ion is for turning round Bent tetragonal pyramid configuration.Three L aniones are different coordination modes, join with three, four and Zn (II) ion respectively Position, is connected as chain structure by coordination compound.
(2) photoluminescent property research (Edinburgh FLSP920 fluorescence spectrophotometer) of coordination compound.
When 312 nm excite, coordination compound has the last one emission peak (Fig. 3) at 373 nm, and the fluorescence decay to coordination compound is bent Line is fitted, and fluorescence lifetime is τ1=1.83 ns(66.17%) and τ2=3.66 ns(33.83%) (Fig. 4).
Table 1 is the predominant crystal data of coordination compound
Table 2 is main bond distance's () and the bond angle [°] of coordination compound*
*Symmetrical code:#1X, y-1, z；#2 X, y+1, z.

Claims (2)

1. the preparation method of the chiral zinc nitrogen complexes of double naphthyl oxalic acid, it is characterised in that: comprise the steps:
The synthetic method of the chiral zinc nitrogen complexes of double naphthyl oxalic acid: take zinc acetate 0.05 mmol, (S)-(-)-1, l '-bis-naphthalenes Base-2,2 '-oxalic acid H2L0.05 mmol puts in politef reactor, molten for mixing with 7 mL water and 1 mL ethanol Agent, places in an oven, is heated to 120 DEG C of constant temperature 72 hours, is then slowly decreased to room temperature and get final product
H2L structural formula.
The chiral zinc nitrogen complexes of the double naphthyl oxalic acid prepared by method the most according to claim 1, it is characterised in that: chemistry Formula is [Zn3(L)3(H2O)3]·H2O, its crystal belongs to monoclinic system, and space group is P21, cell parameter is a=18.3740 (5), b=8.2230 (6), c=21.3210 (4), α=90, β=103.573 (2), γ=90 °, V=3131.4 (3) Å3, basic structure is one-dimensional catenary structure.
CN201410634223.3A 2014-11-12 2014-11-12 Chiral zinc nitrogen complexes of double naphthyl oxalic acid and preparation method thereof Expired - Fee Related CN104447819B (en)

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Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996015136A1 (en) * 1994-11-14 1996-05-23 Dublin Institute Of Technology Novel mn(ii) carboxylate complexes, processes for their preparation and their use as disproportionation catalysts

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
New Types of Homochiral Helical Coordination Polymers Constructed by exo-Bidentate Binaphthol Derivatives;Ruihu Wang et al.;《Eur. J. Inorg. Chem.》;20041231;1595-1599 *
Rational Design of Homochiral Solids Based on Two-Dimensional Metal Carboxylates;Yong Cui et al.;《Angew. Chem. Int. Ed.》;20021231;第41卷(第7期);1159-1162 *

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