利用水熱法及溶劑熱法，將吡啶-2,4,6-三羧酸(Pyridine-2,4,6-tricarboxylic acid, H3PTC)與二價的鋅、鈷、鎳以水或水與乙醇以適當比例當作溶劑進行反應合成，藉由調控不同的反應溫度以及時間合成出五種晶體，並經由元素分析、FT-IR吸收光譜儀、X-ray單晶繞射儀解析得到五種配位高分子的結構，此五種結構分別是[Zn7(μ4-O) (μ-OH)3(PTC)3]n – (1)、{[Ni3(PTC)2(H2O)8]．(H2O)4}n – (2)、{[Co3(PTC)2(H2O)8]．(H2O)4}n – (3)、{[Co(H2O)6][Co(PTC)(H2O)2]2．(H2O)2}n – (4)
、{[Co(H2O)6][Co(PTC)(H2O)]2}n – (5)，其中化合物1具有三維的結構，化合物2及化合物3是二維的結構並互為等結構，化合物4和化合物5為一維的結構，且化合物1、化合物2、化合物3、化合物5為新的結構，並藉由熱重分析及FT-IR吸收光譜儀探討其熱穩定性及配位水和結晶水離去的溫度，可以知道其分解溫度均大於350 ℃，具有相當良好的熱穩定性。

Hydrothermal Synthesis and Structural Characterization of Coordination Polymers Containing Zn(II), Co(II), Ni(II) and Organic Tricarboxylates

Ting-Chang Yeh
Kom-Bei Shiu
Department of Chemistry, National Cheng-Kung University

SUMMARY

Utilizing hydrothermal and solvothermal method to synthesize five coordination polymers from Metal salt [Zn(II), Co(II), Ni(II)] and pyridine-2,4,6-tricarboxylic acid.All coordination polymers were characterizes by elemental analysis, fourier transform infrared spectroscopy, thermogravimetry analysis, powder X-ray diffraction and single-crystal diffractometer.Single crystal structure of each coordination polymer were determined by single diffraction data.

Key words : coordination polymer, hydrothermal method, solvothermal method, pyridine-2,4,6-tricarboxylic acid

INTRODUCTION

Products that obtained from the combination of metal salts [M = Zn(II), Co(II), Ni(II)] and pyridine-2,4,6- tricarboxylic acid are coordination polymers. By controlling temperature and reaction time I synthesize five novel coordination polymers via hydrothermal and solvothermal method. They are [Zn7(μ4-O) (μ-OH)3(PTC)3]n – (1), {[Ni3(PTC)2(H2O)8]．(H2O)4}n – (2), {[Co3(PTC)2(H2O)8]．(H2O)4}n – (3), {[Co(H2O)6][Co(PTC)(H2O)2]2．(H2O)2}n – (4), {[Co(H2O)6][Co(PTC)(H2O)]2}n – (5).

MATERIALS AND METHODS

Pyridine-2,4,6- tricarboxylic acid is synthesized from 2,4,6- trimethylpyridine and potassium permanganate in aqueous solution. Using hydrothermal program oven heating rate is different condition from room temperature to reaction temperature and slowly cooling rate from reaction temperature to room temperature. The reaction temperature and reaction time of compound 1 are 190 °C and 72 hr, compound 2 are 130 °C and 48 hr, compound 3 are 120 °C and 48 hr, compound 4 are 120 °C and 48 hr, compound 5 are 130 °C and 72 hr.

RESULTS AND DISCUSSION

The structrural dimension and metal coordination mode of five compounds are summarized in Table 1 {[Zn7(μ4-O) (μ-OH)3(PTC)3]n – (1), {[Ni3(PTC)2(H2O)8]．(H2O)4}n – (2), {[Co3(PTC)2(H2O)8]．(H2O)4}n – (3), {[Co(H2O)6][Co(PTC)(H2O)2]2．(H2O)2}n – (4), {[Co(H2O)6][Co(PTC)(H2O)]2}n – (5)}. And all of compounds have good thermal stability.

Table 1. Coordination polymers
Compound (1) (2) (3) (4) (5)
Dimension 3 2 2 1 1
M1(M=Zn, Co, Ni) 4 6 6 7 6
M2(M=Zn, Co, Ni) 5 6 6 6 6
M3(M=Zn, Co, Ni) 4 - - - 6
Thermal stability(℃) 455 377 389 389 -

CONLUSION

Utilize hydrothermal and solvothermal method to synthesize five coordination polymers from metal salts and H3PTC. Compound 1 is 3D structure, Compound 2, 3 are 2D structures, Compound 4, 5 are 1D structures. Compound 1, 2, 3, 5 are new coordination polymer structures and compound 2, 3 are isostructural. And all of compounds have good thermal stability.

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