Fabrication of Hybrid Materials Containing Keggin-Type Polyoxometalates Units and 2-Picolinic Acid: Synthesis, Structures and Properties

Yang-Zheng CAO Hao XU Wei PAN Xiang-Hua ZENG Jun-Yong ZHANG Hai-Yang GUO Jin-Sheng LIAO Sui-Jun LIU Jing-Li XIE

Citation:  CAO Yang-Zheng, XU Hao, PAN Wei, ZENG Xiang-Hua, ZHANG Jun-Yong, GUO Hai-Yang, LIAO Jin-Sheng, LIU Sui-Jun, XIE Jing-Li. Fabrication of Hybrid Materials Containing Keggin-Type Polyoxometalates Units and 2-Picolinic Acid: Synthesis, Structures and Properties[J]. Chinese Journal of Inorganic Chemistry, 2020, 36(9): 1613-1619. doi: 10.11862/CJIC.2020.196 shu

含Keggin类型多酸单元和2-吡啶甲酸的杂化材料的合成、结构及表征

    通讯作者: 张俊勇, zhangjy@mail.zjxu.edu.cn
    廖金生, jsliao1209@126.com
    刘遂军, sjliu@jxust.edu.cn
    谢景力, jlxie@mail.zjxu.edu.cn
  • 基金项目:

    国家自然科学基金(No.21771088)、浙江省自然科学基金(No.LY20B010005)、无机合成与制备化学国家重点实验室开放基金(No.2020-9)和结构化学国家重点实验室开放基金(No.20170034)资助项目

    结构化学国家重点实验室开放基金 20170034

    无机合成与制备化学国家重点实验室开放基金 2020-9

    浙江省自然科学基金 LY20B010005

    国家自然科学基金 21771088

摘要: 合成了2例基于2-吡啶甲酸(2-PA)和Keggin类型[SiW12O40]4-、[PMo12O40]3-多酸单元的有机-无机杂化材料:H2[(CH34N]6[Cu(2-PA)2(SiW12O402](1)和(H3O)[Cu6(2-PA)9(PMo12O40)(NO3)](2),并用红外光谱以及X射线衍射对其进行了表征。单晶衍射结构分析表明化合物1为单斜晶系,空间群为P21/c,不对称单元中包含1个二价铜离子、2个2-吡啶甲酸配体以及2个Keggin类型[SiW12O40]4-多酸单元并组成零维结构。循环伏安测试表明化合物1在扫速为100 mV·s-1时,3组半波电位分别为-270、-516、-708 mV。化合物2为三方晶系,空间群为R3c,不对称单元中包含2个晶体学独立的二价铜离子并且具有2种不同的配位模式,是含六核簇合物单元的二维网络结构。

English

  • Polyoxometalates (POMs) are discrete anionic metal oxygen clusters and they exhibit a great diversity of sizes, nuclearities and shapes[1-2]. This kind of materials have attracted widespread attention because they show great potential in the realm of information technology, energy and environment[3-5]. Specifically, several recent examples have shown their candidacy for future application in: (1) information technology, where the POMs cluster containing [(Se(Ⅳ)O3)2]4- central unit could be oxidized to a [Se(Ⅴ)2O6]2- moiety with a {Se(Ⅴ)-Se(Ⅴ)} bond, resulting in a promising molecule for memory devices because of its characteristic“write - once - erase”[6]; (2) energy, where the clusters Na5[H3Pt(Ⅳ)W6O24] (PtW6O24) and Na3K5[Pt(Ⅱ)2(W5O18)2](Pt2(W5O18)2) exhibit higher electrocatalytic activity for hydrogen evolution reaction (HER) compared with metallic Pt0[7]; (3) environment, where supramolecular assembly consist-ing of POMs clusters and cationic organic hosts to achieve novel liquid separation membranes for many liquids, and the separation efficiency of both hydropho-bic and hydrophilic liquids could reach over 99%[8].

    Notably, with their versatial structural characters, inorganic-organic hybrid complexes containing POMs units and organic ligands are a valuable class of compounds since they could be used in the fields of catalysis, magnetism, electrochemistry, etc[9].Recently, several kinds of POMs-based compounds with different organic ligands have been reported by our laboratory[10-12].Following this research line, 2-picolinic acid (2-PA) has been selected to combine with POMs unit to achieve hybrid materials.2-PA, the derivative of pyridine with a carboxylic acid substituent at the 2-position, could provide potential coordination sites with its-N, -O atoms.In this contribution, it has been integrated with Keggin-type [SiW12O40]4- and [PMo12O40]3- units to achieve final products: H2[(CH3)4N]6[Cu(2-PA)2(SiW12O40)2](1) and (H3O)[Cu6(2-PA)9(PMo12O40)(NO3)](2).

    All the chemicals were received as reagent grade and used without any further purification.IR spectra were recorded from solid samples palletized with KBr on a Varian 640 FT/IR spectrometer in a range of 4 000~450 cm-1.Powder X-ray diffraction (PXRD) patterns collected on a DX-2600 spectrometer with Mo radiation (λ=0.071 073 nm) at 293 K (Voltage:40 kV, Current:30 mA, Scan range:0°~60°).

    A mixture of Cu (NO3)2·3H2O (241.6 mg), H4[SiW12O40](200 mg), 2-PA (123 mg) and 10 mL water was stirred at room temperature.The pH value was adjusted to 3.5 with 3.0 mol·L-1 HNO3, then the suspension was transferred to a Teflon-lined reactor and kept under autogenous pressure at 160℃ for 3 days. After slow cooling to room temperature, blue cubic crystals were filtered and washed with distilled water (Yield:48%, based on Cu). IR (KBr, cm-1):3 571 (m), 3 037 (w), 1 642 (m), 1 481 (m), 1 359 (m), 1 015 (m), 972(vs), 924 (vs), 886 (vs), 794 (vs), 534 (s).Anal. Calcd.for C36H82CuN8O84Si2W24 (%):C, 6.65;H, 1.27;N, 1.72. Found (%):C, 6.22;H, 1.05;N, 1.70.

    A mixture of Cu(NO3)2·3H2O (241.6 mg), (NH4)6Mo7O24·4H2O (100 mg), 2-PA (123 mg), 0.2 mL H3PO4 and 10 mL water was stirred at room temperature.The pH value was adjusted to 0.5 with 3.0 mol· L-1 HNO3, and then the suspension was transferred to a 25 mL Teflon-lined reactor and kept under autogenous pressure at 160℃ for 3 days.After slow cooling to room temperature, green cubic crystals were filtered and washed with distilled water (Yield:68%, based on Cu).IR (KBr, cm-1):1 642(w), 1 620(w), 1 595(w), 954(w), 924(vs), 805(m), 689(w). Anal. Calcd. for C54H39Cu6Mo12N10O62P(%):C, 19.17;H, 1.16;N, 4.14. Found(%):C, 19.01;H, 1.35;N, 4.21.

    Single crystal X-ray diffraction analysis data for compounds 1 and 2 were collected with an Oxford Diffraction Gemini R Ultradiffractometer with graphitemonochromated Mo (λ=0.071 073 nm) radiation at 293 K.Then, the structures were solved by direct methods and refined on F2 by full-matrix least-squares methods using the SHELXTL package[13-14]. The hydrogen atoms attached to carbon atoms were placed at geometrically estimated positions.A summary of the crystal data and structure refinements of compounds 1 and 2 is provided in Table 1 and the selected bond lengths and angles are given in Table 2.

    Table 1

    Table 1.  Crystal data and structure refinements for compounds 1 and 2
    下载: 导出CSV
    1 2
    Empirical formula C36H82CuN8O84Si2W24 C54H39Cu6Mo12N10O62P
    Formula weight 6 502.92 3 383.45
    Crystal system Monoclinic Trigonal
    Space group P21/c R3c
    a/nm 1.329 7(3) 1.679 2(12)
    b/nm 2.055 5(6) 1.679 2(12)
    c/nm 2.276 0(6) 5.245 3(19)
    β/(°) 96.064(2)
    Reflection collected 26 121 5 799
    Independent reflection 12 630(Rint=0.053 6) 3 312 (Rint=0.055 9)
    Data, restraint, parameter 12 630, 132, 672 3 312, 7, 436
    Goodness-of-fit on F2 1.081 1.027
    R1, wR2[I>2σ(I)] 0.060 0, 0.129 1 0.048 7, 0.114 7
    R1, wR2(all data) 0.096 7, 0.149 2 0.058 8, 0.127 0
    Largest diff.peak and hole/(e·nm-3) 3 240, -3 460 780, -1 390
    a$ {R_1} = \sum {\left| {\left| {{F_{\rm{O}}}} \right| - \left| {{F_{\rm{C}}}} \right|} \right|/\sum {\left| {{F_{\rm{O}}}} \right|} } $, b$ w{R_2} = \sum {[w(} {F_{\rm{O}}}^2 - {F_{\rm{C}}}^2{)^2}]/\sum {[w(} {F_{\rm{O}}}^2{)^2}{]^{1/2}}$

    Table 2

    Table 2.  Selected bond distances (nm) and bond angles (°) for 1 and 2
    下载: 导出CSV
    1
    Cu1-O1 0.195 9(17) Cu1-N1 0.200 4(18)
    Cu1-O11 0.195 9(17) Cu1-N11 0.200 4(18)
               
    O1-Cu1-O11 180 O1-Cu1-N11 96.1(8) O11-Cu1-N1 96.1(8)
    O1-Cu1-N1 83.9(8) O11-Cu1-N11 83.9(8) N1-Cu1-N11 180.0(11)
    2
    Cu1-O1 0.194 4(15) Cu2-O4#3 0.193 3(12) Cu2-N3 0.193 5(16)
    Cu1-O3 0.192 4(13) Cu2-O6 0.195 5(13) O4-Cu2#4 0.193 3(12)
    Cu1-O5 0.192 6(13) Cu2-O7 0.239(2) N2-Cu2#4 0.191 5(16)
    Cu1-N1 0.195 8(15) Cu2-N2#3 0.191 5(16)
               
    O1-Cu1-N1 83.6(6) O4#3-Cu2-O6 168.3(6) N2#3-Cu2-O7 88.4(7)
    O3-Cu1-O1 175.6(6) O4#3-Cu2-O7 76.6(6) N2#3-Cu2-N3 177.2(7)
    O3-Cu1-O5 98.9(6) O4#3-Cu2-N3 97.6(6) N3-Cu2-O6 83.6(6)
    O3-Cu1-N1 92.4(6) O6-Cu2-O7 115.0(6) N3-Cu2-O7 89.7(7)
    O5-Cu1-O1 85.4(6) N2#3-Cu2-O4#3 83.9(6)
    O5-Cu1-N1 164.6(6) N2#3-Cu2-O6 95.4(6)
    Symmetry codes:#1:1-x, 1-y, 1-z for 1; #1:1+y-x, 2-x, z; #2:2-y, 1+x-y, z; #3:1-y, 1+x-y, z; #4:y-x, 1-x, z for 2.

    CCDC: 1978845, 1; 1978846, 2.

    X-ray single crystal diffraction analysis reveals that compound 1 is a zero-dimensional (0D) structure.It crystalizes in monoclinic system with space group P21/c.The asymmetric unit is composed of one Cu(Ⅱ) ion, two 2-PA ligands and two[SiW12O40]4-Keggin-type polyoxometalate anions.The bond valence calculation shows that the Si atoms are in +4 oxidation state, all the W atoms are in +6 oxidation state, and the Cu atoms are in +2 oxidation state[15].As for the coordination mode of the Cu, the coordination oxygen atoms in the axial direction are from two different[SiW12O 40]4-POMs units (Fig. 1a).Based on the six-coordinated situation, an octahedral structure is fulfilled (Fig. 1b).The bond lengths of Cu-O bond and Cu-N bond are in a range of 0.195 9(17)~0.250 9(14) nm and 0.200 4(18) nm, respectively.

    Figure 1

    Figure 1.  (a) Structure of compound 1; (b) Octahedron configuration of Cu ion

    All hydrogen atoms are omitted for clarity; Symmetry code: #1: 1-x, 1-y, 1-z

    Compound 2 crystallizes in trigonal system with space group R3c, and bond valence sum calculations[15]show that all molybdenum atoms are in +6 oxidation state, phosphorus atom is in +5 oxidation state, and Cu atoms are in +2 oxidation state.There are two crystallographically independent Cu(Ⅱ) ions with two kinds of coordination modes (Fig. 2).Cu1 is coordinated by one N atoms from 2-PA ligand, three O atoms from three 2-PA ligands and one O atom from PMo12 polyoxoanion, showing a distorted quadrilateral cone configuration [CuN1O4](Fig. 2b).Cu2 is five-coordinated by two N atoms from two 2-PA ligands, two O atoms from two 2-PA ligands and one O from NO3- anion to exhibit a distorted quadrilateral cone configuration [CuN2O3](Fig. 2c).The bond lengths of Cu-O bond and Cu-N bond are in a range of 0.192 4(13)~0.239(2) nm and 0.191 5(16)~0.195 8(15) nm, respectively (Table 2).

    Figure 2

    Figure 2.  (a) Asymmetric unit of compound 2; (b, c) Coordination environment of Cu1 and Cu2, respectively

    Adjacent six Cu(Ⅱ) ions are linked by 2-PA ligands and nitrate group, forming a hexanuclear cluster. In the hexanuclear cluster, three Cu2 ions are bound together via nitrate group to form a Cu3(NO3) triangle. Similarly, three Cu1 ions form a larger triangle by the Cu3(NO3) triangle and 2-PA ligands (Fig. 3a). Each PMo12 is wrapped by three hexa-nuclear clusters to form a three-leaf fan shape (Fig. 3b). There is right-handed helical chain presented in compound 2 (Fig. 3c) and furthermore, the hexauclear cluster are linked together to form a two-dimensional (2D) network (Fig. 3d).

    Figure 3

    Figure 3.  Structure of compound 2: (a) hexanuclear Cu cluster structure; (b) three-leaf fan structure; (c) right-handed helical chain; (d) two-dimensional packing structure

    During the crystallographic analysis of POMs clusters, it is generally easy to identify unambiguously the heavy atoms such as Mo and W, but very often it is hard to locate counter cations because of inherent crystallographic disorder issues. The situation becomes worse for the lighter atoms such as N and C. As for compound 1, it is good to see the exact position of the [(CH3)4N]+ cations could be identified and located unambiguously. To keep the charge balance, two isolated protons is included in the structure because of the acidic experimental condition. As for compound 2, to keep the charge balance, the isolated hydronium is included in the structure[16].

    In the IR spectra of compounds 1 and 2, a strong band at 1 643 cm-1 (1) and 1 640 cm-1 (2) can be attributed to the C=O stretching vibration of the carboxyl group. A broad band at 3 571 cm-1 (1) and 3 448 cm-1 (2) can be attributed to the characteristic O-H stretching vibration of carboxyl group. A band at 1 604 cm-1 (1) and 1 604 cm-1(2) can be assigned to the coordinat-ed pyridyl ring vibrations. As for compound 1, the bands at 924, 886, 794, 534 cm-1 can be assigned to the stretching vibration of Si-O, W-O and W-O-W in [SiW12O40]4- polyoxometalates anion (Fig. 4a). For compound 2, the bands at 954, 805 and 689 cm-1 are characteristic absorption peaks of Mo-O, Mo-O-Mo and P-O (Fig. 4b).

    Figure 4

    Figure 4.  IR spectra of compounds (a) 1 and (b) 2

    To test the phase purity of compounds 1 and 2, PXRD experiments were carried out (Fig. 5). The diffraction peaks of both simulated and experimental patterns match well in the key positions, which indicate that the powders of these two compounds are single phase. The intensity differences may arise from the different orientation of samples.

    Figure 5

    Figure 5.  PXRD patterns of compounds 1 and 2

    We try to measure the electrochemical properties of compounds 1 and 2, but unfortunately, compound 2 is not stable in the electrolyte and there is no observable pattern for its cyclic voltammogram. So only the electrochemical property of compound 1 are reported here. When the sweep speed was 100 mV·s-1, in the potential range of -800~0 mV, the half-wave potentials (E1/2=(Ecp+Eap)/2) of Ⅰ-Ⅰ', Ⅱ-Ⅱ' and Ⅲ-Ⅲ' in compound 1 were -270, -516 and -708 mV, which can be attributed to electronic redox process of [SiW12 O40]4- unit (Fig. 6)[11]. As the scanning rate increased, the cathode peak potentials of the compound 1 moved in the negative direction, and the corresponding anode peak potentials moved in the positive direction.

    Figure 6

    Figure 6.  Cyclic voltammogram of 1-CPE (the bulk-modified carbon paste electrode) in 0.5 mol·L-1 Na2SO4+0.1 mol·L-1 H2SO4 aqueous solution at different scan rates

    From inner to outer: scan rate=20, 40, 60, 80, 100, 150, 200, 250, 300, 350, 400, 450, 500 mV·s-1

    In summary, using 2-picolinic acid as organic ligand, two inorganic-organic hybrid compounds containing Keggin-type polyoxometalates units were obtained.Apparently, taking advantage of hydrothermal method, different types of hybrid compounds could be fabricated in a feasible way.Interestingly, under strong acidic experimental condition (pH≈0.5) by using H3PO4/HNO3 in the synthetic process of 2, [Mo7O24]6-unit has transformed to Keggin-type [PMo12O40]3- unit in the presence of PO43- ions.Undoubtedly, the choice of experimental conditions (pH, solvent, temperature, buffer solution, ionic strength, the sort of counter-cations and reducing agents, etc.) could play important role in the process of assembling final POMs clusters.It is anticipated that more interesting compounds with versatile structural characters could be obtained consistently.


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  • Figure 1  (a) Structure of compound 1; (b) Octahedron configuration of Cu ion

    All hydrogen atoms are omitted for clarity; Symmetry code: #1: 1-x, 1-y, 1-z

    Figure 2  (a) Asymmetric unit of compound 2; (b, c) Coordination environment of Cu1 and Cu2, respectively

    Figure 3  Structure of compound 2: (a) hexanuclear Cu cluster structure; (b) three-leaf fan structure; (c) right-handed helical chain; (d) two-dimensional packing structure

    Figure 4  IR spectra of compounds (a) 1 and (b) 2

    Figure 5  PXRD patterns of compounds 1 and 2

    Figure 6  Cyclic voltammogram of 1-CPE (the bulk-modified carbon paste electrode) in 0.5 mol·L-1 Na2SO4+0.1 mol·L-1 H2SO4 aqueous solution at different scan rates

    From inner to outer: scan rate=20, 40, 60, 80, 100, 150, 200, 250, 300, 350, 400, 450, 500 mV·s-1

    Table 1.  Crystal data and structure refinements for compounds 1 and 2

    1 2
    Empirical formula C36H82CuN8O84Si2W24 C54H39Cu6Mo12N10O62P
    Formula weight 6 502.92 3 383.45
    Crystal system Monoclinic Trigonal
    Space group P21/c R3c
    a/nm 1.329 7(3) 1.679 2(12)
    b/nm 2.055 5(6) 1.679 2(12)
    c/nm 2.276 0(6) 5.245 3(19)
    β/(°) 96.064(2)
    Reflection collected 26 121 5 799
    Independent reflection 12 630(Rint=0.053 6) 3 312 (Rint=0.055 9)
    Data, restraint, parameter 12 630, 132, 672 3 312, 7, 436
    Goodness-of-fit on F2 1.081 1.027
    R1, wR2[I>2σ(I)] 0.060 0, 0.129 1 0.048 7, 0.114 7
    R1, wR2(all data) 0.096 7, 0.149 2 0.058 8, 0.127 0
    Largest diff.peak and hole/(e·nm-3) 3 240, -3 460 780, -1 390
    a$ {R_1} = \sum {\left| {\left| {{F_{\rm{O}}}} \right| - \left| {{F_{\rm{C}}}} \right|} \right|/\sum {\left| {{F_{\rm{O}}}} \right|} } $, b$ w{R_2} = \sum {[w(} {F_{\rm{O}}}^2 - {F_{\rm{C}}}^2{)^2}]/\sum {[w(} {F_{\rm{O}}}^2{)^2}{]^{1/2}}$
    下载: 导出CSV

    Table 2.  Selected bond distances (nm) and bond angles (°) for 1 and 2

    1
    Cu1-O1 0.195 9(17) Cu1-N1 0.200 4(18)
    Cu1-O11 0.195 9(17) Cu1-N11 0.200 4(18)
               
    O1-Cu1-O11 180 O1-Cu1-N11 96.1(8) O11-Cu1-N1 96.1(8)
    O1-Cu1-N1 83.9(8) O11-Cu1-N11 83.9(8) N1-Cu1-N11 180.0(11)
    2
    Cu1-O1 0.194 4(15) Cu2-O4#3 0.193 3(12) Cu2-N3 0.193 5(16)
    Cu1-O3 0.192 4(13) Cu2-O6 0.195 5(13) O4-Cu2#4 0.193 3(12)
    Cu1-O5 0.192 6(13) Cu2-O7 0.239(2) N2-Cu2#4 0.191 5(16)
    Cu1-N1 0.195 8(15) Cu2-N2#3 0.191 5(16)
               
    O1-Cu1-N1 83.6(6) O4#3-Cu2-O6 168.3(6) N2#3-Cu2-O7 88.4(7)
    O3-Cu1-O1 175.6(6) O4#3-Cu2-O7 76.6(6) N2#3-Cu2-N3 177.2(7)
    O3-Cu1-O5 98.9(6) O4#3-Cu2-N3 97.6(6) N3-Cu2-O6 83.6(6)
    O3-Cu1-N1 92.4(6) O6-Cu2-O7 115.0(6) N3-Cu2-O7 89.7(7)
    O5-Cu1-O1 85.4(6) N2#3-Cu2-O4#3 83.9(6)
    O5-Cu1-N1 164.6(6) N2#3-Cu2-O6 95.4(6)
    Symmetry codes:#1:1-x, 1-y, 1-z for 1; #1:1+y-x, 2-x, z; #2:2-y, 1+x-y, z; #3:1-y, 1+x-y, z; #4:y-x, 1-x, z for 2.
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  • 发布日期:  2020-09-01
  • 收稿日期:  2020-03-08
  • 修回日期:  2020-05-15
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