Syntheses, Crystal Structures, and Luminescent Property of Two 1D Cadmium(Ⅱ) Coordination Polymers Assembled from an Ether-Bridged Tetracarboxylic Acid

Yu LI Zhen-Yu ZHAO Xun-Zhong ZOU An-Sheng FENG Wen-Da QIU

Citation:  LI Yu, ZHAO Zhen-Yu, ZOU Xun-Zhong, FENG An-Sheng, QIU Wen-Da. Syntheses, Crystal Structures, and Luminescent Property of Two 1D Cadmium(Ⅱ) Coordination Polymers Assembled from an Ether-Bridged Tetracarboxylic Acid[J]. Chinese Journal of Inorganic Chemistry, 2020, 36(9): 1728-1734. doi: 10.11862/CJIC.2020.181 shu

由醚氧桥联四羧酸配体构筑的两个一维镉(Ⅱ)配位聚合物的合成、晶体结构及荧光性质

    通讯作者: 赵振宇, shzhzhao123@163.com
    邱文达, qiuwd123@163.com
  • 基金项目:

    广东省高等职业院校珠江学者岗位计划资助项目 2018

    广州市科技计划项目 201904010381

    广东省高校创新团队项目 2017GKCXTD001

    广东省高等职业院校珠江学者岗位计划资助项目 2015

    深圳市科技计划项目 GGFW2017041209483817

    深圳市科技计划项目 JCYJ20170817112445033

    广东省大学生科技创新培育专项 pdjh2019b0690

    广东轻院珠江学者人才类项目 RC2015-001

    广东省高等职业院校珠江学者岗位计划资助项目(2015,2018)、广东轻院珠江学者人才类项目(No.RC2015-001)、广东省高校创新团队项目(No.2017GKCXTD001)、广州市科技计划项目(No.201904010381)、深圳市科技计划项目(No.JCYJ20170817112445033,GGFW2017041209483817)和广东省大学生科技创新培育专项(No.pdjh2019b0690)资助

摘要: 采用水热方法,用醚氧桥联四羧酸配体(H4L)和菲咯啉(phen)、2,2'-联吡啶(2,2'-bipy)与CdCl2·H2O反应,合成了2个一维配位聚合物[Cd2μ5-L)(phen)2]n1)和{[Cd2μ4-L)(2,2'-bipy)2(H2O)2]·2H2O}n2),并对其结构和荧光性质进行了研究。结构分析结果表明2个配合物分别属于单斜和三斜晶系,P21/cP1空间群。聚合物12分别具有基于四核Cd4和Cd2单元的一维链结构。研究表明,配合物12在室温下能发出蓝色荧光。

English

  • The design and synthesis of functional coordination polymers have become the subjects of extensive investigation owing to their intriguing architectures and functional properties, such as magnetism, catalysis, luminescence, and gas storage[1-5]. However, there still remains a great challenge for directional construction of functional coordination polymers with predictable molecular structures and expected properties, because a lot of factors influence the construction of complexes, such as the structural features of organic ligands, the coordination requirements of metal ions, solvent systems, temperatures, and pH values[6-10].

    In this context, various types of aromatic polycarboxylic acids have been extensively utilized to synthesize various coordination polymers owing to their strong coordination ability in diverse modes and the fact that they are able to satisfy the geometric requirement of the metal centers[2-3, 6, 10-14].

    As a combination of the aforementioned aspects and our previous research work, we have selected a new asymmetric tetracarboxylate ligand, 2, 3, 3′, 4′-diphenyl ether tetracarboxylic acid (H4L, Scheme 1) and explored it for the construction of novel coordination polymers. The selection of H4L has been governed by the following reasons. (1) This ligand contains two phenyl rings that are interconnected by a rotatable O-ether group providing a subtle conformational adaptation. (2) H4L contains two different types of functionalities (i.e., -COOH and O-ether) and has nine potential coordination sites, which can result in diverse coordination patterns and high dimensionalities, especially when acting as a multiply bridging spacer. (3) This tetracarboxylic acid block remains poorly used for the generation of coordination polymers.

    Scheme 1

    Scheme 1.  Structures of H4L and the auxiliary ligands

    In this work, we report the syntheses, crystal structures, and luminescent properties of two Cd(Ⅱ) coordination polymers constructed from the tetracarboxylate ligand.

    All chemicals and solvents were of AR grade and used without further purification. H4L was acquired from Jinan Henghua Sci. & Technol. Co., Ltd. Carbon, hydrogen and nitrogen were determined using an Elementar Vario EL elemental analyzer. IR spectra were recorded using KBr pellets and a Bruker EQUINOX 55 spectrometer. Thermogravimetric analysis (TGA) data were collected on a LINSEIS STA PT1600 thermal analyzer with a heating rate of 10 ℃·min-1. Excitation and emission spectra were recorded on an Edinburgh FLS920 fluorescence spectrometer using the solid samples at room temperature.

    A mixture of CdCl2·H2O (0.040 g, 0.20 mmol), H4L (0.035 g, 0.10 mmol), phen (0.040 g, 0.20 mmol), NaOH (0.016 g, 0.40 mmol), and H2O (10 mL) was stirred at room temperature for 15 min, and then sealed in a 25 mL Teflon-lined stainless steel vessel, and heated at 160 ℃ for 3 days, followed by cooling to room temperature at a rate of 10 ℃ ·h-1. Colourless block - shaped crystals of 1 were isolated manually, and washed with distilled water. Yield: 43% (based on H4L). Anal. Calcd. for C40H22Cd2N4O9(%): C 51.80, H 2.39, N 6.04; Found(%): C 51.93, H 2.38, N 6.01. IR (KBr, cm-1): 1 588s, 1 515w, 1 431w, 1 397s, 1 363m, 1 256w, 1 240w, 1 144w, 1 099w, 1 060w, 980w, 924w, 851m, 783w, 727m, 699w, 637w.

    The preparation of 2 was similar to that of 1 except 2, 2′-bipy was used instead of phen. After cooling the reaction mixture to room temperature, colourless block-shaped crystals of 2 were isolated manually, washed with distilled water, and dried. Yield: 48% (based on H4L). Anal. Calcd. for C36H30Cd2N4O13(%): C 45.44, H 3.18, N 5.89; Found(%): C 45.21, H 3.16, N 5.93. IR (KBr, cm-1): 3 390w, 3 074w, 1 567s, 1 470w, 1 436m, 1 391s, 1 313w, 1 256w, 1 234m, 1 154w, 1 060w, 1 015w, 980w, 856w, 823w, 806w, 766m, 733w, 699w, 654w.

    The compounds are insoluble in water and common organic solvents, such as methanol, ethanol, acetone, and DMF.

    Two single crystals with dimensions of 0.22 mm× 0.21 mm×0.19 mm (1) and 0.21 mm×0.20 mm×0.18 mm (2) were collected at 293(2) K on a Bruker SMART APEX Ⅱ CCD diffractometer with Mo radiation (λ= 0.071 073 nm). The structures were solved by direct methods and refined by full matrix least-square on F2 using the SHELXTL-2014 program[15]. All non-hydrogen atoms were refined anisotropically. All the hydrogen atoms were positioned geometrically and refined using a riding model. A summary of the crystallography data and structure refinements for 1 and 2 is given in Table 1. The selected bond lengths and angles for compounds 1 and 2 are listed in Table 2. Hydrogen bond parameters of compound 2 are given in Table 3.

    Table 1

    Table 1.  Crystal data for compounds 1 and 2
    下载: 导出CSV
    Compound 1 2
    Chemical formula C40H22Cd2N4O9 C36H30Cd2N4O13
    Formula weight 927.41 951.44
    Crystal system Monoclinic Triclinic
    Space group P21/c P1
    a / nm 1.184 09(8) 0.930 77(8)
    b / nm 1.178 61(11) 1.191 97(11)
    c / nm 2.389 62(18) 1.713 64(11)
    α / (°) 97.116(6)
    β / (°) 91.964(6) 92.986(6)
    γ / (°) 109.187(8)
    V / nm3 3.332 9(5) 1.773 0(3)
    Z 4 2
    F(000) 1832 948
    θ range for data collection / (°) 3.412~25.042 3.389~25.050
    Limiting indices -14 ≤ h ≤ 14, -14 ≤ k ≤ 11, -28 ≤ l ≤ 23 -11 ≤ h ≤ 11, -14 ≤ k ≤ 13, -20 ≤ l ≤ 17
    Reflection collected, unique (Rint) 20 338, 5 885 (0.107 9) 11 174, 6 248 (0.068 6)
    Dc / (Mg·m-3) 1.848 1.782
    μ / mm-1 1.345 1.274
    Data, restraint, parameter 5 885, 0, 496 6 248, 0, 496
    Goodness-of-fit on F2 0.848 1.056
    Final R indices [I≥2σ(I)] R1, wR2 0.056 7, 0.080 6 0.063 9, 0.080 4
    R indices (all data) R1, wR2 0.101 2, 0.110 8 0.103 8, 0.131 1
    Largest diff. peak and hole / (e·nm-3) 916 and -707 785 and -928

    Table 2

    Table 2.  Selected bond distances (nm) and bond angles (°) for compounds 1 and 2
    下载: 导出CSV
    1
    Cd(1)-O(1) 0.253 3(5) Cd(1)-O(3) 0.232 3(5) Cd(1)-O(4)A 0.224 7(5)
    Cd(1)-O(8)B 0.218 9(6) Cd(1)-N(1) 0.237 0(6) Cd(1)-N(2) 0.238 1(6)
    Cd(2)-O(1) 0.233 1(5) Cd(2)-O(2) 0.236 8(5) Cd(2)-O(6)B 0.240 1(5)
    Cd(2)-O(7)B 0.231 8(5) Cd(2)-N(3) 0.232 2(7) Cd(2)-N(4) 0.228 6(6)
    O(8)B-Cd(1)-O(4)A 97.8(2) O(8)B-Cd(1)-O(3) 151.7(2) O(4)A-Cd(1)-O(3) 96.82(18)
    N(1)-Cd(1)-O(8)B 91.3(2) O(4)A-Cd(1)-N(1) 151.6(2) O(3)-Cd(1)-N(1) 87.15(19)
    O(8)B-Cd(1)-N(2) 123.8(2) O(4)A-Cd(1)-N(2) 82.67(19) O(3)-Cd(1)-N(2) 82.0(2)
    N(1)-Cd(1)-N(2) 70.0(2) O(8)B-Cd(1)-O(1) 75.1(2) O(1)-Cdo(1)-O(4)A 106.77(18)
    O(3)-Cd(1)-O(1) 77.60(18) O(1)-Cd(1)-N(1) 101.6(2) O(1)-Cd(1)-N(2) 158.38(17)
    O(7)B-Cd(2)-N(4) 132.1(2) N(3)-Cd(2)-N(4) 72.2(2) O(7)B-Cd(2)-N(3) 103.3(2)
    N(4)-Cd(2)-O(1) 117.2(2) O(1)-Cd(2)-O(7)B 99.83(19) O(1)-Cd(2)-N(3) 134.6(2)
    O(2)-Cd(2)-N(4) 134.2(2) O(7)B-Cd(2)-O(2) 91.06(19) O(2)-Cd(2)-N(3) 85.06(19)
    O(1)-Cd(2)-O(2) 55.76(17) O(6)B-Cd(2)-N(4) 84.4(2) O(7)B-Cd(2)-O(6)B 55.24(17)
    N(3)-Cd(2)-O(6)B 118.7(2) O(1)-Cd(2)-O(6)B 106.64(19) O(2)-Cd(2)-O(6)B 140.98(18)
    2
    Cd(1)-O(1) 0.256 2(6) Cd(1)-O(2) 0.228 4(5) Cd(1)-O(4)A 0.227 9(6)
    Cd(1)-O(10) 0.235 5(6) Cd(1)-N(1) 0.233 3(7) Cd(1)-N(2) 0.232 3(6)
    Cd(2)-O(6)B 0.250 0(6) Cd(2)-O(7)B 0.236 2(7) Cd(2)-O(8) 0.236 6(5)
    Cd(2)-O(9) 0.242 7(6) Cd(2)-O(11) 0.238 4(6) Cd(2)-N(3) 0.229 7(8)
    Cd(2)-N(4) 0.230 2(7)
    O(2)-Cd(1)-O(4)A 108.2(2) O(4)A-Cd(1)-N(2) 97.8(2) O(2)-Cd(1)-N(2) 153.9(2)
    N(1)-Cd(1)-O(4)A 117.7(2) O(2)-Cd(1)-N(1) 97.2(2) N(2)-Cd(1)-N(1) 69.8(2)
    O(4)A-Cd(1)-O(10) 79.0(2) O(10)-Cd(1)-O(2) 95.0(2) O(10)-Cd(1)-N(2) 89.9(2)
    N(1)-Cd(1)-O(10) 154.6(2) O(4)A-Cd(1)-O(1) 149.9(2) O(1)-Cdo(1)-O(2) 53.56(18)
    N(2)-Cd(1)-O(1) 102.6(2) O(1)-Cd(1)-N(1) 90.2(2) O(1)-Cd(1)-O(10) 79.3(2)
    N(3)-Cd(2)-N(4) 70.9(3) N(3)-Cd(2)-O(7)B 96.5(3) O(7)B-Cd(2)-N(4) 130.1(2)
    N(3)-Cd(2)-O(8) 99.3(2) N(4)-Cd(2)-O(8) 139.7(2) O(7)B-Cd(2)-O(8) 89.1(2)
    O(11)-Cd(2)-N(3) 165.4(3) O(11)-Cd(2)-N(4) 95.8(3) O(7)B-Cd(2)-O(11) 96.8(2)
    O(8)-Cd(2)-O(11) 86.9(2) O(9)-Cd(2)-N(3) 88.5(2) O(9)-Cd(2)-N(4) 86.4(2)
    O(7)B-Cd(2)-O(9) 142.8(2) O(8)-Cd(2)-O(9) 53.73(19) O(11)-Cd(2)-O(9) 84.5(2)
    N(3)-Cd(2)-O(6)B 109.5(2) N(4)-Cd(2)-O(6)B 85.9(2) O(7)B-Cd(2)-O(6)B 52.1(2)
    O(8)-Cd(2)-O(6)B 132.9(2) O(11)-Cd(2)-O(6)B 74.5(2) O(9)-Cd(2)-O(6)B 156.8(3)
    Symmetry transformations used to generate equivalent atoms: A: -x, -y+2, -z+1; B: x-1, y, z for 1; A: -x+1, -y+1, -z+1; B: -x, -y, -z+2 for 2.

    Table 3

    Table 3.  Hydrogen bond parameters of compound 2
    下载: 导出CSV
    D—H…A d(D-H) / nm d(H…A) / nm d(D…A) / nm ∠DHA / (°)
    O(10)—H(1W)…O(1)A 0.085 0 0.196 5 0.281 5 179.74
    O(10)—H(2W)…O(12) 0.089 0 0.177 9 0.264 7 164.37
    O(11)—H(3W)…O(8)B 0.081 3 0.194 6 0.275 3 172.06
    O(11)—H(4W)…O(13)C 0.072 2 0.208 2 0.278 5 164.98
    O(12)—H(5W)…O(2)D 0.085 0 0.202 0 0.287 0 179.20
    O(12)—H(6W)…O(3) 0.085 0 0.1873 0.272 3 178.95
    O(13)—H(7W)…O(7)E 0.079 9 0.1580 0.237 2 170.57
    Symmetry codes: A: -x+2, -y+1, -z+1; B: -x, -y, -z+2; C: x, y-1, z+1; D: -x+1, -y+1, -z+1; E: x, y+1, z-1.

    CCDC: 1971327, 1; 1971328, 2.

    2.1.1   [Cd2(μ5-L)(phen)2]n (1)

    The molecular structure of compound 1 is shown in Fig. 1. The asymmetric unit contains two Cd atoms (Cd1 and Cd2), a μ5-L4- ligand, and two phen moieties. The six-coordinated Cd1 center displays a distorted octahedral {CdN2O4} environment filled by four carboxylate O atoms from three individual μ5-L4- blocks and two N atoms from the phen moiety. The Cd2 center is also six-coordinated and features a distorted octahedral {CdN2O4} geometry that is taken by four carboxylate O atoms from two different μ5-L4- blocks and two N atoms from the phen moiety. The lengths of the Cd-O and Cd- N bonds are 0.218 9(6)~0.253 3(5) and 0.228 6(6)~ 0.238 1(6) nm, respectively, which are within the normal values for related Cd(Ⅱ) derivatives[6, 10, 16]. In 1, the L4- block acts as a μ5-ligand, wherein the COO- groups are monodentate, bidentate or tridentate (mode Ⅰ, Scheme 2). The carboxylate groups of four μ5 - L4- blocks link the adjacent Cd(Ⅱ) centers into a Cd4 subunit (Fig. 2). Such subunits are further assembled via the remaining COO- groups of μ5 - L4- blocks to a 1D chain (Fig. 2).

    Figure 1

    Figure 1.  Drawing of asymmetric unit of compound 1 with 30% probability thermal ellipsoids

    H atoms were omitted for clarity; Symmetry codes: A:-x, -y+2, -z+1; B: x-1, y, z

    Scheme 2

    Scheme 2.  Coordination modes of L4- ligands in compounds 1 and 2

    Figure 2

    Figure 2.  View of 1D chain in compound 1 along b axis

    Phen ligands are omitted for clarity; Symmetry codes: A:-x, -y+2, -z+1; B: x-1, y, z; C: x+1, y, z

    2.1.2   {[Cd2(μ4-L)(2, 2′-bipy)2(H2O)2]·2H2O}n (2)

    The asymmetric unit of 2 bears two Cd(Ⅱ) centers (Cd1 and Cd2), one μ4 -L4- linker, two 2, 2′ - bipy moieties, two terminal water ligands and two lattice water molecules (Fig. 3). The seven - coordinated Cd1 center adopts a distorted pentagonal bipyramid {CdN2O5} environment taken by four carboxylate O atoms from two independent μ4-L4- blocks, one O atom from the H2O ligand, and a pair of N atoms from the 2, 2′-bipy moiety. The Cd2 center is six-coordinated and reveals a distort- ed octahedral {CdN2O4} geometry. It is completed by three carboxylate O donors from two μ4-L4- blocks, one O atom from the H2O ligand, and two N donors from the 2, 2′ - bipy moiety. The Cd - O (0.227 9(6)~0.256 2(6) nm) and Cd - N (0.229 7(8)~0.233 3(7) nm) bonds are within standard values[14, 16-17]. The L4- block behaves as a heptadentate μ4-linker (Scheme 2, mode Ⅱ). Two μ4- L4- blocks link adjacent Cd(Ⅱ) centers to form a Cd2 unit (Fig. 4). Furthermore, these Cd2 units are further extended by μ4-L4- blocks into a 1D chain (Fig. 4). Com- pounds 1 and 2 were obtained under similar reaction conditions except using different auxiliary ligands (phen for 1 and 2, 2′-bipy for 2), which result in differ- ent structures.

    Figure 3

    Figure 3.  Drawing of asymmetric unit of compound 2 with 30% probability thermal ellipsoids

    Lattice water molecule and H atoms were omitted for clarity; Symmetry codes: A:-x+1, -y+1, -z+1; B: -x, -y, -z+2

    Figure 4

    Figure 4.  View of 1D chain in compound 2 along a axis

    2, 2′-Bipy ligands are omitted for clarity; Symmetry codes: A:-x+1, -y+1, -z+1; B: -x, -y, -z+2; C: x+1, y+1, z-1

    To determine the thermal stability of compounds 1 and 2, their thermal behaviors were investigated under nitrogen atmosphere by thermogravimetric analysis (TGA). As shown in Fig. 5, TGA curve of compound 1 shows that the sample remained stable until 327 ℃. Compound 2 lost its two lattice water molecules and two H2O ligands in a range of 45~157 ℃ (Obsd. 7.2%; Calcd. 7.6%), followed by the decomposition at 254 ℃.

    Figure 5

    Figure 5.  TGA curves of compounds 1 and 2

    Solid-state emission spectra of H4L and cadmium(Ⅱ) compounds 1 and 2 were measured at room temperature (Fig. 6). The spectrum of H4L revealed a weak emission with a maximum at 384 nm (λex=320 nm). In comparison with H4L, compounds 1 and 2 exhibited more extensive emission with maximum at 376 and 381 nm (λex=320 nm). These emissions correspond to intraligand π-π* or n-π* transition of H2L[6, 10, 17]. Enhancement of the luminescence in 1 and 2 compared to H4L can be explained by the coordination of ligands to Cd(Ⅱ); the coordination can augment a rigidity of ligands and reduce an energy loss due to radiationless decay[10, 16-17].

    Figure 6

    Figure 6.  Solid-state emission spectra of H4L and compounds 1 and 2 at room temperature

    In summary, we have successfully synthesized and characterized two new cadmium coordination polymers by using a tetracarboxylate acid as a ligand under hydrothermal condition. Compounds 1 and 2 show 1D chains composed of Cd4 and Cd2 units, respectively. Besides, the luminescent properties were also investigated and discussed. The results show that such tetracarboxylic acid can be used as a versatile multifunctional building block toward the generation of new coordination polymers.


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  • Scheme 1  Structures of H4L and the auxiliary ligands

    Figure 1  Drawing of asymmetric unit of compound 1 with 30% probability thermal ellipsoids

    H atoms were omitted for clarity; Symmetry codes: A:-x, -y+2, -z+1; B: x-1, y, z

    Scheme 2  Coordination modes of L4- ligands in compounds 1 and 2

    Figure 2  View of 1D chain in compound 1 along b axis

    Phen ligands are omitted for clarity; Symmetry codes: A:-x, -y+2, -z+1; B: x-1, y, z; C: x+1, y, z

    Figure 3  Drawing of asymmetric unit of compound 2 with 30% probability thermal ellipsoids

    Lattice water molecule and H atoms were omitted for clarity; Symmetry codes: A:-x+1, -y+1, -z+1; B: -x, -y, -z+2

    Figure 4  View of 1D chain in compound 2 along a axis

    2, 2′-Bipy ligands are omitted for clarity; Symmetry codes: A:-x+1, -y+1, -z+1; B: -x, -y, -z+2; C: x+1, y+1, z-1

    Figure 5  TGA curves of compounds 1 and 2

    Figure 6  Solid-state emission spectra of H4L and compounds 1 and 2 at room temperature

    Table 1.  Crystal data for compounds 1 and 2

    Compound 1 2
    Chemical formula C40H22Cd2N4O9 C36H30Cd2N4O13
    Formula weight 927.41 951.44
    Crystal system Monoclinic Triclinic
    Space group P21/c P1
    a / nm 1.184 09(8) 0.930 77(8)
    b / nm 1.178 61(11) 1.191 97(11)
    c / nm 2.389 62(18) 1.713 64(11)
    α / (°) 97.116(6)
    β / (°) 91.964(6) 92.986(6)
    γ / (°) 109.187(8)
    V / nm3 3.332 9(5) 1.773 0(3)
    Z 4 2
    F(000) 1832 948
    θ range for data collection / (°) 3.412~25.042 3.389~25.050
    Limiting indices -14 ≤ h ≤ 14, -14 ≤ k ≤ 11, -28 ≤ l ≤ 23 -11 ≤ h ≤ 11, -14 ≤ k ≤ 13, -20 ≤ l ≤ 17
    Reflection collected, unique (Rint) 20 338, 5 885 (0.107 9) 11 174, 6 248 (0.068 6)
    Dc / (Mg·m-3) 1.848 1.782
    μ / mm-1 1.345 1.274
    Data, restraint, parameter 5 885, 0, 496 6 248, 0, 496
    Goodness-of-fit on F2 0.848 1.056
    Final R indices [I≥2σ(I)] R1, wR2 0.056 7, 0.080 6 0.063 9, 0.080 4
    R indices (all data) R1, wR2 0.101 2, 0.110 8 0.103 8, 0.131 1
    Largest diff. peak and hole / (e·nm-3) 916 and -707 785 and -928
    下载: 导出CSV

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

    1
    Cd(1)-O(1) 0.253 3(5) Cd(1)-O(3) 0.232 3(5) Cd(1)-O(4)A 0.224 7(5)
    Cd(1)-O(8)B 0.218 9(6) Cd(1)-N(1) 0.237 0(6) Cd(1)-N(2) 0.238 1(6)
    Cd(2)-O(1) 0.233 1(5) Cd(2)-O(2) 0.236 8(5) Cd(2)-O(6)B 0.240 1(5)
    Cd(2)-O(7)B 0.231 8(5) Cd(2)-N(3) 0.232 2(7) Cd(2)-N(4) 0.228 6(6)
    O(8)B-Cd(1)-O(4)A 97.8(2) O(8)B-Cd(1)-O(3) 151.7(2) O(4)A-Cd(1)-O(3) 96.82(18)
    N(1)-Cd(1)-O(8)B 91.3(2) O(4)A-Cd(1)-N(1) 151.6(2) O(3)-Cd(1)-N(1) 87.15(19)
    O(8)B-Cd(1)-N(2) 123.8(2) O(4)A-Cd(1)-N(2) 82.67(19) O(3)-Cd(1)-N(2) 82.0(2)
    N(1)-Cd(1)-N(2) 70.0(2) O(8)B-Cd(1)-O(1) 75.1(2) O(1)-Cdo(1)-O(4)A 106.77(18)
    O(3)-Cd(1)-O(1) 77.60(18) O(1)-Cd(1)-N(1) 101.6(2) O(1)-Cd(1)-N(2) 158.38(17)
    O(7)B-Cd(2)-N(4) 132.1(2) N(3)-Cd(2)-N(4) 72.2(2) O(7)B-Cd(2)-N(3) 103.3(2)
    N(4)-Cd(2)-O(1) 117.2(2) O(1)-Cd(2)-O(7)B 99.83(19) O(1)-Cd(2)-N(3) 134.6(2)
    O(2)-Cd(2)-N(4) 134.2(2) O(7)B-Cd(2)-O(2) 91.06(19) O(2)-Cd(2)-N(3) 85.06(19)
    O(1)-Cd(2)-O(2) 55.76(17) O(6)B-Cd(2)-N(4) 84.4(2) O(7)B-Cd(2)-O(6)B 55.24(17)
    N(3)-Cd(2)-O(6)B 118.7(2) O(1)-Cd(2)-O(6)B 106.64(19) O(2)-Cd(2)-O(6)B 140.98(18)
    2
    Cd(1)-O(1) 0.256 2(6) Cd(1)-O(2) 0.228 4(5) Cd(1)-O(4)A 0.227 9(6)
    Cd(1)-O(10) 0.235 5(6) Cd(1)-N(1) 0.233 3(7) Cd(1)-N(2) 0.232 3(6)
    Cd(2)-O(6)B 0.250 0(6) Cd(2)-O(7)B 0.236 2(7) Cd(2)-O(8) 0.236 6(5)
    Cd(2)-O(9) 0.242 7(6) Cd(2)-O(11) 0.238 4(6) Cd(2)-N(3) 0.229 7(8)
    Cd(2)-N(4) 0.230 2(7)
    O(2)-Cd(1)-O(4)A 108.2(2) O(4)A-Cd(1)-N(2) 97.8(2) O(2)-Cd(1)-N(2) 153.9(2)
    N(1)-Cd(1)-O(4)A 117.7(2) O(2)-Cd(1)-N(1) 97.2(2) N(2)-Cd(1)-N(1) 69.8(2)
    O(4)A-Cd(1)-O(10) 79.0(2) O(10)-Cd(1)-O(2) 95.0(2) O(10)-Cd(1)-N(2) 89.9(2)
    N(1)-Cd(1)-O(10) 154.6(2) O(4)A-Cd(1)-O(1) 149.9(2) O(1)-Cdo(1)-O(2) 53.56(18)
    N(2)-Cd(1)-O(1) 102.6(2) O(1)-Cd(1)-N(1) 90.2(2) O(1)-Cd(1)-O(10) 79.3(2)
    N(3)-Cd(2)-N(4) 70.9(3) N(3)-Cd(2)-O(7)B 96.5(3) O(7)B-Cd(2)-N(4) 130.1(2)
    N(3)-Cd(2)-O(8) 99.3(2) N(4)-Cd(2)-O(8) 139.7(2) O(7)B-Cd(2)-O(8) 89.1(2)
    O(11)-Cd(2)-N(3) 165.4(3) O(11)-Cd(2)-N(4) 95.8(3) O(7)B-Cd(2)-O(11) 96.8(2)
    O(8)-Cd(2)-O(11) 86.9(2) O(9)-Cd(2)-N(3) 88.5(2) O(9)-Cd(2)-N(4) 86.4(2)
    O(7)B-Cd(2)-O(9) 142.8(2) O(8)-Cd(2)-O(9) 53.73(19) O(11)-Cd(2)-O(9) 84.5(2)
    N(3)-Cd(2)-O(6)B 109.5(2) N(4)-Cd(2)-O(6)B 85.9(2) O(7)B-Cd(2)-O(6)B 52.1(2)
    O(8)-Cd(2)-O(6)B 132.9(2) O(11)-Cd(2)-O(6)B 74.5(2) O(9)-Cd(2)-O(6)B 156.8(3)
    Symmetry transformations used to generate equivalent atoms: A: -x, -y+2, -z+1; B: x-1, y, z for 1; A: -x+1, -y+1, -z+1; B: -x, -y, -z+2 for 2.
    下载: 导出CSV

    Table 3.  Hydrogen bond parameters of compound 2

    D—H…A d(D-H) / nm d(H…A) / nm d(D…A) / nm ∠DHA / (°)
    O(10)—H(1W)…O(1)A 0.085 0 0.196 5 0.281 5 179.74
    O(10)—H(2W)…O(12) 0.089 0 0.177 9 0.264 7 164.37
    O(11)—H(3W)…O(8)B 0.081 3 0.194 6 0.275 3 172.06
    O(11)—H(4W)…O(13)C 0.072 2 0.208 2 0.278 5 164.98
    O(12)—H(5W)…O(2)D 0.085 0 0.202 0 0.287 0 179.20
    O(12)—H(6W)…O(3) 0.085 0 0.1873 0.272 3 178.95
    O(13)—H(7W)…O(7)E 0.079 9 0.1580 0.237 2 170.57
    Symmetry codes: A: -x+2, -y+1, -z+1; B: -x, -y, -z+2; C: x, y-1, z+1; D: -x+1, -y+1, -z+1; E: x, y+1, z-1.
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  • 发布日期:  2020-09-10
  • 收稿日期:  2019-12-12
  • 修回日期:  2020-03-26
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