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Syntheses, Supramolecular Structures and Spectroscopic Properties of Cu(Ⅱ) and Ni(Ⅱ) Complexes with Schiff Base Containing Oxime Group

Hong-Jia ZHANG ,  Jian CHANG ,  Hao-Ran JIA ,  Yin-Xia SUN

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Citation:  ZHANG Hong-Jia, CHANG Jian, JIA Hao-Ran, SUN Yin-Xia. Syntheses, Supramolecular Structures and Spectroscopic Properties of Cu(Ⅱ) and Ni(Ⅱ) Complexes with Schiff Base Containing Oxime Group[J]. Chinese Journal of Inorganic Chemistry, 2018, 34(12): 2261-2270. doi: 10.11862/CJIC.2018.261 shu

含肟基的Schiff碱Cu（Ⅱ）和Ni（Ⅱ）配合物的合成、超分子结构和光谱性质

  • .

    兰州交通大学化学与生物工程学院, 兰州 730070

    • 通讯作者: 孙银霞, sun_yinxia@163.com
  • 基金项目:

    甘肃省重点研发计划项目 18YF1GA054

    兰州交通大学优秀科研平台 201706

    兰州交通大学优秀科研平台（No.201706）、甘肃省重点研发计划项目（No.18YF1GA054）支持

摘要: 合成了2个含肟基Schiff碱的Cu（Ⅱ）和Ni（Ⅱ）配合物[Cu（L1）2]·（1，4-dioxane）（1）和[Ni（L2）2]（2），并通过元素分析、红外光谱、紫外可见光谱，荧光光谱及X射线单晶衍射分析进行了表征和分析。结果表明，配合物1和2均包含1个中心金属离子和2个双齿配体单元，且金属离子的配位数均为4，均具有轻微扭曲的平面四边形几何构型。不同的是配合物1通过分子间氢键以及π…π堆积作用相连接形成了三维超分子结构，而配合物2仅通过分子间的π…π堆积作用形成了一条一维超分子链。

English

  • 0.   Introduction

    Much attention has been focused on oxime-based ligands in recent years due to their high stability and playing an important role in the development of coor-dination chemistry[1-5]. The design of new Schiff-base compounds has received long-lasting research interest because of not only their appealing structural and topological novelty[6-10] but also their potential wide application in the fields of biochemistry[11-16], cataly-sis[17-20] and optical[21-33], magnetic materials[34-40] and constructing supramolecular structures [41-52]. Schiff-base compounds and its derivatives are very important as versatile ligands, properties of interest in materials science. Also, the Schiff base ligands with N- and O- group are strong donors and therefore the oxime-containing ligands were found to efficiently stabilize high oxidation states of metal ions and prepare complexes with different structures and functionalities like Cu(Ⅱ) and Ni(Ⅱ) complexes[53-58]. So, as an extension of our work[9-10, 55, 59], two new Cu(Ⅱ) and Ni(Ⅱ) complexes, [Cu(L1)2]·(1, 4-dioxane) (1) (HL1=8-(((4-(1-((benzyloxy)imino)ethyl)phenyl)imino)methyl)- 7- hydroxy- 4 - methyl-2H-chromen-2-one) and [Ni(L2)2] (2) (HL2=1-(4-(((2-hydroxynaphthalen-1-yl)methylene)amino)phenyl)etha-none O-benzyloxime), have been synthesized and characterized. Complexes 1 and 2 are both mononu-clear structures and the central metal Cu(Ⅱ) and Ni(Ⅱ) ions are all four-coordinated with the slightly distorted square-planar geometry. In addition, the fluorescence property of HL1, HL2 and their metal complexes 1 and 2 are discussed.

    1.   Experimental

    1.1   Materials

    7-Hydroxy-4-methyl-chromen-2-one, hexamethyl-enetetramine, 4-aminoacetophenone, O-benzylhydroxy-lamine, 2-hydroxy-1-naphthaldehyde were purchased from Alfa Aesar and used without further purification. The other reagents and solvents were analytical grade reagents from Tianjin Chemical Reagent Factory, and were used without further purification.

    1.2   Instruments and methods

    C, H and N analyses were carried out with a GmbH Vario EL V3.00 automatic elemental analyzer. FT-IR spectra were recorded on a VERTEX70 FT-IR spectrophotometer, with samples prepared as KBr (400~4 000 cm-1) pellets. UV-Vis absorption spectra were recorded on a Shimadzu UV-3900 spectrometer. Luminescence spectra in solution were recorded on a Hitachi F-7000 spectrometer. X-ray single crystal structure was determined on a Bruker Smart 1000 CCD area detector. Melting points were measured by the use of a microscopic melting point apparatus made in Beijing Taike Instrument Limited Company and the thermometer was uncorrected.

    1.3   Syntheses of HL1 and HL2

    HL1 and HL2 were synthesized according to the following steps shown in Scheme 1.

    Scheme 1

    Scheme 1.  Synthetic routes of HL1 and HL2
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    HL1: Firstly, 7-hydroxy-4-methyl-chromen-2-one 8.0 g (50 mmol) and hexamethylenetetramine 14.0 g (100 mmol) were dissolved in 50 mL glacial acetic acid, and the mixed solution was stirred and refluxed for 5~6 h. A 5% hydrochloric acid solution was added to adjust the pH value to about 4.5, and then refluxed and stirred for 30 min. The mixed solution was allowed to come to room temperature, then extracted with ether, washed with sodium chloride solution and dried with anhydrous MgSO4. After removing solvent and recrystallizing from absolute ethanol, 1.7 g crystalline solid of 7-hydroxy-4-methyl-2-oxo-2H-chromene-8-carbaldehyde was collected. Yield: 17%. m.p. 178~180 ℃. Anal. Calcd. for C11H8O4(%): C, 64.71; H, 3.95. Found(%): C, 65.04; H, 4.02.

    Secondly, 1-(4-aminophenyl)ethan-1-one O-benzyl oxime was synthesized according to the reported method[53] as yellow crystals. Yield: 874.3 mg, 80.6%. m.p. 80~81 ℃. Anal. Calcd. for C15H16N2O(%): C, 74.97; H, 6.71; N, 11.66. Found(%): C, 75.07; H, 7.35. N, 12.43.

    At last, a solution of 1-(4-aminophenyl)ethan-1-one O-benzyl oxime (480.6 mg, 2.00 mmol) in ethanol (7.5 mL) was added to a solution of 7-hydroxy-4-methyl-2-oxo-2H-chromene-8-carbaldehyde (404.4 mg, 2.00 mmol) in ethanol (7.5 mL) and the mixture was heated to reflux at 65~70 ℃ for 7~8 h. After being cooled by ice-water bath, washed with an anhydrous ethanol solution and dried under reduced pressure, orange-red powder was obtained. Yield: 569.1 mg, 64.3%. m.p. 229~230 ℃. Anal. Calcd. for C26H22N2O4(%): C, 73.23; H, 5.20; N, 6.57. Found(%): C, 74.07; H, 6.05. N, 6.43.

    HL2: The synthesis of HL2 is similar to that of HL1 except substituting 7-hydroxy-4-methyl-2-oxo-2H-chromene-8-carbaldehyde with 2-hydroxy-1-naphthal-dehyde. The precipitate was filtered and washed successively with ethanol and ethanol/n-hexane (1:4, V/V), respectively. The product was dried in vacuum to obtain yellow powder. Yield: 79.43%. m.p. 127~129 ℃. Anal. Calcd. for C26H22N2O2(%): C, 79.17; H, 5.62; N, 7.10. Found(%): C, 80.03; H, 6.05. N, 7.46.

    1.4   Syntheses of [Cu(L1)2]·(1, 4-dioxane) (1) and [Ni(L2)2] (2)

    Complex 1: A solution of copper(Ⅱ) acetate monohydrate (0.51 mg, 0.002 5 mmol) in methanol (2 mL) was added dropwise to a solution of HL1 (1.9 mg, 0.005 mmol) in 1, 4-dioxane (2 mL) at room temper-ature. The color of the mixing solution turned to pale green immediately, and then the solution was filtered and the filtrate was allowed to stand at room temper-ature for about one week. Brown block-shape single crystals suitable for X-ray structural determination were obtained. Anal. Calcd. for C56H50CuN4O10(%): C, 67.13; H, 5.03; N, 5.60. Found(%): C, 68.09; H, 5.64; N, 5.98.

    Complex 2: The synthesis of complex 2 was same as above, and red-brown prismatic single crystals suitable for X-ray crystallographic analysis were obtained. Anal. Calcd. for C52H42NiN4O4(%): C, 73.91; H, 5.01; N, 6.63. Found(%): C, 73.46; H, 4.68; N, 6.85.

    1.5   X-ray crystallography of complexes 1 and 2

    The single crystals of complexes with approxi-mate dimensions of 0.11 mm× 0.16 mm× 0.21 mm (1) and 0.28 mm×0.03 mm×0.02 mm (2) were placed on a Bruker Smart 1000 CCD area detector, respectively. The diffraction data of complexes 1 and 2 were collected using a graphite monochromated Mo Kα radiation (λ=0.071 073 nm) at 293.4(1) and 293.6(2) K, respec-tively. The Lp corrections were applied to the SAINT program[60] and semi-empirical correction were applied to the SADABS program[61]. The crystal structures were solved by the direct methods (SHELXS-2014)[62]. All nonhydrogen atoms were refined anisotropically. All the hydrogen atoms were generated geometrically and refined isotropically using the riding model. Details of the data collection parameters and crystallographic information for complexes 1 and 2 are summarized in Table 1.

    Table 1

    Table 1.  Crystal data and structure refinement for complexes 1 and 2
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    1 2
    Empirical formula C56H50CuN4O10 C52H42NiN4O4
    Formula weight 1 002.54 845.60
    T / K 293.4(1) 293.6(1)
    Crystal system Triclinic Triclinic
    Space group P1 P1
    a / nm 0.990 6(3) 0.566 02(6)
    b / nm 1.293 8(4) 1.058 5(2)
    c / nm 1.958 3(5) 1.805 3(3)
    α / (°) 76.981(7) 76.312(17)
    β / (°) 79.958(6) 89.215(11)
    γ / (°) 81.130(5) 78.818(13)
    V / nm3 2.390 5(12) 1.030 3(3)
    Z 2 1
    Dc / (g·cm-3) 1.393 1.363
    μ / mm-1 0.524 0.524
    F(000) 1 046 442
    θ range / (°) 2.2~25.0 3.800 0~20.172 0
    Limiting indices -11 ≤ h ≤ 11, -15 ≤ k ≤ 15, -16 ≤ l ≤ 23 6 ≤ h ≤ 6, -12 ≤ k ≤ 13, -18≤ l ≤ 22
    Reflection collected, unique 12 625, 8 276 (Rint=0.073) 6 936, 1 749 (Rint=0.081 3)
    Completeness to θ / % 98.40 (25.0°) 99.86 (26.32°)
    Max. and min. transmission 1.000 00 and 0.896 1.000 00 and 0.662 92
    Data, restraint, parameter 8 276, 0, 645 4 034, 0, 278
    GOF on F2 1.015 1.025
    R1, wR2[I > 2σ(I)] 0.096 3, 0.235 0 0.086 6, 0.135 3
    Largest diff. peak and hole / (e·nm-3) 1 550 and -1 230 646 and -323

    CCDC: 1542901, 1; 1857932, 2.

    2.   Results and discussion

    2.1   IR spectra analyses

    The FT-IR spectra of HL1, HL2 and complexes 1 and 2 exhibited various bands in the 400~4 000 cm-1 region. The most important FT-IR bands for HL1, complex 1 and HL2, complex 2 are given in Table 2. HL1 and HL2 exhibited characteristic stretching bands of C=N group at 1 610 and 1 612 cm-1, respectively[63-69]. While those of complexes 1 and 2 were observed at the 1 580 and 1 597 cm-1, respectively. Compared to the ligands, the C=N stretching frequencies of complexes 1 and 2 were both shifted to lower frequencies by ca. 30 and 15 cm-1, respectively, which indicated that the Cu(Ⅱ) and Ni(Ⅱ) ions coordinate with the oxime nitrogen lone pair[70-72] in the C=N group, lowering the bond energy of the C=N bond. The stretching bands at 3 053 cm-1 (in HL1) and 3 453 cm-1 (in HL2) were assigned to the characteristic vibration of O-H in phenolic hydroxyl groups, respectively, which disapp-eared in complexes 1 and 2, indicating that the phenolic hydroxyl groups in HL1 and HL2 are deprotonated and coordinate with Cu(Ⅱ) and Ni(Ⅱ) ions to form coordination bonds, respectively. The Ar-O stretching bands at 1 076 and 1 140 cm-1 of complexes 1 and 2 shifted toward lower frequencies by ca. 85 and 24 cm-1 compared with those of HL1 and HL2 at 1 165 and 1 164 cm-1, respectively. The reason maybe is due to that coordination of Cu(Ⅱ) and Ni(Ⅱ) ions with the phenolic oxygen atoms of ligands result in reducing the Ar-O bond energy[73]. The FT-IR spectrum of complex 1 showed ν(M-N) and ν(M-O) vibration frequencies at 578, 517 and 458 cm-1 (or 463 and 427 cm-1 for complex 2), respectively. These assignments are consistent with the literature[49].

    Table 2

    Table 2.  Main bands in IR spectra of H2L1, H2L2 and their Cu(Ⅱ) and Ni(Ⅱ) complexes
    下载: 导出CSV
    cm-1
    Compound ν(C=N) ν(Ar-O) ν(O-H) ν(M-N) ν(M-O)
    HL1 1 610 1 165 3 053 — —
    Complex 1 1 580 1 076 — 578, 517 458
    HL2 1 612 1 164 3 453 — —
    Complex 2 1 597 1 140 — 463 427

    2.2   UV-Vis absorption spectra analyses

    The absorption spectra of HL1 and its correspond-ing Cu(Ⅱ) complex 1, ligand HL2 and its corresponding Ni(Ⅱ) complex 2 were determined in diluted DMSO solution as shown in Fig. 1 and 2, respectively. UV-Vis spectrum of HL1 exhibited two absorption peaks at ca. 281 and 328 nm. The former at 281 nm can be assigned to the π-π* transition of the benzene rings, which blue-shifted to high energy region by ca. 23 nm in complex 1, indicating Cu(Ⅱ) ion coordinated with the O and N atoms of deprotonated (L1)- ligand. The later at 328 nm attributed to the intra-ligand π-π* transition of C=N bonds[74] was absent in complex 1, indicating the oxime nitrogen atom is involved in the coordination with Cu(Ⅱ) ion[75]. However, a new absor-ption peak observed at 410 nm in complex 1 can be ascribed to the d-d forbidden transition of Cu(Ⅱ) ion.

    Figure 1

    Figure 1.  UV-Vis absorption spectra of HL1 and complex 1 in diluted DMSO solution at room temperature

    c=40 μmol·L-1

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    It can be seen that the absorption peaks of complex 2 are obviously different from those of HL2 upon coordination (Fig. 2). Compared with complex 2, an important feature of the absorption spectrum of HL2 was that three absorption peaks were observed at 390, 446 and 470 nm attributed to the intra-ligand π-π* transition of C=N bonds and conjugated aromatic chromophore, which are absent in the spectrum of complex 2. A new absorption peak owing to L→M charge-transfer transitions[75] was observed at 426 nm in complex 2, which are characteristic of the transition metallic coordination compounds with N2O2 coordina-tion spheres. And the absorption peak at 324 nm assigned to the π-π* transitions of phenyl rings in HL2 was shifted to 323 nm in complex 2 indicating the coordination of Ni(Ⅱ) ion with HL2.

    Figure 2

    Figure 2.  UV-Vis absorption spectra of HL2 and complex 2 in diluted DMF solution at room temperature

    c=10 μmol·L-1

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    2.3   Structural description of complexes 1 and 2

    The molecular structures of complexes 1 and 2 are shown in Fig. 3 and 4, respectively, and selected bond lengths and angles are listed in Table 2. Complexes 1 and 2 are all mononuclear structures and crystallize in the triclinic system, P1 space group. Both of complexes 1 and 2 consist of one metal ion M(Ⅱ) (M=Cu or Ni), two bidentate L- units, in which the difference is that complex 1 contains a crystallizing 1, 4-dioxane molecule. In the molecular structures of complexes 1 and 2, the metal centers M(Ⅱ) (M=Cu for 1 and Ni for 2) are tetra-coordinated in a trans-MN2O2 slightly distorted square-planar geometries, with two phenolic O and two imino N atoms from two N, O-bidentate oxime-type Schiff ligands (HL1 and HL2). In complex 1, the four atoms of the donor set (N1, N3, O1, O5) and Cu1 approximately lie in a plane with the distance being 0.000 7 nm and 0.017 3~0.017 4 nm of Cu(Ⅱ) and N/O atoms to the square plane. The dihedral angle between the coordination plane of N1-Cu1-O1 and that of N3-Cu1-O5 is 14.22°, indicating slight distortion toward tetrahedral geometry from the square planar structure. And the four atoms of the donor set (N1, N1a, O1, O1a) and Ni1 are completely coplanar. In addition, the bond lengths of M-N (0.203 3(6) and 0.202 1(6) nm for Cu-N, 0.189 0(5) nm for Ni-N) are longer than M-O bond (0.188 4(6) and 0.189 3(5) nm for Cu-O, 0.182 8(4) nm for Ni-O) in complexes 1 and 2, which is probably due to the weakening of the coordination abilities of coordinating nitrogen atoms by the larger electronegativity of oxygen atoms of phenolic hydroxyl groups. The signifi-cant elongation has been observed in other metal complexes with Schiff ligands[47].

    Figure 3

    Figure 3.  Molecular structure of complex 1 showing 30% probability displacement ellipsoids

    Hydrogen atoms are omitted for clarity

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    Figure 4

    Figure 4.  Molecular structure of complex 2 showing 30% probability displacement ellipsoids

    Hydrogen atoms are omitted for clarity; Symmetry codes: a:-x, -y, -z

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    Table 3

    Table 3.  Selected bond lengths (nm) and bond angles (°) for complexes 1 and 2
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    Complex 1
    Cu1-O1 0.189 3(5) Cu1-O5 0.188 4(6) Cu1-N1 0.203 3(6)
    Cu1-N3 0.202 1(6)
    O1-Cu1-O5 169.0(2) O1-Cu1-N1 91.7(2) O1-Cu1-N3 89.4(2)
    O5-Cu1-N1 88.3(2) O15-Cu1-N3 92.4(2) N1-Cu1-N 170.6(2)
    Complex 2
    Ni1-O1 0.182 8(4) Ni1-N1 0.189 0(5)
    O1a-Ni1-O1 180.0 O1-Ni1-N1a 87.51(19) O1a-Ni1-N1 87.51(19)
    O1-Ni1-N1 92.49(19) O1a-Ni1-N1a 92.50(19) N1-Ni1-N1a 180.0
      Symmetry codes: a: -x, -y, -z.

    2.4   Supramolecular interaction of complexes 1 and 2

    The main hydrogen bond and π…π stacking interactions parameters of complexes 1 and 2 are given in Table 4 and Table 5. As shown in Fig. 5, a pair of intermolecular non-classical hydrogen bonds C13-H13…O7a have stabilized a pair of complex 1 molecules to form a dimer unit. Synchronously, this dimer unit is further stabilized via two hydrogen bonds C22-H22…O9 and C34-H34…O10 between the crystallizing 1, 4-dioxane molecule and complex 1 molecule (Fig. 6). Furthermore, this linkage is linked via two pairs of intermolecular C6c-H6c…O3 and C51d-H51d…O3 hydrogen bonds to form an infinite 1D band-like supramolecular structure (Fig. 6). Thus, complex 1 molecules are linked together into an infinite 2D-layer supramolecular structure via intermolecular non-classical C-H…O hydrogen bonds interactions (Fig. 7). In addition, this adjacent 2D-layer are further held together by the intermolecular compli-cated π…π stacking interactions to form 3D network supramolecular structure (Table 5)[76-80]. Consequently, the intermolecular non-classical hydrogen-bonding plays a very important role in the construction of supramolecular networks structure[81-85]. Whereas, in complex 2, the molecules linked only via a intermole-cular πcentroid(C21~C26) …πcentroid (C21e~C26e) stacking interactions of benzene rings of the neighboring molecules to form a 1D infinite chain parallel to the a axis (Fig. 8, Table 5).

    Figure 5

    Figure 5.  View of dimer unit stabilized by hydrogen bonds of complex 1

    Symmetry codes: a:-x, 1-y, 1-z

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    Figure 6

    Figure 6.  View of infinite 1D band-like supramolecular structure linked by hydrogen bonds of complex 1

    Symmetry codes: b: 1-x, 1-y, 1-z; c: 2-x, -y, 1-z; d:-1+x, y, 1+z

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    Figure 7

    Figure 7.  View of 2D-layer supramolecular stabilized by hydrogen bonds of complex 1
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    Figure 8

    Figure 8.  View of 1D infinite supramolecular chain linked by π…π stacking interaction of complex 2

    Symmetry codes: e: 2-x, -1-y, 1-z

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    Table 4

    Table 4.  Hydrogen bonds parameters for complex 1
    下载: 导出CSV
    D-H…A d(D-H) / nm d(H…A) / nm d(D…A) / nm ∠D-H…A / (°)
    C13-H13…O7a 0.093 0.257 0.350 0(10) 176
    C27-H27…O9b 0.093 0.256 0.342 6(13) 156
    C34-H34…O10b 0.093 0.247 0.336 6(11) 163
    C6c-H6c…O3 0.093 0.254 0.343 2(10) 160
    C51d-H51d…O3 0.093 0.247 0.338 5(11) 169
      Symmetry codes: a: -x, 1-y, 1-z; b: 1-x, 1-y, 1-z; c: 2-x, -y, 1-z; d: -1+x, y, 1+z.

    Table 5

    Table 5.  π-π stacking interactions parameters for complexes 1 and 2
    下载: 导出CSV
    Ring(i) Ring(j) d(Cg…Cg) / nm Dihedral angle / (°) d(Cg(i)-perp) / nm d(Cg(j)-perp) / nm Slippage / nm
    Complex 1
    Cg1 Cg2a 0.351 8(4) 8.0(3) 0.329 8(3) 0.339 1(3) 0.093 3
    Cg3 Cg1a 0.382 2(4) 9.5(3) 0.302 9(3) 0.335 3(3) 0.183 4
    Cg4 Cg1a 0.346 4(4) 8.6(2) 0.320 8(3) 0.330 7(3) 0.102 9
    Cg5 Cg5a 0.330 9(4) 0.0(3) 0.327 3(3) 0.327 3(3) 0.049 0
    Cg5 Cg6b 0.382 3(4) 16.0(3) 0.343 3(3) 0.357 9(3) 0.134 2
    Cg3 Cg6b 0.363 6(5) 14.0(4) 0.323 5(3) 0.352 5(3) 0.089 0
    Cg2 Cg7c 0.385 1(5) 13.5(4) 0.337 4(3) 0.363 7(3) 0.126 6
    Cg8 Cg9d 0.381 2(5) 6.4(4) 0.334 4(4) 0.352 5(4) 0.145 1
    Complex 2
    Cg10 Cg10e 0.394 1(4) 0.0(3) 0.371 8(3) 0.371 8(3) 0.130 7
      Cg1, Cg2, Cg3, Cg4, Cg5, Cg6, Cg7, Cg8 and Cg9 are the centroids of the rings Cu1-O1-C1-C9-C11-N1, O6-C28~C30-C32-C33, C32~C37, O6-C28~C30-C32-C34~C36, Cu1-O5-C36~C38-N3, O2-C4~C8, C1~C4-C8~C9, C39~C44, C48~C53; Cg10 is the centroids of benzene ring C21~C26; Symmetry codes: a: -x, 1-y, 1-z; b: 1-x, 1-y, 1-z; c: -x, 1-y, 1-z; d: -x, 1-y, 2-z for 1; e: 2-x, -1-y, 1-z for 2.

    2.5   Fluorescence spectra

    The fluorescence emission spectra of HL1, HL2 and complexes 1 and 2 in diluted DMSO and DMF solution at room temperature are shown in Fig. 9 and Fig. 10, respectively. With excitation at 350 nm, HL1 exhibited an intense emission at 530 nm and show a strong yellow-green fluorescence, which may be assigned to the intra-ligand π-π* transition[86-87]. In comparison with HL1, an extremely weak fluorescence intensity of complex 1 was observed, indicating that the change of fluorescence is due to the coordination of Cu(Ⅱ) ion to HL1. However, both HL2 and complex 2 show strong fluorescence emission at 502 and 511 nm with the excitation at 323 nm, respectively. Compared with HL2, the emission peak of complex 2 is slightly red shifted ca. 9 nm, indicating that Ni(Ⅱ) ion coordinates with the N and O atoms and occurs electron transition.

    Figure 9

    Figure 9.  Emission spectra of HL1 and complex 1 in diluted DMSO at room temperature

    c=40 μmol·L-1, λex=350 nm

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    Figure 10

    Figure 10.  Emission spectra of HL2 and complex 2 in diluted DMF at room temperature

    c=10 μmol·L-1, λex=323 nm

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    3.   Conclusions

    Two Schiff base mononuclear complexes 1 and 2 have been synthesized and characterized structurally. Complexes 1 and 2 are tetra-coordinated by two nitrogen atoms and two oxygen atoms of two depro-tonated (L1)- units defining the N2O2 basal plane. The coordination environment around the metal ions M(Ⅱ) (M=Cu for 1 and Ni for 2) are best regarded as the slightly distorted square-planar geometries. Complex 1 forms a 3D network supramolecular structure by inter-molecular non-classical C-H…O hydrogen bonds and π…π stacking interactions. Whereas, complex 2 just forms a 1D infinite chain held together by intermole-cular π…π stacking interaction. The fluorescence of complex 1 was quenched by Cu(Ⅱ) but that of complex 2 was red-shifted ca. 9 nm upon complexation comp-ared to HL1 and HL2, respectively.

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  • Scheme 1  Synthetic routes of HL1 and HL2

    下载: 全尺寸图片 幻灯片

    Figure 1  UV-Vis absorption spectra of HL1 and complex 1 in diluted DMSO solution at room temperature

    c=40 μmol·L-1

    下载: 全尺寸图片 幻灯片

    Figure 2  UV-Vis absorption spectra of HL2 and complex 2 in diluted DMF solution at room temperature

    c=10 μmol·L-1

    下载: 全尺寸图片 幻灯片

    Figure 3  Molecular structure of complex 1 showing 30% probability displacement ellipsoids

    Hydrogen atoms are omitted for clarity

    下载: 全尺寸图片 幻灯片

    Figure 4  Molecular structure of complex 2 showing 30% probability displacement ellipsoids

    Hydrogen atoms are omitted for clarity; Symmetry codes: a:-x, -y, -z

    下载: 全尺寸图片 幻灯片

    Figure 5  View of dimer unit stabilized by hydrogen bonds of complex 1

    Symmetry codes: a:-x, 1-y, 1-z

    下载: 全尺寸图片 幻灯片

    Figure 6  View of infinite 1D band-like supramolecular structure linked by hydrogen bonds of complex 1

    Symmetry codes: b: 1-x, 1-y, 1-z; c: 2-x, -y, 1-z; d:-1+x, y, 1+z

    下载: 全尺寸图片 幻灯片

    Figure 7  View of 2D-layer supramolecular stabilized by hydrogen bonds of complex 1

    下载: 全尺寸图片 幻灯片

    Figure 8  View of 1D infinite supramolecular chain linked by π…π stacking interaction of complex 2

    Symmetry codes: e: 2-x, -1-y, 1-z

    下载: 全尺寸图片 幻灯片

    Figure 9  Emission spectra of HL1 and complex 1 in diluted DMSO at room temperature

    c=40 μmol·L-1, λex=350 nm

    下载: 全尺寸图片 幻灯片

    Figure 10  Emission spectra of HL2 and complex 2 in diluted DMF at room temperature

    c=10 μmol·L-1, λex=323 nm

    下载: 全尺寸图片 幻灯片

    Table 1.  Crystal data and structure refinement for complexes 1 and 2

    1 2
    Empirical formula C56H50CuN4O10 C52H42NiN4O4
    Formula weight 1 002.54 845.60
    T / K 293.4(1) 293.6(1)
    Crystal system Triclinic Triclinic
    Space group P1 P1
    a / nm 0.990 6(3) 0.566 02(6)
    b / nm 1.293 8(4) 1.058 5(2)
    c / nm 1.958 3(5) 1.805 3(3)
    α / (°) 76.981(7) 76.312(17)
    β / (°) 79.958(6) 89.215(11)
    γ / (°) 81.130(5) 78.818(13)
    V / nm3 2.390 5(12) 1.030 3(3)
    Z 2 1
    Dc / (g·cm-3) 1.393 1.363
    μ / mm-1 0.524 0.524
    F(000) 1 046 442
    θ range / (°) 2.2~25.0 3.800 0~20.172 0
    Limiting indices -11 ≤ h ≤ 11, -15 ≤ k ≤ 15, -16 ≤ l ≤ 23 6 ≤ h ≤ 6, -12 ≤ k ≤ 13, -18≤ l ≤ 22
    Reflection collected, unique 12 625, 8 276 (Rint=0.073) 6 936, 1 749 (Rint=0.081 3)
    Completeness to θ / % 98.40 (25.0°) 99.86 (26.32°)
    Max. and min. transmission 1.000 00 and 0.896 1.000 00 and 0.662 92
    Data, restraint, parameter 8 276, 0, 645 4 034, 0, 278
    GOF on F2 1.015 1.025
    R1, wR2[I > 2σ(I)] 0.096 3, 0.235 0 0.086 6, 0.135 3
    Largest diff. peak and hole / (e·nm-3) 1 550 and -1 230 646 and -323
    下载: 导出CSV

    Table 2.  Main bands in IR spectra of H2L1, H2L2 and their Cu(Ⅱ) and Ni(Ⅱ) complexes

    cm-1
    Compound ν(C=N) ν(Ar-O) ν(O-H) ν(M-N) ν(M-O)
    HL1 1 610 1 165 3 053 — —
    Complex 1 1 580 1 076 — 578, 517 458
    HL2 1 612 1 164 3 453 — —
    Complex 2 1 597 1 140 — 463 427
    下载: 导出CSV

    Table 3.  Selected bond lengths (nm) and bond angles (°) for complexes 1 and 2

    Complex 1
    Cu1-O1 0.189 3(5) Cu1-O5 0.188 4(6) Cu1-N1 0.203 3(6)
    Cu1-N3 0.202 1(6)
    O1-Cu1-O5 169.0(2) O1-Cu1-N1 91.7(2) O1-Cu1-N3 89.4(2)
    O5-Cu1-N1 88.3(2) O15-Cu1-N3 92.4(2) N1-Cu1-N 170.6(2)
    Complex 2
    Ni1-O1 0.182 8(4) Ni1-N1 0.189 0(5)
    O1a-Ni1-O1 180.0 O1-Ni1-N1a 87.51(19) O1a-Ni1-N1 87.51(19)
    O1-Ni1-N1 92.49(19) O1a-Ni1-N1a 92.50(19) N1-Ni1-N1a 180.0
      Symmetry codes: a: -x, -y, -z.
    下载: 导出CSV

    Table 4.  Hydrogen bonds parameters for complex 1

    D-H…A d(D-H) / nm d(H…A) / nm d(D…A) / nm ∠D-H…A / (°)
    C13-H13…O7a 0.093 0.257 0.350 0(10) 176
    C27-H27…O9b 0.093 0.256 0.342 6(13) 156
    C34-H34…O10b 0.093 0.247 0.336 6(11) 163
    C6c-H6c…O3 0.093 0.254 0.343 2(10) 160
    C51d-H51d…O3 0.093 0.247 0.338 5(11) 169
      Symmetry codes: a: -x, 1-y, 1-z; b: 1-x, 1-y, 1-z; c: 2-x, -y, 1-z; d: -1+x, y, 1+z.
    下载: 导出CSV

    Table 5.  π-π stacking interactions parameters for complexes 1 and 2

    Ring(i) Ring(j) d(Cg…Cg) / nm Dihedral angle / (°) d(Cg(i)-perp) / nm d(Cg(j)-perp) / nm Slippage / nm
    Complex 1
    Cg1 Cg2a 0.351 8(4) 8.0(3) 0.329 8(3) 0.339 1(3) 0.093 3
    Cg3 Cg1a 0.382 2(4) 9.5(3) 0.302 9(3) 0.335 3(3) 0.183 4
    Cg4 Cg1a 0.346 4(4) 8.6(2) 0.320 8(3) 0.330 7(3) 0.102 9
    Cg5 Cg5a 0.330 9(4) 0.0(3) 0.327 3(3) 0.327 3(3) 0.049 0
    Cg5 Cg6b 0.382 3(4) 16.0(3) 0.343 3(3) 0.357 9(3) 0.134 2
    Cg3 Cg6b 0.363 6(5) 14.0(4) 0.323 5(3) 0.352 5(3) 0.089 0
    Cg2 Cg7c 0.385 1(5) 13.5(4) 0.337 4(3) 0.363 7(3) 0.126 6
    Cg8 Cg9d 0.381 2(5) 6.4(4) 0.334 4(4) 0.352 5(4) 0.145 1
    Complex 2
    Cg10 Cg10e 0.394 1(4) 0.0(3) 0.371 8(3) 0.371 8(3) 0.130 7
      Cg1, Cg2, Cg3, Cg4, Cg5, Cg6, Cg7, Cg8 and Cg9 are the centroids of the rings Cu1-O1-C1-C9-C11-N1, O6-C28~C30-C32-C33, C32~C37, O6-C28~C30-C32-C34~C36, Cu1-O5-C36~C38-N3, O2-C4~C8, C1~C4-C8~C9, C39~C44, C48~C53; Cg10 is the centroids of benzene ring C21~C26; Symmetry codes: a: -x, 1-y, 1-z; b: 1-x, 1-y, 1-z; c: -x, 1-y, 1-z; d: -x, 1-y, 2-z for 1; e: 2-x, -1-y, 1-z for 2.
    下载: 导出CSV
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  • 发布日期:  2018-12-10
  • 收稿日期:  2018-07-25
  • 修回日期:  2018-08-23
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