

Two Novel Mercury(II) and Copper(II) Complexes Based on (5-Chloro-quinolin-8-yloxy)acetic Acid①
English
Two Novel Mercury(II) and Copper(II) Complexes Based on (5-Chloro-quinolin-8-yloxy)acetic Acid①
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1 INTRODUCTION
In the past several years, luminescent complexes with nitrogen-containing ligands have attracted much attention due to their good performance in electroluminescent devices and sensor technologies[1-5]. Recently, Hg (II) and Cu (II) complexes with nitrogen-containing ligands have begun to receive attention[6-15]. On one hand, some Hg (II) and Cu (II) complexes of nitrogen-containing ligands exhibit efficient luminescent properties which show that this new class of luminescent metal compounds may be potential applications in optoelectronic devices[6-12]. On the other hand, the design and synthesis of efficient luminescent chelating Hg (II) complexes is also of importance for the detection of Hg (II), as mercury presents one of the most hazardous and toxic pollutants that impact on the environment and biological systems[13-15]. Therefore, the synthesis of new Hg (II) and Cu (II) complexes with nitrogen-containing ligands is of great significance. Quinoline derivatives are well known nitrogen-containing ligands, and their complexes have been intensively studied due to their intriguing diversity and potential applications as functional materials[16-21]. 8-Quinolinyloxyacetic acid and their derivatives exhibit a rich structural variety, and reports on the complexes with such as quinolin-8-yloxy acetic acid and (5-chloro-quinolin-8-yloxy) acetic acid ligands have increased in recent years[22-30]. The carboxylate groups exhibit diverse coordination modes in these complexes due to deprotonation. As a continuation of our work[23, 24, 27-30], HgII and CuII complexes of (5-chloro-quinolin-8-yloxy) acetic acid were prepared. Interestingly, when (5-chloro-quinolin-8- yloxy) acetic acid reacted respectively with HgII and CuII ions by the synthesis method of PbII complex[29], the complexes of deprotonation ligand are not be prepared. Unexpectedly, complexes HgII (1) and CuII (2) of the ester product were obtained. In this paper, we report here the crystal structures and luminescent properties of 1 and 2.
2 EXPERIMENTAL
2.1 Materials and general methods
All reagents for syntheses and analyses were of analytical grade. (5-Chloro-quinolin-8-yloxy) acetic acid ligand was prepared by reported procedures[29]. Complexes 1 and 2 were prepared by solvothermal method. FT-IR spectra (KBr pellet) were taken on a FT-IR 170 SX (Nicolet) spectrometer in the 4000~ 400 cm-1 region. Elemental analysis (C, H and N) was carried out on a Perkin-Elmer 240C analytical instrument. X-ray powder diffraction (XRPD) was recorded on a Rigaku D/Max-3C diffractometer at 40 kV, 30 mA for a Cu-target tube and a graphitemonochromator. Thermal analysis (TGA) of the complexes was performed with a SDT 2960 thermoanalyzer at a heating rate of 10 ℃/min from 30 to 800 ℃ under a 50.0 mL/min nitrogen gas flow. UV-Vis-NIR spectra were measured with a Shimadzu UV-3150 spectrometer at room temperature. Solid fluorescence spectra were determined on an Eclipse Cary fluorescence spectrometer.
2.2 Syntheses
HgLBr2 (1) In a thick Pyrex tube with the length of 15 cm and inner diameter of 1 cm, (5-chloro-quinolin-8-yl-oxy) acetic acid (0.0238 g, 0.1 mmol), methanol (4 mL), triethylamine (10.1 mg, 0.1 mmol) and HgBr2(36.0 mg, 0.1 mmol) were placed successively. The mixture was heated at 120 ℃ for 3 days. After cooling at a rate of 5 ℃/h to ambient, colorless block crystals were collected. The product was washed with anhydrous ethanol and dried at room temperature, obtaining 65.3% yield based on (5-chloro-quinolin-8-yloxy) acetic acid. IR (KBr pellet, cm-1): 2957w, 2915w, 2839w, 1744vs, 1592m, 1502m, 1366s, 1222s, 1109m, 865m, 796s, 807m. Analysis found (%): C, 23.57; H, 1.66; N, 2.30. Calcd. (%) for C12H10Br2ClHgNO3: C, 23.53; H, 1.63; N, 2.29.
CuL2Cl2 (2) A green block crystal of 2 suitable for X-ray analysis was obtained by a similar method described for 1. Yield: 59%. IR (KBr pellet, cm-1): 2960w, 2913w, 2841w, 1739vs, 1597m, 1502m, 1373s, 1231s, 1047m. Anal. found: C, 44.33; H, 3.35; N, 4.41. Calcd. for C24H20Cl4CuN2O6: C, 45.20; H, 3.16; N, 4.39.
2.3 Structure determination
The crystals (0.28mm × 0.12mm × 0.06mm for 1 and 0.50mm × 0.20mm × 0.20mm for 2) were mounted on a glass fiber in a random orientation. All measurements were made on a Bruker APEX-II CCD with graphite-monochromated MoKα radiation (λ = 0.71070 Å). The data were collected at 223(2) K in the ranges of 3.03≤θ≤27.49° for 1 and 3.0 ≤ θ ≤ 27.50° for 2. A total of 6953 reflections for 1 and 11669 for 2 were collected with 3388 unique ones (Rint = 0.0453) for 1 and 5717 (Rint = 0.0312) for 2, of which 2615 with I > 2σ(I) for 1 and 4174 for 2 were observed and used in the succeeding refinements. Their intensity data were corrected for Lp factors and empirical absorption. The structures were solved by direct methods and expanded by using difference Fourier techniques with SHELXS-97[31]. All of the non-hydrogen atoms were located with successive difference Fourier syntheses and refined by full-matrix least-squares methods on F2 with anisotropic thermal parameters[32]. H atoms were added geometrically and refined as riding. The final refinement gave R = 0.0351 for 1 / 0.0408 for 2 and wR = 0.0504 for 1 / 0.0922 for 2 (For 1, w = 1/[σ2(Fo)2 + (0.0013P)2 + 0.0000P], where P = (Fc 2 + 2Fc 2)/3, (Δ/σ) max = 0.001, S = 0.946, (Δρ) max = 1.197 and (Δρ) min = -1.295 e/Å3; For 2, w = 1/[σ2(Fo)2 + (0.0420P)2 + 0.0000P], where P = (Fo 2 + 2Fc 2)/3, (Δ/σ) max = 0.001, S = 1.018, (Δρ) max = 0.465 and (Δρ) min = -0.414 e/Å3). Selected bond lengths and bond angles are listed in Table 1.
1 Bond Dist. Bond Dist. Bond Dist. Hg(1)-Br(1) 2.4381(6) Hg(1)-Br(2) 2.4301(7) Hg(1)-N(1) 2.570(6) Angle (°) Angle (°) Angle (°) Br(2)-Hg(1)-Br(1) 163.47(3) Br(2)-Hg(1)-N(1) 101.94(10) Br(1)-Hg(1)-N(1) 92.15(10) 2 Bond Dist. Bond Dist. Bond Dist. Cu(1)-N(1) 2.038(2) Cu(1)-N(2) 2.060(2) Cu(1)-O(1) 2.4308(19) Cu(1)-Cl(4) 2.2530(8) Cu(1)-Cl(3) 2.2679(7) Cu(1)-O(4) 2.4313(19) Angle (°) Angle (°) Angle (°) N(1)-Cu(1)-N(2) 89.34(8) Cl(4)-Cu(1)-O(1) 103.39(5) N(1)-Cu(1)-Cl(4) 89.49(6) N(2)-Cu(1)-Cl(4) 158.81(6) N(1)-Cu(1)-O(4) 106.69(8) N(1)-Cu(1)-Cl(3) 159.61(6) N(2)-Cu(1)-Cl(3) 90.85(6) Cl(4)-Cu(1)-O(4) 88.87(5) Cl(4)-Cu(1)-Cl(3) 97.49(3) N(1)-Cu(1)-O(1) 72.01(7) O(1)-Cu(1)-O(4) 167.58(6) N(2)-Cu(1)-O(1) 96.34(8) Cl(3)-Cu(1)-O(1) 87.72(4) N(2)-Cu(1)-O(4) 71.24(7) Cl(3)-Cu(1)-O(4) 92.64(5) Table 1. Selected Bond Lengths (Å) and Bond Angles (°)3 RESULTS AND DISCUSSION
3.1 Crystal structures
Complex 1 is a mononuclear compound consisting of one HgII ion, two Br anions and one L ligand (Fig. 1). The HgII centre has a distorted trigonal planar geometry comprised of two Br atoms and one quinoline N atom of the L ligand. The Hg-N bond length is 2.570(6) Å and the Hg-Br bond lengths are 2.4381(6) and 2.4301(7) Å. The angles around the Hg atom are 92.15(10), 101.94(10) and 163.47(3)°, respectively. Weak Hg…O interactions with distances of 2.766(1) and 2.849(1) Å are observed. If these are considered to be chemically significant interactions, a grossly distorted trigonal biyramid coordination about Hg is thus resulted (Fig. 1). The centroid-centroid separation (3.656(1) Å) between the pyridine moieties of the quinoline rings of centrosymmetrically related complex molecules indicate the presence of intermolecular face-to-face π-π stacking interactions (Fig. 2)[33]. Intermolecular C-H…π stacking interactions are also observed between methyl hydrogen atom H (12B) from one ligand and the centroid of the quinoline ring of the adjacent ligand, with a separation of 2.859(1) Å (Fig. 2)[34]. Intermolecular C-H…Br hydrogen bonds also exist in the H (3A) atoms of quinoline rings and the boromide atoms Br (2) (symmetry code: 1-x, -y, 1-z) of adjacent complex molecule as well as the methylene hydrogen atoms H (10B) and the boromide atoms Br (1) (symmetry code: -x, -y, 2-z) of adjacent complex molecule, as shown in Fig. 2 and Table 2[35]. Furthermore, the quasi one-dimensional chains are assembled by these intermolecular π-π, C-H…π interactions and intermolecular C-H…Br hydrogen bonds (Fig. 2).
D-H…A d(D-H) d(H…A) d(D…A) ∠D-H…A C(3)-H(3A)…Br(2)i 0.93 2.995 3.845(10) 153 C(10)-H(10B)… Br(1)ii 0.97 2.988 3.922(10) 162 C(19)-H(19)…Cl(3)iii 0.94 2.71 3.641(3) 174 C(22)-H(22B)…Cl(3)iii 0.98 2.65 3.574(3) 157 C(10)-H(10B)…Cl(4)iv 0.98 2.82 3.414(2) 120 Symmetry codes: (i) 1-x, -y, 1-z; (ii) -x, -y, 2-z; (iii) 1-x, 1-y, 1-z; (iv) 2-x, 1-y, -z Table 2. Hydrogen Bond Lengths (Å) and Bond Angles (°)Complex 2 is a neutral mononuclear complex consisting of one copper (II) ion, two Cl anions and two L ligands (Fig. 3). Each CuII center has a distorted octahedral geometry (Table 1) comprised of two chloride ions, two quinoline N atoms and two O atoms of two L ligands. The coordination basal plane is defined by N (1), N (2), Cl (3) and Cl (4), and the apical position is occupied by O (1) and O (4). Atoms N (1), N (2), Cl (3) and Cl (4) show deviations of -0.4153(1), 0.4065(1), -0.3363(1) and 0.3452(1)°, respectively from their leastsquares mean plane. Intermolecular C-H…Cl hydrogen bonds exist in the quinoline rings H (19) atoms, the methylene hydrogen atoms H (22B) and the chloride atoms Cl (3) (symmetry code: 1-x, 1-y, 1-z) of one adjacent complex molecule as well as the methylene hydrogen atoms H (10B) and the chloride atoms Cl (4) (symmetry code: 2-x, 1-y, -z) of another adjacent complex molecule, as shown in Fig. 4 and Table 2[35]. Then, the quasi one-dimensional chains are assembled by intermolecular C-H…Cl hydrogen bonds (Fig. 4).
The structural differences between 1 and 2 exhibit the influences of different metal ions, and may mainly attribute to the differences of their coordination abilities. The atomic radius of Hg is greater than that of Cu, resulting in trigonal planar geometry of HgII centre and octahedron geometry of CuII centre. However, compared with complex [C11H7Cl2NO3Pb][29], no (5-chloro-quinolin-8-yloxy) acetate exists in complexes 1 and 2 while ligand L is formed in 1 and 2. This shows triethylamine does not have the effect of neutralizing protons of (5-chloro-quinolin-8-yloxy) acetic acid. So, it indicates HgII and CuII ions may play a catalytic role in the formation of L.
3.2 XRPD results and thermal analysis
In order to confirm whether the crystal structures are truly representative of the bulk materials, X-ray powder diffraction experiments have been carried out for 1 and 2. The XRPD experimental and computer simulated patterns of the corresponding complexes are shown in Figs. 5 and 6. Their peaks are in good agreement with those calculated from X-ray single-crystal diffraction data, indicating the phase purity of the as-synthesized sample.
Thermal decomposition behaviors of complexes 1 and 2 have been studied by TG in the nitrogen atmosphere. The TG curves of 1 and 2 are illustrated in Fig. 7. Complex 1 occurs in two distinct decomposition stages. It is thermally stable up to 155 ℃ and the first mass loss takes place between 155 and 316 ℃. The experimental mass loss of 68.54% corresponds to the elimination of ligand L and Br anions. The weight loss of 68.54% is close to that calculated (67.23%) for the formula. The second stage in the range of 316 ~ 598 ℃ is complete evaporation of the residual metallic mercury with a mass loss 31.46% (theoretical value 32.77%). So, no remaining residue is observed. The thermal decomposition process of 2 has two steps. It is thermally stable up to 235 ℃. The first weight loss appears at 235~377 ℃, with the weight loss of 34.10% corresponding to the removal of CH2COOCH3 and coordinated Cl anion and close to that calculated (34.05%). The second weight loss (54.78%) from 377 to 622 ℃ is attributed to the elimination of residue ligands (56.00%). Because of the nitrogen atmosphere, the remaining residue is metallic copper (11.12%), which is consistent with the theoretical value of 9.95%.
3.3 Solid fluorescence spectra and optical property of complexes 1 and 2
Solid fluorescence behaviors of complexes 1 and 2 were determined by 350 nm excitation wavelengths at room temperature (Fig. 8). Complexes 1 and 2 exhibit respectively narrow fluorescence emission at 406 and 410 nm, which are similar to that of complex [C11H7Cl2NO3Pb][29] with a fluorescence emission at 407 nm. Thus, compared with the ligand, the emission peak of the complex may be attributed to the ligand-to-metal charge transfer transition.
UV-VIS-NIR diffuse reflectance spectra of 1 were determined at room temperature. The absorption (α/S) data were calculated by the Kubelka- Munk function, α/S = (1 - R)2/2R[36]. The optical band gaps (Eonset) are obtained by the extrapolation of linear portion of the absorption edges. The optical bandgap of 3.2 eV is estimated approximately in complex 1 (Fig. 9), which indicates that it maybe has potential semiconductor property.
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Table 1. Selected Bond Lengths (Å) and Bond Angles (°)
1 Bond Dist. Bond Dist. Bond Dist. Hg(1)-Br(1) 2.4381(6) Hg(1)-Br(2) 2.4301(7) Hg(1)-N(1) 2.570(6) Angle (°) Angle (°) Angle (°) Br(2)-Hg(1)-Br(1) 163.47(3) Br(2)-Hg(1)-N(1) 101.94(10) Br(1)-Hg(1)-N(1) 92.15(10) 2 Bond Dist. Bond Dist. Bond Dist. Cu(1)-N(1) 2.038(2) Cu(1)-N(2) 2.060(2) Cu(1)-O(1) 2.4308(19) Cu(1)-Cl(4) 2.2530(8) Cu(1)-Cl(3) 2.2679(7) Cu(1)-O(4) 2.4313(19) Angle (°) Angle (°) Angle (°) N(1)-Cu(1)-N(2) 89.34(8) Cl(4)-Cu(1)-O(1) 103.39(5) N(1)-Cu(1)-Cl(4) 89.49(6) N(2)-Cu(1)-Cl(4) 158.81(6) N(1)-Cu(1)-O(4) 106.69(8) N(1)-Cu(1)-Cl(3) 159.61(6) N(2)-Cu(1)-Cl(3) 90.85(6) Cl(4)-Cu(1)-O(4) 88.87(5) Cl(4)-Cu(1)-Cl(3) 97.49(3) N(1)-Cu(1)-O(1) 72.01(7) O(1)-Cu(1)-O(4) 167.58(6) N(2)-Cu(1)-O(1) 96.34(8) Cl(3)-Cu(1)-O(1) 87.72(4) N(2)-Cu(1)-O(4) 71.24(7) Cl(3)-Cu(1)-O(4) 92.64(5) Table 2. Hydrogen Bond Lengths (Å) and Bond Angles (°)
D-H…A d(D-H) d(H…A) d(D…A) ∠D-H…A C(3)-H(3A)…Br(2)i 0.93 2.995 3.845(10) 153 C(10)-H(10B)… Br(1)ii 0.97 2.988 3.922(10) 162 C(19)-H(19)…Cl(3)iii 0.94 2.71 3.641(3) 174 C(22)-H(22B)…Cl(3)iii 0.98 2.65 3.574(3) 157 C(10)-H(10B)…Cl(4)iv 0.98 2.82 3.414(2) 120 Symmetry codes: (i) 1-x, -y, 1-z; (ii) -x, -y, 2-z; (iii) 1-x, 1-y, 1-z; (iv) 2-x, 1-y, -z -

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