English

• 1. INTRODUCTION

  Chiral metal-organic frameworks, also known as chiral coordination polymers, are a class of crystalline materials having chiral infinite structures built with multitopic organic ligands and metal ions. Although chiral functional coordination polymers could be obtained from achiral ligands^[1], the preparations of chiral coordination polymers through the self-assembly of optically pure chiral organic ligands with metal ions are the major process^[2-12]. Natural amino acids are one of the rich sources among the chiral organic linkers for the construction of chiral complexes, resulting in the development of various structures of fascinating architectures^{[13, 14]}. Retention of chirality by incorporating chiral linker to a coupling product is one of the most powerful strategies for the synthesis of chiral materials. A number of small chiral molecules are luring the great interests of material chemist to design and synthesize the new chiral product of their choice^{[15, 16]}.

  4, 5-Dihydrothiazole-4-darboxylic acid is the chiral building block in firefly luciferin (D-(-)-luciferin). This chiral functional moiety can be synthesized by the reaction between carbonitrile and chiral cysteine. Although this kind of molecules has been applied in bioluminescence imaging and sensors^{[17, 18]}, the derivatives bearing 4, 5-dihydrothiazole-4-darboxylic acid has rarely been used as ligands involving in the preparation of metal complexes so far^{[19, 20]}. Due to the fact that there are multiple coordination sites in 4, 5-dihydrothiazole-4-darboxylic acid and their chiral nature, it would be of great significance to design and synthesize new chiral ligands derived from 4, 5-dihydrothiazole-4-darboxylic acid by the reaction between the carbonitrile and chiral cysteine.

  Herein we report the synthesis of a pair of chiral ligands, namely (R)- and (S)-2-(4-carboxyphenyl)-4, 5-dihydrothiazole-4-carboxylic acid (H₂L^R and H₂L^S), and the preparation and characterization of four coordination polymers obtained from this pair of ligands.

  2. EXPERIMENTAL

  2.1 Instruments and reagents

  All chemicals purchased from commercial sources were of reagent grade and used as received without further purification unless otherwise stated. ¹H and ¹³C NMR spectra were measured on a Bruker AVANCE Ⅲ HD 400 spectrometer in DMSO-d₆ at 293 K with TMS as the internal standard unless otherwise specified. HRMS for the ligand were recorded on a Waters Micro mass Q-TOF Premier Mass Spectrometer in negative model. The capillary voltage, source temperature, desolvation temperature, desolvation gas, scan range, scan time and interscan time were set at 350 ^oC, 600 l/hr, m/z 100~1500, 1s and 0.02 s, respectively, and the quoted m/z values are for the major peaks in the isotopic distribution. Circular dichroism (CD) spectra of the ligands and the complexes were recorded on a JASCO T-815 spectropolarimeter fitted with DRCD apparatus. The UV-visible (UV-Vis) absorption spectra were recorded using a Lambda 35 UV/Vis Spectrometer (Perkin Elmer, Inc., USA). Melting points were measured with SGW X-4 micro melting point apparatus. The fluorescence spectra were performed on a Perkin Elmer LS 55 fluorescence spectrophotometer.

  2.2 Synthesis of the ligands (H₂L^R) and (H₂L^S)^{[19, 20]}

  4-Cyanobenzoic acid (2.68 g, 20.0 mmol), L-cysteine or D cysteine (3.63 g, 30.0 mmol) and NaHCO₃ (2.52 g, 30.0 mmol) were mixed in a solution of CH₃OH (200 mL) and H₂O (120 mL), then a catalytic amount of NaOH (40.0 mg, 1.00 mmol) was added (pH ~7.5). The reaction mixture was stirred at room temperature until TLC analysis indicated the disappearance of 4-cyanobenzoic acid (48 h). Then CH₃OH was removed from the mixture by evaporation under reduced pressure at 40 ^ᴼC. The resulting crude mixture was acidified with dilute hydrochloride acid to pH about 2 (indicator paper) while cooling in a water/ice bath. The precipitated solid was collected by filtration and washed several times with cold water and dried in vacuum, obtaining the ligands as white powder.

  H₂L^R, yield 3.51 g (70%); m.p. 220~222 ℃. ¹H-NMR (400 MHz, DMSO-d₆): δ = 13.29 (s, 1H), 8.06~8.04 (d, 2H), 7.92~7.90 (d, 2H), 5.35(t, 1H), 3.79~3.73 (m, 1H), 3.69~3.64 (m, 1H); ¹³C NMR (151 MHz, DMSO-d₆): δ =171.65, 167.77, 166.66, 135.86, 133.45, 129.83, 128.36, 78.48, 35.23. H RMS Calcd. for [H₂L^R]^- m/z = 250.0179, Obs. 250.0189 (100%) with insource fragmentation peak of [H₂L^R-CO₂]^- at m/z 206.0296 (95%).

  H₂L^S, yield 3.60 g (72%); m.p. 220~222 ℃. ¹H NMR (400 MHz, DMSO-d₆): δ = 13.19 (s, 1H), 8.05~8.03 (d, 2H), 7.91~7.89 (d, 2H), 5.35(t, 1H), 3.78~3.73 (m, 1H), 3.68~3.63 (m, 1H); ¹³C NMR (151 MHz, DMSO-d₆): δ =171.65, 167.77, 166.66, 135.86, 133.45, 129.83, 128.36, 78.48, 39.52 (DMSO), 35.23. H RMS: Calcd. for [H₂L^R]^- m/z = 250.0179, Obs. 250.0186 (100%) with insource fragmentation peak of [H₂L^S-CO₂]^- at m/z 206.0286 (80%).

  2.3 Syntheses of the complexes 1R, 1S, 2R, and 2S

  Complexes 1R and 1S Ligand (R)-2-(4-carboxyphenyl)-4, 5-dihydrothiazole-4-carboxylic acid (H₂L^R) (37.5 mg, 0.15 mmol) was dissolved in water (3.0 mL) in a straight test tube followed by the addition of pyridine (dropwise slowly) until the ligand was completely dissolved to get a transparent solution. A solution of Ni(ClO₄)₂·6H₂O (54.9 mg, 0.15 mmol) in acetonitrile (1.0 mL) was carefully layered on the above solution. The test tube was covered and kept undisturbed. Needle like blue crystals of complex 1^R suitable for X-ray diffraction analysis were obtained after a week period. Yield 27.0 mg (42% based on the ligand). Complex 1S (blue crystal) was synthesized by a similar method as that of complex 1R except that the ligand H₂L^R was replaced by the ligand H₂L^S. Yield 28.3 mg (44% based on the ligand).

  Complexes 2R and 2S Ligand (R)-2-(4-carboxyphenyl)-4, 5-dihydrothiazole-4-carboxylic acid (H₂L^R) (37.5 mg, 0.15 mmol) was dissolved in water (3.0 mL) in a straight test tube followed by the addition of (CH₃)₄NOH solution (dropwise slowly) until the ligand was completely dissolved to get a transparent solution. A solution of Zn(ClO₄)₂·6H₂O (56.0 mg, 0.15 mmol) in acetonitrile (1.0 mL) was carefully layered on the above solution. The test tube was covered and kept undisturbed. Needle like colorless crystals of complex 2R suitable for X-ray diffraction analysis were obtained after a week. Yield 31.0 mg (57% based on the ligand). Complex 2S was prepared by a similar method as that of complex 2R except that the ligand H₂L^R was replaced by the ligand H₂L^S. Yield 28.5 mg (52% based on the ligand).

  2.4 Crystallographic measurements and structure determination

  The crystals of the complexes with suitable size were selected for X-ray single-crystal diffraction. The data were collected on a Bruker D8 VENTURE CMOS photon 100 diffractometer with Helios MX multilayer monochromator Cu-Kα radiation (λ = 1.54178 Å). The multi-scan absorption correction was applied by using the SADABS program (SMART-CCD Software, version 5.0; Siemens Analytical X-ray Instruments: Madison, WI, 1996). Data collection and reduction were performed using the SMART and SAINT software. Structures were solved by direct methods and refined with full-matrix least-squares on F² using SHELXT-2014^[21] and SHELXL-2014^[22]. Non-hydrogen atoms were refined with anisotropic displacement parameters during the final cycles, and the hydrogen atoms of organic ligands were placed in calculated sites and included as riding atoms with isotropic displacement parameters set to 1.2U_eq of the attached C atoms. All the calculations were carried out using SHELXTL program^{[21, 22]}. For complex 1R, a total of 10451 reflections were collected and 3125 were independent (R_int = 0.0275). For complex 1S, a total of 16586 reflections were collected and 3104 were independent (R_int = 0.0643); the maximum residual density during the refinement is 1.49, which is near the nickel center in complex 1S (0.66 Å). For complex 2R, a total of 12361 reflections were collected and 5132 were independent (R_int = 0.0346), and for complex 2S, out of the 16149 total reflections, 55245 were independent (R_int = 0.0246). The crystallographic data and structure refinement details of the complexes are summarized in Table 1. Selected bond lengths and bond angles of complexes 1R and 1S are collected in Table 2, and bond lengths and bond angles of complexes 2R and 2S are listed in Table 3.

  Table 1

  

  Table 1.  Data Collection and Processing Parameters for Complexes 1 and 2

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  Complex	1R	1S	2R	2S
  Formula	C16H16N2NiO6S	C16H16N2NiO6S	C24H23N3O11S2Zn2	C24H23N3O11S2Zn2
  Mr	423.06	423.06	724.31	724.31
  Temperature/K	172(2)	296(2)	294(2)	223(2)
  Wavelength	1.54178	1.54178	1.54178	1.54178
  Crystal system	Monoclinic	Monoclinic	Monoclinic	Monoclinic
  Space group	P21	P21	P21	P21
  a/Å	9.068(2)	9.1623(9)	14.5983(6)	14.6154(4)
  b/Å	6.043(2)	6.0742(9)	5.9838(3)	5.9671(2)
  c/Å	16.069(3)	16.0735(19)	17.4345(7)	17.3506(5)
  α/°	90	90	90	90
  β/°	97.61(3)	97.234(4)	106.668(2)	107.0940(10)
  γ/°	90	90°	90	90
  V/Å3	872.8(4)	887.43(19)	1458.97(11)	1446.33(8)
  Z	2	2	2	2
  Crystal size/mm	0.29 × 0.22 × 0.14	0.31 × 0.24 × 0.17	0.26 × 0.19 × 0.16	0.25 ×0.14 × 0.12
  ρcalcd (Mg/m3)	1.610	1.583	1.649	1.663
  μ/mm-1	3.059	3.008	3.914	3.949
  F(000)	436	436	736	736
  θ range/°	2.774 to 68.478°.	2.771 to 66.534°.	2.645 to 68.344°.	3.163 to 68.307°.
  Reflections collected 7351	10451	16586	12361	16149
  Independent reflections	3125 (0.0275)	3104 (0.0634)	5132 (0.0346)	5245 (0.0246)
  Data/restraints/parameters	3125/7/252	3104/7/252	5132/17/390	5245/22/422
  GOF (F2)	1.045	1.020	1.046	1.046
  Final Rindices (I > 2σ(I)) R, wR	0.0227, 0.0615	0.0628, 0.1566	0.0373, 0.0897	0.0184, 0.0478
  Rindices (all data)	0.0234, 0.0655	0.0647, 0.1614	0.0438, 0.0936	0.0186, 0.0480
  Flack	0.04(2)	0.16(5)	0.028(14)	0.025(16)
  (Δρ)max, (Δρ)min (e·Å-3)	0.218 and –0.308	1.491 and –0.398	0.761 and –1.648	0.302 and –0.268

  Table 2

  

  Table 2.  Selected Bond Lengths (Å) and Bond Angles (°) for Complexes 1R and 1S

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  Complex 1R
  Bond	Dist.		Bond	Dist.		Bond	Dist.
  Ni(1)–N(2)	1.995(2)		Ni(1)–O(1)	1.981(2)		Ni(1)–O(5)	2.206(3)
  Ni(1)–N(1)#A	1.999(2)		Ni(1)–O(4)#A	2.019(2)
  Angle	(°)		Angle	(°)		Angle	(°)
  O(1)–Ni(1)–N(2)	91.13(9)		N(2)–Ni(1)–O(4)#A	91.71(9)		N(1)#A–Ni(1)–O(5)	85.00(10)
  O(1)–Ni(1)–N(1)#A	94.84(9)		N(1)#A–Ni(1)–O(4)#A	82.46(9)		O(4)#A–Ni(1)–O(5)	97.98(9)
  N(2)–Ni(1)–N(1)#A	173.84(10)		O(1)–Ni(1)–O(5)	114.78(9)
  O(1)–Ni(1)–O(4)#A	146.83(9)		N(2)–Ni(1)–O(5)	93.88(10)
  Complex 1S
  Bond	Dist.		Bond	Dist.		Bond	Dist.
  Ni(1)–N(2)	1.992(5)		Ni(1)–O(1)	1.986(4)		Ni(1)–O(5)	2.239(6)
  Ni(1)–N(1)#A	2.002(5)		Ni(1)–O(4)#A	2.015(5)
  Angle	(°)		Angle	(°)		Angle	(°)
  O(1)–Ni(1)–N(2)	91.08(19)		N(2)–Ni(1)–O(4)#A	91.9(2)		N(1)#A–Ni(1)–O(5)	84.5(2)
  O(1)–Ni(1)–N(1)#A	95.2(2)		N(1)#A–Ni(1)–O(4)#A	82.2(2)		O(4)#A–Ni(1)–O(5)	97.8(2)
  N(2)–Ni(1)–N(1)#A	173.6(2)		O(1)–Ni(1)–O(5)	114.7(2)
  O(1)–Ni(1)–O(4)#A	147.01(19)		N(2)–Ni(1)–O(5)	94.0(3)
  Symmetry code: #A –x+1, y–1/2, –z+1

  Table 3

  

  Table 3.  Hydrogen Bond Lengths (Å) and Bond Angles (°) for Complexes 1R and 1S

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  D–H···A	d(D–H)	d(H···A)	d(D···A)	∠DHA	Symmetry code
  Complex 1R
  O(5)–H(51)···O(W)	0.87(1)	1.95	2.699(3)	145
  O(5)–H(52)···O(2)	0.86(1)	1.89	2.736(3)	166	x, y–1, z
  O(W)–H(W1)···O(3)	0.86(1)	1.94	2.802(3)	177	x–1, y–1, z–1
  O(W)–H(W2)···O(3)	0.86(1)	1.90	2.723 (3)	158	–x+1, y–3/2, –z+1
  C(12)–H(12A)···O(2)	0.93(1)	2.33	3.234 (3)	164	x, y–1, z
  C(16)–H(16A)···O(4)	0.93(1)	2.58	3.027(3)	110	–x+1, y–1/2, –z+1
  Complex 1S
  O(5)–H(51)···N(2)	0.85(1)	2.52	3.100(6)	126
  O(5)–H(52)···O(2)	0.86(1)	1.91	2.749(6)	164	x, y+1, z
  O(W1)–H(1W1)···O(3)	0.86(1)	1.89	2.710 (6)	160
  O(W1)–H(1W2)···O(3)	0.85(1)	2.02	2.804(6)	153	–x+2, y–1/2, –z+2
  C(12)–H(12A)···O(2)	0.93(1)	2.38	3.282(6)	164	x, y+1, z
  C(16)–H(16A)···O(4)	0.93(1)	2.58	3.040(6)	111	–x+1, y+1/2, –z+1

  3. RESULTS AND DISCUSSION

  3.1 Preparation of the ligands

  The ligands H₂L^R and H₂L^S were prepared with good yields by the reactions between 4-cyanobenzoic acid (Sch. 1) and L-cysteine or D-cysteine in water/methanol mixture under a slightly basic condition (pH≈7.5) at room temperature. The ¹H and ¹³C NMR spectra of the ligands indicate that they are quite pure, and the resonance signals of the protons of two ligands match each other very well. The circular dichroism (CD) spectra of the ligands H₂L^R and H₂L^S are mirror images of each other (Fig. 1), and the observation indicates their enantiomeric nature. The main peak at m/z 250.0189 in negative mode corresponding to the species (HL^R)^- was observed from the electrospray ionization mass spectrometry (ESI-MS) of the ligand H₂L^R with insource fragmentation peak of (H₂L^R-CO₂)^- at m/z 206.0296. The main peak of ESI-MS of the ligand H₂L^S is at m/z 250.0186, corresponding to the species (HL^S)^- while the insource fragmentation peak of (H₂L^S-CO₂)^- is at m/z 206.0286. All these characterizations indicate that the ligands H₂L^R and H₂L^S are as per the design.

  Scheme 1

  

  Scheme 1.  Synthesis of ligands H₂L^R and H₂L^S

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  Figure 1

  

  Figure 1.  UV-Vis and CD spectra of ligands H₂L^R and H₂L^S in MeOH

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  3.2 X-ray single-crystal structure analysis

  As shown in Table 1, the space groups of complexes 1R and 1S are the same and the cell parameters are similar, so complexes 1R and 1S are iso-structural. Therefore, only the structure of complex 1^R is described in detail. The coordination environment of the central Ni(Ⅱ) ion in complex 1R is shown in Fig. 2, where the Ni(Ⅱ) ion is coordinated by an oxygen atom from carboxylate group of a ligand (L^R)^2-, a NO unit from another ligand, a nitrogen atom of pyridine, and an oxygen atom of a water molecule, forming a tetragonal pyramidal geometry. The O(1), O(4A), N(2), and N(1A) atoms are located in the basal plane, and O(5) atom occupies the axial (apical) positions. The Ni–N bond distances fall in the range of 1.995(2)~1.999(2) Å, the Ni–O bond distances are 1.981(2) and 2.206(3) Å. The bond angles vary from 82.46(9) to 173.84(10)° (Table 2). The geometric parameter τ value of the polyhedron NiN₂O₃ is 0.450, calculated by using the literature method^[23]. Each Ni(Ⅱ) ion coordinates to two ligands, and each ligand bridges two nickel(Ⅱ), forming a one-dimensional left hand helical chain along the b axis, as shown in Fig. 3. The result implies that the helical configuration of the complex may be controlled by the structural feature of the chiral ligand. To confirm the influence of the ligand chirality on the helical structure in the complex, an enantiomer ligand H₂L^S and the Ni(Ⅱ) complex 1S have been prepared successfully. Just as expected, the Ni(Ⅱ) ion and ligand bridge each other to form a one-dimensional right hand helical chain along the b axis in the crystal of complex 1S. As shown in Fig. 4, the circular dichroism (CD) spectra of complexes 1R and 1S made from R- and S-enantiomers of the ligand are mirror images of each other, which indicate their enantiomeric nature. The observations confirm that chiral helical configuration of the complexes is controlled by the structural feature of the chiral ligands. There are hydrogen bonds between O and H atoms within the helical one-dimensional chain in the crystal of complex 1R (Fig. 5), with the hydrogen bond data of complex 1R and 1S listed in Table 3.

  Figure 2

  

  Figure 2.  Coordination environments of the center ions in complexes 1R (left) and 1S (right)

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  Figure 3

  

  Figure 3.  Helical chain in complexes 1R and 1S

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  Figure 4

  

  Figure 4.  Circular dichroism (CD) spectra of complexes 1R and 1S

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  Figure 5

  

  Figure 5.  Packing diagram of complex 1R

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  The fact that complexes 2R and 2S have the same space groups and similar cell parameters (Table 1) indicates they are iso-structural. Therefore, only the structure of complex 2R is described here. As shown in Fig. 6a, considering the distances of Zn(1)–O(3) and Zn(2)–O(8A) are 2.399(3) and 2.432(3) respectively (Table 4), the coordination is ignored. There are two unique zinc centers with ZnO₄N units in complex 2R. Zn(1) coordinates to three different ligands and a water molecule, while Zn(2) is coordinated by two ligands and two water molecules. Both of the zinc centers with ZnO₄N units in 2R are tetragonal pyramidal geometry, in which the geometric parameter τ values of the polyhedral ZnNO₄ units calculated by using the literature method^[23] are 0.302 and 0.370 for Zn(1) and Zn(2), respectively. In the crystal of complex 2R, the ligand containing N(1) and S(1) atoms connects two zinc centers while the ligand containing N(2) and S(2) atoms bridges three zinc atoms. As shown in Fig. 6c, each zinc center connects two ligands and each ligand bridges two or three zinc atoms, generating a two-dimensional sheet. The Zn(1) centers are connected by the ligands to form a left-hand chain, the Zn(2) centers are bridged by the ligands to generate another left-hand chain, and the two left-hand chains are connected via the oxygen atom O(5) to give the 2-D sheet. The circular dichroism (CD) spectra of complexes 2R and 2S (Fig. 7) made from R- and S-enantiomers of the ligand are mirror images of each other, which confirm their enantiomeric nature. There are hydrogen bonds between O or N atom and H atom in the crystal of complex 2R, as shown in Fig. 8. The neighboring two-dimensional sheets were connected into a three-dimensional structure by hydrogen bonds. The hydrogen bond data of complexes 2R and 2S are listed in Table 5.

  Figure 6

  

  Figure 6.  (a) Coordination environments of zinc(Ⅱ) ions in complex 2R, (b) Coordination environments of zinc(Ⅱ) ions in complex 2S; (c) 2-D sheet and the coordination polyhedra around the Zn(1) (in purple) and Zn(2) (in green) centers in complex 2R; (d) 2-D sheet and the coordination polyhedra around the Zn(1) (in purple) and Zn(2) (in green) centers in complex 2S

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  Table 4

  

  Table 4.  Selected Bond Lengths (Å) and Bond Angles (°) for Complexes 2R and 2S

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  Complex 2R
  Bond	Dist.		Bond	Dist.		Bond	Dist.
  Zn(1)–O(4)	2.038(4)		Zn(1)–N(1)#B	2.190(5)		Zn(2)–O(9)	2.021(5)
  Zn(1)–O(2)#B	2.054(4)		Zn(1)–O(3)	2.406(6)		Zn(2)–O(10)	2.091(4)
  Zn(1)–O(5)	2.081(4)		Zn(2)–O(7)#A	2.026(4)		Zn(2)–N(2)	2.242(5)
  Zn(1)–O(11)	2.082(5)		Zn(2)–O(6)	2.015(4)		Zn(2)–O(8)#A	2.445(5)
  Angle	(°)		Angle	(°)		Angle	(°)
  O(4)–Zn(1)–O(2)#B	145.9(2)		O(4)–Zn(1)–O(3)	57.44(19)		O(7)#A–Zn(2)–O(10)	93.13(17)
  O(4)–Zn(1)–O(11)	106.6(2)		O(2)#B–Zn(1)–O(3)	88.53(17)		O(6)–Zn(2)–N(2)	77.58(16)
  O(2)#B–Zn(1)–O(11)	107.05(18)		O(11)–Zn(1)–O(3)	163.47(17)		O(9)–Zn(2)–N(2)	95.56(19)
  O(4)–Zn(1)–O(5)	94.37(16)		O(5)–Zn(1)–O(3)	94.05(19)		O(7)#1–Zn(2)–N(2)	94.48(17)
  O(2)#B–Zn(1)–O(5)	90.29(16)		N(1)#B–Zn(1)–O(3)	90.2(2)		O(10)–Zn(2)–N(2)	167.76(19)
  O(5)–Zn(1)–O(11)	91.41(18)		O(6)–Zn(2)–O(9)	98.77(18)		O(6)–Zn(2)–O(8)#A	92.66(17)
  O(4)–Zn(1)–N(1)#B	96.92(16)		O(6)–Zn(2)–O(7)#A	149.0(2)		O(9)–Zn(2)–O(8)#A	168.08(16)
  O(2)#B–Zn(1)–N(1)#B	79.15(16)		O(9)–Zn(2)–O(7)#A	111.93(18)		O(7)#1–Zn(2)–O(8)#A	57.04(17)
  O(11)–Zn(1)–N(1)#B	87.4(2)		O(6)–Zn(2)–O(10)	91.00(18)		O(10)–Zn(2)–O(8)#A	86.0(2)
  O(5)–Zn(1)–N(1)#B	168.51(16)		O(9)–Zn(2)–O(10)	90.5(2)		N(2)–Zn(2)–O(8)#A	90.1(2)
  Symmetry codes: #A –x+1, y+1/2, –z+2; #B –x, y–1/2, –z+3; #C –x, y+1/2, –z+3; #D –x+1, y–1/2, –z+2
  Complex 2S
  Bond	Dist.		Bond	Dist.		Bond	Dist.
  Zn(1)–O(2)	2.056(2)		Zn(1)–N(1)	2.190(2)		Zn(2)–O(7)#B	2.032(2)
  Zn(1)–O(3)#A	2.044(2)		Zn(1)–O(4)#A	2.370(2)		Zn(2)–O(10)	2.085(2)
  Zn(1)–O(5)	2.089(2)		Zn(2)–O(6)	2.019(2)		Zn(2)–N(2)	2.240(2)
  Zn(1)–O(11)	2.076(2)		Zn(2)–O(9)	2.028(2)		Zn(2)–O(8)#B	2.426(2)
  Angle	(°)		Angle	(°)		Angle	(°)
  O(3)#A–Zn(1)–O(2)	147.69(8)		O(3)#A–Zn(1)–O(4)#A	58.71(8)		O(7)#B–Zn(2)–O(10)	93.36(8)
  O(3)#A–Zn(1)–O(11)	105.21(9)		O(2)–Zn(1)–O(4)#A	89.11(7)		O(6)–Zn(2)–N(2)	77.63(7)
  O(2)–Zn(1)–O(11)	106.64(8)		O(11)–Zn(1)–O(4)#A	163.44(8)		O(9)–Zn(2)–N(2)	96.05(8)
  O(3)#A–Zn(1)–O(5)	94.73(7)		O(5)–Zn(1)–O(4)#A	94.05(8)		O(7)#B–Zn(2)–N(2)	94.23(8)
  O(2)–Zn(1)–O(5)	90.02(7)		N(1)–Zn(1)–O(4)#A	90.01(8)		O(10)–Zn(2)–N(2)	167.61(8)
  O(11)–Zn(1)–O(5)	91.11(8)		O(6)–Zn(2)–O(9)	98.54(8)		O(6)–Zn(2)–O(8)#B	92.89(7)
  O(3)#A–Zn(1)–N(1)	96.60(8)		O(6)–Zn(2)–O(7)#B	150.00(8)		O(9)–Zn(2)–O(8)#B	167.98(7)
  O(2)–Zn(1)–N(1)	79.24(7)		O(9)–Zn(2)–O(7)#B	111.10(8)		O(7)#B–Zn(2)–O(8)#B	57.93(7)
  O(11)–Zn(1)–N(1)	87.99(8)		O(6)–Zn(2)–O(10)	90.95(8)		O(10)–Zn(2)–O(8)#B	85.73(9)
  O(5)–Zn(1)–N(1)	168.46(7)		O(9)–Zn(2)–O(10)	90.33(8)		N(2)–Zn(2)–O(8)#B	90.01(9)
  Symmetry codes: #A –x+1, y+1/2, –z+2; #B –x, y–1/2, –z+3; #C –x, y+1/2, –z+3; #D –x+1, y–1/2, –z+2

  Figure 7

  

  Figure 7.  Circular dichroism (CD) spectra of complexes 2R and 2S

  DownLoad: Full-Size Img PowerPoint

  Figure 8

  

  Figure 8.  Packing diagram of complex 2R

  DownLoad: Full-Size Img PowerPoint

  Table 5

  

  Table 5.  Hydrogen Bond Lengths (Å) and Bond Angles (°) for Complexes 2R and 2S

  DownLoad: CSV

  D–H···A	d(D–H)	d(H···A)	d(D···A)	∠DHA	Symmetry code
  Complex 2R
  O(9)–H(9B)···O(8)	0.86(1)	1.786	2.640(6)	173	–x+1, y–1/2, –z+2
  O(9)–H(9C)···O(2)	0.86(1)	1.946	2.772(6)	161	–x, y–3/2, –z+3
  O(10)–H(10B)···O(1)	0.86(1)	1.849	2.679(6)	163	–x, y–3/2, –z+3
  O(10)–H(10C)···O(1)	0.86(1)	2.283	2.870(6)	125	x, y–1, z–1
  O(11)–H(11A)···O(3)	0.86(1)	1.927	2.645(6)	140	x, y–1, z
  O(11)–H(11B)···O(6)	0.86(1)	1.975	2.733(6)	147
  C(23)–H(23B)···O(5)	1.00(1)	2.561	3.450(6)	148	–x+1, y+1/2, –z+3
  C(23)–H(23A)···N(3)	1.00(1)	2.605	3.417(6)	138	–x+1, y–1/2, –z+3
  Complex 2S
  O(9)–H(9C)···O(2)	0.84(1)	1.927	2.769(2)	175	x, y+1, z
  O(10)–H(10B)···O(1)	0.84(1)	2.132	2.867(2)	146	–x+2, y+1/2, –z+2
  O(10)–H(10C)···O(1)	0.83(1)	1.847	2.670(2)	172	x, y+1, z
  O(11)–H(11A)···O(4)	0.84(1)	1.827	2.655(2)	171	–x+2, y+1/2, –z+1
  O(11)–H(11B)···O(6)	0.85(1)	1.975	2.718(2)	145
  C(23)–H(23A)···O(5)	0.99(1)	2.548	3.404(2)	145
  C(23)–H(23B)···N(3)	0.99(1)	2.644	3.443(2)	137	–x+1, y+1/2, –z+1
  C(23)–H(23E)···O(3)	1.00(1)	2.626	3.435(2)	139	–x+2, y–1/2, –z+1

  3.3 Photoluminescence spectra

  The solid state photoluminescence spectra of the ligands and the complexes have been measured at room temperature (Fig. 9). For ligands H₂L^R and H₂L^S, the main peak at 498 nm (λ_ex = 342 nm) may account for the π*-π transition of phenyl linker in the ligands^[24]. Emission peaks are at 446 nm (λ_ex = 328 nm) for complexes 1R and 1S, and 449 nm (λ_ex = 330 nm) for complexes 2R and 2S, respectively, and the emissions may be attributed to the ligandcentered π*-π transitions^[24]. In respect to the ligands, the emission peaks for the complexes are blue shifted by 49 to 56 nm and their photoluminescence intensities are decreased significantly, which can be attributed to the coordination effect of the ligands with metal ions^{[25, 26]}.

  Figure 9

  

  Figure 9.  Photoluminescence spectra of the ligands and the complexes

  DownLoad: Full-Size Img PowerPoint

  4. CONCLUSION

  In summary, a pair of new enantiomeric ligands has been synthesized in one step at moderate reaction conditions, and the ligands were utilized in constructing two pairs of chiral coordination polymers with one-dimensional helical architectures or two-dimensional sheets. The chiral structural features of the coordination polymers were controlled by the chirality of ligands. The complexes have blue-shift in luminescent spectrum compared with the free ligands. The chiral ligands based on 4, 5-dihydrothiazole-4-carboxylic acid may be a potential ligand for the design and synthesis of new chiral materials, and more detailed and systematic researches about them are under way.

  
  
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• 

  Scheme 1  Synthesis of ligands H₂L^R and H₂L^S

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  Figure 1  UV-Vis and CD spectra of ligands H₂L^R and H₂L^S in MeOH

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  Figure 2  Coordination environments of the center ions in complexes 1R (left) and 1S (right)

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  Figure 3  Helical chain in complexes 1R and 1S

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  Figure 4  Circular dichroism (CD) spectra of complexes 1R and 1S

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  Figure 5  Packing diagram of complex 1R

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  Figure 6  (a) Coordination environments of zinc(Ⅱ) ions in complex 2R, (b) Coordination environments of zinc(Ⅱ) ions in complex 2S; (c) 2-D sheet and the coordination polyhedra around the Zn(1) (in purple) and Zn(2) (in green) centers in complex 2R; (d) 2-D sheet and the coordination polyhedra around the Zn(1) (in purple) and Zn(2) (in green) centers in complex 2S

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  Figure 7  Circular dichroism (CD) spectra of complexes 2R and 2S

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  Figure 8  Packing diagram of complex 2R

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  Figure 9  Photoluminescence spectra of the ligands and the complexes

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  Table 1.  Data Collection and Processing Parameters for Complexes 1 and 2

  Complex	1R	1S	2R	2S
  Formula	C16H16N2NiO6S	C16H16N2NiO6S	C24H23N3O11S2Zn2	C24H23N3O11S2Zn2
  Mr	423.06	423.06	724.31	724.31
  Temperature/K	172(2)	296(2)	294(2)	223(2)
  Wavelength	1.54178	1.54178	1.54178	1.54178
  Crystal system	Monoclinic	Monoclinic	Monoclinic	Monoclinic
  Space group	P21	P21	P21	P21
  a/Å	9.068(2)	9.1623(9)	14.5983(6)	14.6154(4)
  b/Å	6.043(2)	6.0742(9)	5.9838(3)	5.9671(2)
  c/Å	16.069(3)	16.0735(19)	17.4345(7)	17.3506(5)
  α/°	90	90	90	90
  β/°	97.61(3)	97.234(4)	106.668(2)	107.0940(10)
  γ/°	90	90°	90	90
  V/Å3	872.8(4)	887.43(19)	1458.97(11)	1446.33(8)
  Z	2	2	2	2
  Crystal size/mm	0.29 × 0.22 × 0.14	0.31 × 0.24 × 0.17	0.26 × 0.19 × 0.16	0.25 ×0.14 × 0.12
  ρcalcd (Mg/m3)	1.610	1.583	1.649	1.663
  μ/mm-1	3.059	3.008	3.914	3.949
  F(000)	436	436	736	736
  θ range/°	2.774 to 68.478°.	2.771 to 66.534°.	2.645 to 68.344°.	3.163 to 68.307°.
  Reflections collected 7351	10451	16586	12361	16149
  Independent reflections	3125 (0.0275)	3104 (0.0634)	5132 (0.0346)	5245 (0.0246)
  Data/restraints/parameters	3125/7/252	3104/7/252	5132/17/390	5245/22/422
  GOF (F2)	1.045	1.020	1.046	1.046
  Final Rindices (I > 2σ(I)) R, wR	0.0227, 0.0615	0.0628, 0.1566	0.0373, 0.0897	0.0184, 0.0478
  Rindices (all data)	0.0234, 0.0655	0.0647, 0.1614	0.0438, 0.0936	0.0186, 0.0480
  Flack	0.04(2)	0.16(5)	0.028(14)	0.025(16)
  (Δρ)max, (Δρ)min (e·Å-3)	0.218 and –0.308	1.491 and –0.398	0.761 and –1.648	0.302 and –0.268

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  Table 2.  Selected Bond Lengths (Å) and Bond Angles (°) for Complexes 1R and 1S

  Complex 1R
  Bond	Dist.		Bond	Dist.		Bond	Dist.
  Ni(1)–N(2)	1.995(2)		Ni(1)–O(1)	1.981(2)		Ni(1)–O(5)	2.206(3)
  Ni(1)–N(1)#A	1.999(2)		Ni(1)–O(4)#A	2.019(2)
  Angle	(°)		Angle	(°)		Angle	(°)
  O(1)–Ni(1)–N(2)	91.13(9)		N(2)–Ni(1)–O(4)#A	91.71(9)		N(1)#A–Ni(1)–O(5)	85.00(10)
  O(1)–Ni(1)–N(1)#A	94.84(9)		N(1)#A–Ni(1)–O(4)#A	82.46(9)		O(4)#A–Ni(1)–O(5)	97.98(9)
  N(2)–Ni(1)–N(1)#A	173.84(10)		O(1)–Ni(1)–O(5)	114.78(9)
  O(1)–Ni(1)–O(4)#A	146.83(9)		N(2)–Ni(1)–O(5)	93.88(10)
  Complex 1S
  Bond	Dist.		Bond	Dist.		Bond	Dist.
  Ni(1)–N(2)	1.992(5)		Ni(1)–O(1)	1.986(4)		Ni(1)–O(5)	2.239(6)
  Ni(1)–N(1)#A	2.002(5)		Ni(1)–O(4)#A	2.015(5)
  Angle	(°)		Angle	(°)		Angle	(°)
  O(1)–Ni(1)–N(2)	91.08(19)		N(2)–Ni(1)–O(4)#A	91.9(2)		N(1)#A–Ni(1)–O(5)	84.5(2)
  O(1)–Ni(1)–N(1)#A	95.2(2)		N(1)#A–Ni(1)–O(4)#A	82.2(2)		O(4)#A–Ni(1)–O(5)	97.8(2)
  N(2)–Ni(1)–N(1)#A	173.6(2)		O(1)–Ni(1)–O(5)	114.7(2)
  O(1)–Ni(1)–O(4)#A	147.01(19)		N(2)–Ni(1)–O(5)	94.0(3)
  Symmetry code: #A –x+1, y–1/2, –z+1

  下载: 导出CSV

  Table 3.  Hydrogen Bond Lengths (Å) and Bond Angles (°) for Complexes 1R and 1S

  D–H···A	d(D–H)	d(H···A)	d(D···A)	∠DHA	Symmetry code
  Complex 1R
  O(5)–H(51)···O(W)	0.87(1)	1.95	2.699(3)	145
  O(5)–H(52)···O(2)	0.86(1)	1.89	2.736(3)	166	x, y–1, z
  O(W)–H(W1)···O(3)	0.86(1)	1.94	2.802(3)	177	x–1, y–1, z–1
  O(W)–H(W2)···O(3)	0.86(1)	1.90	2.723 (3)	158	–x+1, y–3/2, –z+1
  C(12)–H(12A)···O(2)	0.93(1)	2.33	3.234 (3)	164	x, y–1, z
  C(16)–H(16A)···O(4)	0.93(1)	2.58	3.027(3)	110	–x+1, y–1/2, –z+1
  Complex 1S
  O(5)–H(51)···N(2)	0.85(1)	2.52	3.100(6)	126
  O(5)–H(52)···O(2)	0.86(1)	1.91	2.749(6)	164	x, y+1, z
  O(W1)–H(1W1)···O(3)	0.86(1)	1.89	2.710 (6)	160
  O(W1)–H(1W2)···O(3)	0.85(1)	2.02	2.804(6)	153	–x+2, y–1/2, –z+2
  C(12)–H(12A)···O(2)	0.93(1)	2.38	3.282(6)	164	x, y+1, z
  C(16)–H(16A)···O(4)	0.93(1)	2.58	3.040(6)	111	–x+1, y+1/2, –z+1

  下载: 导出CSV

  Table 4.  Selected Bond Lengths (Å) and Bond Angles (°) for Complexes 2R and 2S

  Complex 2R
  Bond	Dist.		Bond	Dist.		Bond	Dist.
  Zn(1)–O(4)	2.038(4)		Zn(1)–N(1)#B	2.190(5)		Zn(2)–O(9)	2.021(5)
  Zn(1)–O(2)#B	2.054(4)		Zn(1)–O(3)	2.406(6)		Zn(2)–O(10)	2.091(4)
  Zn(1)–O(5)	2.081(4)		Zn(2)–O(7)#A	2.026(4)		Zn(2)–N(2)	2.242(5)
  Zn(1)–O(11)	2.082(5)		Zn(2)–O(6)	2.015(4)		Zn(2)–O(8)#A	2.445(5)
  Angle	(°)		Angle	(°)		Angle	(°)
  O(4)–Zn(1)–O(2)#B	145.9(2)		O(4)–Zn(1)–O(3)	57.44(19)		O(7)#A–Zn(2)–O(10)	93.13(17)
  O(4)–Zn(1)–O(11)	106.6(2)		O(2)#B–Zn(1)–O(3)	88.53(17)		O(6)–Zn(2)–N(2)	77.58(16)
  O(2)#B–Zn(1)–O(11)	107.05(18)		O(11)–Zn(1)–O(3)	163.47(17)		O(9)–Zn(2)–N(2)	95.56(19)
  O(4)–Zn(1)–O(5)	94.37(16)		O(5)–Zn(1)–O(3)	94.05(19)		O(7)#1–Zn(2)–N(2)	94.48(17)
  O(2)#B–Zn(1)–O(5)	90.29(16)		N(1)#B–Zn(1)–O(3)	90.2(2)		O(10)–Zn(2)–N(2)	167.76(19)
  O(5)–Zn(1)–O(11)	91.41(18)		O(6)–Zn(2)–O(9)	98.77(18)		O(6)–Zn(2)–O(8)#A	92.66(17)
  O(4)–Zn(1)–N(1)#B	96.92(16)		O(6)–Zn(2)–O(7)#A	149.0(2)		O(9)–Zn(2)–O(8)#A	168.08(16)
  O(2)#B–Zn(1)–N(1)#B	79.15(16)		O(9)–Zn(2)–O(7)#A	111.93(18)		O(7)#1–Zn(2)–O(8)#A	57.04(17)
  O(11)–Zn(1)–N(1)#B	87.4(2)		O(6)–Zn(2)–O(10)	91.00(18)		O(10)–Zn(2)–O(8)#A	86.0(2)
  O(5)–Zn(1)–N(1)#B	168.51(16)		O(9)–Zn(2)–O(10)	90.5(2)		N(2)–Zn(2)–O(8)#A	90.1(2)
  Symmetry codes: #A –x+1, y+1/2, –z+2; #B –x, y–1/2, –z+3; #C –x, y+1/2, –z+3; #D –x+1, y–1/2, –z+2
  Complex 2S
  Bond	Dist.		Bond	Dist.		Bond	Dist.
  Zn(1)–O(2)	2.056(2)		Zn(1)–N(1)	2.190(2)		Zn(2)–O(7)#B	2.032(2)
  Zn(1)–O(3)#A	2.044(2)		Zn(1)–O(4)#A	2.370(2)		Zn(2)–O(10)	2.085(2)
  Zn(1)–O(5)	2.089(2)		Zn(2)–O(6)	2.019(2)		Zn(2)–N(2)	2.240(2)
  Zn(1)–O(11)	2.076(2)		Zn(2)–O(9)	2.028(2)		Zn(2)–O(8)#B	2.426(2)
  Angle	(°)		Angle	(°)		Angle	(°)
  O(3)#A–Zn(1)–O(2)	147.69(8)		O(3)#A–Zn(1)–O(4)#A	58.71(8)		O(7)#B–Zn(2)–O(10)	93.36(8)
  O(3)#A–Zn(1)–O(11)	105.21(9)		O(2)–Zn(1)–O(4)#A	89.11(7)		O(6)–Zn(2)–N(2)	77.63(7)
  O(2)–Zn(1)–O(11)	106.64(8)		O(11)–Zn(1)–O(4)#A	163.44(8)		O(9)–Zn(2)–N(2)	96.05(8)
  O(3)#A–Zn(1)–O(5)	94.73(7)		O(5)–Zn(1)–O(4)#A	94.05(8)		O(7)#B–Zn(2)–N(2)	94.23(8)
  O(2)–Zn(1)–O(5)	90.02(7)		N(1)–Zn(1)–O(4)#A	90.01(8)		O(10)–Zn(2)–N(2)	167.61(8)
  O(11)–Zn(1)–O(5)	91.11(8)		O(6)–Zn(2)–O(9)	98.54(8)		O(6)–Zn(2)–O(8)#B	92.89(7)
  O(3)#A–Zn(1)–N(1)	96.60(8)		O(6)–Zn(2)–O(7)#B	150.00(8)		O(9)–Zn(2)–O(8)#B	167.98(7)
  O(2)–Zn(1)–N(1)	79.24(7)		O(9)–Zn(2)–O(7)#B	111.10(8)		O(7)#B–Zn(2)–O(8)#B	57.93(7)
  O(11)–Zn(1)–N(1)	87.99(8)		O(6)–Zn(2)–O(10)	90.95(8)		O(10)–Zn(2)–O(8)#B	85.73(9)
  O(5)–Zn(1)–N(1)	168.46(7)		O(9)–Zn(2)–O(10)	90.33(8)		N(2)–Zn(2)–O(8)#B	90.01(9)
  Symmetry codes: #A –x+1, y+1/2, –z+2; #B –x, y–1/2, –z+3; #C –x, y+1/2, –z+3; #D –x+1, y–1/2, –z+2

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  Table 5.  Hydrogen Bond Lengths (Å) and Bond Angles (°) for Complexes 2R and 2S

  D–H···A	d(D–H)	d(H···A)	d(D···A)	∠DHA	Symmetry code
  Complex 2R
  O(9)–H(9B)···O(8)	0.86(1)	1.786	2.640(6)	173	–x+1, y–1/2, –z+2
  O(9)–H(9C)···O(2)	0.86(1)	1.946	2.772(6)	161	–x, y–3/2, –z+3
  O(10)–H(10B)···O(1)	0.86(1)	1.849	2.679(6)	163	–x, y–3/2, –z+3
  O(10)–H(10C)···O(1)	0.86(1)	2.283	2.870(6)	125	x, y–1, z–1
  O(11)–H(11A)···O(3)	0.86(1)	1.927	2.645(6)	140	x, y–1, z
  O(11)–H(11B)···O(6)	0.86(1)	1.975	2.733(6)	147
  C(23)–H(23B)···O(5)	1.00(1)	2.561	3.450(6)	148	–x+1, y+1/2, –z+3
  C(23)–H(23A)···N(3)	1.00(1)	2.605	3.417(6)	138	–x+1, y–1/2, –z+3
  Complex 2S
  O(9)–H(9C)···O(2)	0.84(1)	1.927	2.769(2)	175	x, y+1, z
  O(10)–H(10B)···O(1)	0.84(1)	2.132	2.867(2)	146	–x+2, y+1/2, –z+2
  O(10)–H(10C)···O(1)	0.83(1)	1.847	2.670(2)	172	x, y+1, z
  O(11)–H(11A)···O(4)	0.84(1)	1.827	2.655(2)	171	–x+2, y+1/2, –z+1
  O(11)–H(11B)···O(6)	0.85(1)	1.975	2.718(2)	145
  C(23)–H(23A)···O(5)	0.99(1)	2.548	3.404(2)	145
  C(23)–H(23B)···N(3)	0.99(1)	2.644	3.443(2)	137	–x+1, y+1/2, –z+1
  C(23)–H(23E)···O(3)	1.00(1)	2.626	3.435(2)	139	–x+2, y–1/2, –z+1

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