English

• 0.   Introduction

  Coordination polymers (CPs) are a new class of solids consisting of metal-based nodes (single ions or clusters) bridged by organic linking groups, which have attracted much attention due to their excellent pros-pects in many applications, such as luminescence, car-bon capture, and heterogeneous catalysis^[1-4]. Fluores-cent CPs showed prospects in many applications such as sensing and detecting^[5], light-emitting diode^[6-7], up-conversion luminescence^[8], and bioimaging^[9].

  Using organic ligands that can form strong metal-ligand bonds and exhibit highly fluorescent emissions is one strategy for building fluorescent CPs. Anthra-cene and pyrene derivatives^[10] and anthracene and pyrene-based CPs showed interesting prospects in met-al ions sensing^[11-12], optical properties modulation^[13-14], CO₂ reduction^[15-16], and fluorophores in living cells^[17], etc. Fluorescent properties of those functional CPs were enhanced by using ligands containing polycyclic aro-matic moiety of large conjugated systems.

  We designed two highly fluorescent organic ligands based on anthracene or pyrene, 1, 6-di(1H-imidazol-1-yl)pyrene (dip) and 9, 10-di(1H-imidazol-1-yl)anthra-cene (dia), and synthesized five CPs using transitional metals, dip/dia, and anionic ligands [cyclohexane-1, 4-dicarboxylic acid (H₂cda) and camphoric acid (H₂cpa)] (Scheme 1). We herein report the synthesis, structures, thermal stability, and fluorescent properties of these CPs.

  Scheme 1

  

  Scheme 1.  Organic ligands used in this work

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  1.   Experimental

  1.1   Materials and methods

  Both dia and dip ligands were synthesized follow-ing reported procedures^[18-19]. All reagents and solvents for the synthesis and analysis were of analytical grade and were used without further purification. The NMR experiment was recorded using a Bruker Advanced Triple HD 400 Spectrometer. Powder X-ray diffraction (PXRD) data were collected over the 2θ range of 3°-50° using a Bruker Advance D8 diffractometer with Cu Kα₁ radiation (λ=0.154 056 nm, 40 kV, 40 mA). Thermogravimetric analysis (TGA) was performed using a PerkinElmer Diamond Thermogravimetric-Differential Thermal Analysis Analyzer, and the heat-ing rate was 5 ℃·min-1. The fluorescence spectrum was recorded using a Hitachi F-4600 fluorescence spectrophotometer equipped with a plotter.

  1.2   Synthesis of CP [Cd(dip)(cda)]·4H₂O}_n (1)

  Cd(NO₃)₂·4H₂O (12 mg, 0.04 mmol), H₂cda (8 mg, 0.04 mmol) and dip (12 mg, 0.04 mmol) were dissolved in DMF (4 mL) and H₂O (4 mL). The reaction mixture was transferred into a 25 mL Teflon-lined autoclave and sealed. The reaction took place at 90 ℃ for two days and afforded yellow crystals, which were collected by filtration, and washed with fresh DMF and acetone (Yield: 60% based on dip ligand).

  1.3   Synthesis of CP {[Cd(dip)(cpa)]·4H₂O}_n (2)

  Cd(NO₃)₂·4H₂O (12 mg, 0.04 mmol), H₂cpa (8 mg, 0.04 mmol), and dip (12 mg, 0.04 mmol) were dis-solved in DMF (8 mL) and H₂O (2 mL). The reaction mixture was transferred into a 25 mL Teflon-lined auto-clave and sealed. The reaction took place at 90 ℃ for two days and afforded colorless crystals, which were collected by filtration, and washed with fresh DMF and acetone (Yield: 50% based on dip ligand).

  1.4   Synthesis of CP {[Ni(dia)₂Cl₂]·DMF}_n (3)

  NiCl₂·4H₂O (8 mg, 0.04 mmol) and dia (12 mg, 0.04 mmol) were dissolved in MeOH (12 mL). Thereaction mixture was transferred into a 25 mL Teflon-lined autoclave and sealed. The reaction took place at 70 ℃ for two days and afforded green crystals, which were collected by filtration, and washed with fresh MeOH and acetone (Yield: 80% based on dia ligand).

  1.5   Synthesis of CP {[Cd(dia)₂(H₂O)₂](NO₃)₂·2DMSO}_n (4)

  Cd(NO₃)₂·4H₂O (12 mg, 0.01 mmol) and dia (12 mg, 0.04 mmol) were dissolved in DMSO (8 mL) and H₂O (4 mL). The reaction mixture was transferred into a 25 mL Teflon-lined autoclave and sealed. The reac-tion took place at 120 ℃ for two days and afforded col-orless crystals, which were collected by filtration, and washed with fresh DMSO and acetone (Yield: 50 % based on dia ligand).

  1.6   Synthesis of CP [Zn(dip)Cl₂]_n (5)

  ZnCl₂ (2 mg, 0.01 mmol) and dip (12 mg, 0.04 mmol) were dissolved in N-methyl-2-pyrrolidone (NMP, 8 mL) and H₂O (2 mL). The reaction mixture was trans-ferred into a 25 mL Teflon-lined autoclave and sealed. The reaction took place at 120 ℃ for two days and afforded colorless crystals, which were collected by filtration, and washed with fresh NMP and acetone (Yield: 50% based on dip ligand).

  1.7   Single crystal X-ray diffraction analysis

  The single-crystal X-ray diffraction data were collected using a Bruker SMART APEX Ⅱ diffractom-eter with molybdenum source radiation (Mo Kα, λ=0.071 073 nm). The crystal structure was solved by the SHELXT and OLEX2 programs with intrinsic phasing and refined by the SHELXL program. All the H-atoms were generated geometrically with isotropic thermal factors. The residual electron density belonging to dis-ordered solvent molecules in complex 2 was treated with a solvent mask, and the type and amount of sol-vent molecules in the structure were estimated by con-sidering the residual electron density and TGA result. The crystal data and refinement parameters are listed in Table 1.

  Table 1

  

  Table 1.  Crystal structure data of CPs 1-5

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  Parameter	1	2	3	4	5
  Formula	C60H64Cd2N8O16	C64H56Cd2N8O8	C46H42Cl2N10NiO2	C44H44CdN10O10S2	C22H14Cl2N4Zn
  Formula weight	1 377.99	1 289.96	896.50	1 049.41	470.64
  Crystal system	Monoclinic	Monoclinic	Triclinic	Triclinic	Monoclinic
  Space group	P21/c	P21	P1	P1	P21/c
  a/nm	1.421 90(9)	0.794 90(3)	0.885 50(3)	0.877 41(7)	0.902 69(4)
  b/nm	2.533 52(16)	2.241 04(9)	1. 195 78(4)	1. 109 6(1)	1.645 63(7)
  c/nm	0.751 50(5)	1.828 50(6)	1. 197 35(4)	1.239 7(1)	1.349 68(7)
  α/(°)			111. 152(1)	82.682(3)
  β/(°)	94.481(2)	97.208(2)	100.401(1)	83.491(3)	101.777(2)
  γ/(°)			100. 175(1)	88.435(3)
  V/nm3	2.698 9(3)	3.231 6(2)	1.121 85(7)	1. 189 3(1)	1.962 7(1)
  Z	2	2	1	1	4
  F(000)	1 408	1 312	466	538	952
  μ/mm-1	0.872	0.731	0.601	0.614	1.540
  Dc/(g·cm-3)	1.696	1.474	1.327	1.465	1.593
  Rint	0.097 6	0.048 5	0.056 0	0.049 6	0.067 7
  GOF on F2	1.079	0.977	1.065	1.062	1.027
  R1 [I > 2σ(I)]	0.084 1	0.033 1	0.047 0	0.030 9	0.060 9
  wR2 [I > 2σ(I)]	0.191 7	0.071 0	0.138 0	0.084 9	0.173 2

  2.   Results and discussion

  2.1   Crystal structure

  CP 1 crystallizes in space group P2₁/c. The asym-metric unit of 1 contains one Cd²⁺ ion, one cda^2- ligand, one dip ligand, and four lattice water molecules. The Cd²⁺ ionis in a twisted octahedral coordination environ-ment including two N atoms from dip ligands and four O atoms from cda^2- ligands (Fig. 1a). There are two dip ligands and two cda^2- ligands around one Cd²⁺ ion. Therefore, the Cd²⁺ ions, acting as tetrahedral nodes, are linked with four Cd²⁺ ions into a diamondoid (dia) net (Fig. 1b) following the classification from RCSR (reticular chemistry structure resource)^[20]. The adaman-tane cage in the dia net is distorted with maximum intra-cage dimensions of 3.27 nm×1.76 nm×1.71 nm (Fig. 1c). The spacious nature of a single dia network allows four other identical networks to penetrate, result-ing in a five-fold interpenetrating dia array (Fig. 1d). The interpenetration vector of these five nets is the c-axis. The π … π interactions formed between pyrene groups of dip ligands stabilize the interpenetrating net-works (Cg…Cg distance: 0.376 nm, Fig.S1).

  Figure 1

  

  Figure 1.  (a) Coordination environment of the Cd²⁺ ion in CP 1 with an ellipsoid probability level of 50%;(b)dia network structure in 1; (c) 3D network of topology diain 1; (d) 5-fold interpenetration in 1

  Symmetry code: A: x-1, 1.5-y, z-0.5.

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  CP 2 crystallizes in space group P2₁. The asymmetric unit of 2 contains one Cd²⁺ ion, one cpa^2- ligand, one dip ligand, and four lattice water molecules. The Cd²⁺ ionis in a twisted octahedral coordination environ-ment with two N atoms from dip ligands and four O atoms from cpa^2- ligands (Fig. 2a). The cpa^2- ligands link the Cd²⁺ ions into an infinite 1D chain along the c-axis, and the dip ligands act as a bridge to connect the infinite chain into a 3D framework (Fig. 2b). The topology of the network in 2 is cds following the classifi-cation from RCSR, where the Cd²⁺ ions function as a 4-connector (Fig. 2c). The π … π interactions are observed between the pyrene groups of dip ligands (Cg…Cg distance: 0.362 nm, Fig.S2).

  Figure 2

  

  Figure 2.  (a) Coordination environment of the Cd²⁺ ion in CP 2 with an ellipsoid probability level of 50%; (b) 3D network structure in 2; (c) 3D network of topology cds in 2

  Symmetry code: A: 1-x, 0.5+y, 1-z.

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  CP 3 crystallizes in space group P1. The asymmet-ric unit of 3 contains one Ni²⁺ ion, two Cl^- anions, two dia ligands, and one uncoordinated DMF molecule. The Ni²⁺ ion is in an octahedral coordination environ-ment with four N atoms from dia ligands in the equato-rial plane and two Cl^- ions in the axial positions (Fig. 3a).

  Figure 3

  

  Figure 3.  (a) Coordination environment of the Ni²⁺ ion in CP 3 with an ellipsoid probability level of 50%; (b) 2D layer constructed by dia and Ni²⁺ in 3; (c) 1D tubes along the b-axis formed between adjacent layers in 3

  Symmetry code: A: 1-x, 1-y, 1-z.

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  The Ni²⁺ ionis linked by four dia ligands with four adjacent Ni²⁺ ions into a layer structure (Fig. 3b). Nano-tubes are formed between adjacent layers along the b-axis with across-section of 1.35 nm×0.96 nm consid-ering van der Waals radii (Fig. 3c). The uncoordinated DMF molecules reside in the tubes. The C—H … π interactions are observed between anthracene groups of dia ligands from adjacent layers (Fig. S3), and the H … Cg(anthracene) separation is 0.263 nm.

  CP 4 crystallizes in space group P1. The asymmet-ric unit of 4 contains one Cd²⁺ ion, two dia ligands, two coordinated water molecules, two NO₃^- anions, and two DMSO molecules. The Cd²⁺ ionis in an octahedral coor-dination environment with four N atoms from dia ligands in the equatorial plane and two water mole-cules in the axial positions (Fig. 4a). Two NO₃^- ions neu-tralize the positive charge on the [Cd(dia)₂(H₂O)₂]²⁺ unit.

  Figure 4

  

  Figure 4.  (a) Coordination environment of the Cd²⁺ ion in CP 4 with an ellipsoid probability level of 50%; (b) 2D layer constructed by dia and Cd²⁺ in 4, where DMSO molecules are shown in space-filling mode; (c) 1D tubes along the b-axis formed between adjacent layers in 4

  Symmetry code: A: 2-x, 1-y, 1-z.

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  The dia ligands connect Cd²⁺ ions into a 2D layer (Fig. 4b). The 1D channels are formed between adjacent layers along the b-axis with across-section of 0.87 nm×0.43 nm taking van der Waals radii into consideration (Fig. 4c). There are two NO₃^- ions and two DMSO mole-cules in the channels.

  CP 5 crystallizes in space group P2₁/c. The asym-metric unit of 5 contains one Zn²⁺ ion, one dip ligand, and two Cl^- anions. The Zn²⁺ ion is in a distorted tetra-hedral coordination environment including two N atoms from dip ligands and two Cl^- ions (Fig. 5a). The Zn²⁺ ion is linked by dip ligands into an infinite 1D chain (Fig. 5b). The C—H … π interactions are observed between pyrene groups of dip ligands from adjacent lay-ers (Fig. S5), and the H…Cg(pyrene) separations range from 0.286 to 0.296 nm.

  Figure 5

  

  Figure 5.  (a) Coordination environment of the Zn²⁺ ion in CP 5 with an ellipsoid probability level of 50%; (b) Infinite 1D chain in 5

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  2.2   PXRD and TGA characterization

  The PXRD patterns of as-synthesized samples of CPs 1-5 fitted well with the simulated patterns from single-crystal X-ray diffraction results, and indicated that pure phase samples were obtained (Fig. 6). TGA results showed well thermal stability for the five CPs, and their decomposition temperatures were in a range of 320-450 ℃ (Fig. S6). For example, CP 1 showed a weight loss of 6% below 110 ℃ corresponding to the loss of hydrogen-bonded H₂O solvent, and a weight loss after 450 ℃ corresponding to the loss of organic ligand and collapse of the polymeric structure (Fig.S6a).

  Figure 6

  

  Figure 6.  PXRD patterns for complexes 1-5

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  2.3   Fluorescent properties

  Fluorescent spectra for organic ligands dia and dip in solid state and in dilute solution, and for com-plexes 1-5 in solid state were collected at room temper-ature (Fig. 7). The dia ligand in dilute DMF solution showed two peaks and a shoulder at 397, 417, and 441 nm under excitation at 365 nm, and the dia solid sam-ple showed a broad peak at 507 nm, which should be attributed to the aggregation of dia molecules in the solid state. The emission peaks of solid samples 3 and 4 were similar to dia ligand in DMF solution and red-shifted by 27 and 30 nm, respectively (424, 439, and 470 nm for 3, 427, 450, and 478 nm for 4), and the emission peaks for 3 were broadened. This observation of the emission peaks for 3 and 4 indicated that there is not much interaction involved in the organic dia ligands, which is consistent with the crystal structure analysis, while in 3 and 4, the dia ligands are well separated by metal centers and cda^2- ligands.

  Figure 7

  

  Figure 7.  Fluorescent emissions for CPs 1-5 and ligands dip and dia

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  The dip ligand in dilute DMF solution showed two peaks and a shoulder at 381, 399, and 424 nm under excitation at 365 nm, and the dip solid sample showed much broader peaks around 490 nm, which should be attributed to the aggregation of dip molecules in the sol-id state. The emission peaks of solid sample 5 were similar to dip ligand in DMF solution and red-shifted by 23 nm, respectively (404, 423, and 449 nm). Com-plexes 1 and 2 showed broad emission peaks around 473 and 504 nm. The difference in fluorescent emis-sions of solid samples 1, 2, and 5 should originate from different intermolecular interactions and packing modes of dip in these three CPs, which is consistent with the results of crystal structure analysis. In 1 and 2, there are strong π-π interactions between the anthra-cene groups (Fig. S1), while in 5, the dip ligands are well separated by metal centers.

  3.   Conclusions

  We reported five coordination polymers (CPs) based on highly fluorescent anthracene and pyrene-derivative ligands. In [Cd(dip) (cda)]·4H₂O}_n (1), the Cd²⁺ ions, acting as tetrahedral nodes, are linked by dip and cda^2- ligands into a five-fold interpenetrating net-work array of topology of dia. In {[Cd(dip)(cpa)]·4H₂O}_n (2), the Cd²⁺ ions, acting as a 4-connector, are linked by cpa^2- and dip ligands into a 3D framework of cdsto-pology. In {[Ni(dia)₂Cl₂]·DMF}_n (3), the Ni²⁺ ion is linked by four dia ligands into a layer structure, and 1D channels of across-section of 1.35 nm×0.96 nm are formed. In {[Cd(dia)2(H₂O)2] (NO₃)2·2DMSO}_n (4), the dia ligands connect Cd²⁺ ions into a 2D layer, and 1D channels are formed between adjacent layers with a cross-section of 0.87 nm×0.43 nm. In [Zn(dip)Cl²]_n (5), the Zn²⁺ ion is linked by dip ligands into an infinite 1D chain. The five CPs showed good thermal stability and strong fluorescent emission, in which, 1 showed a ther-mal decomposition temperature as high as 450 ℃ and also very strong blue fluorescent emission at 473 nm.

  Supporting information is available at http://www.wjhxxb.cn

  
  
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• 

  Scheme 1  Organic ligands used in this work

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  Figure 1  (a) Coordination environment of the Cd²⁺ ion in CP 1 with an ellipsoid probability level of 50%;(b)dia network structure in 1; (c) 3D network of topology diain 1; (d) 5-fold interpenetration in 1

  Symmetry code: A: x-1, 1.5-y, z-0.5.

  下载: 全尺寸图片 幻灯片
  

  Figure 2  (a) Coordination environment of the Cd²⁺ ion in CP 2 with an ellipsoid probability level of 50%; (b) 3D network structure in 2; (c) 3D network of topology cds in 2

  Symmetry code: A: 1-x, 0.5+y, 1-z.

  下载: 全尺寸图片 幻灯片
  

  Figure 3  (a) Coordination environment of the Ni²⁺ ion in CP 3 with an ellipsoid probability level of 50%; (b) 2D layer constructed by dia and Ni²⁺ in 3; (c) 1D tubes along the b-axis formed between adjacent layers in 3

  Symmetry code: A: 1-x, 1-y, 1-z.

  下载: 全尺寸图片 幻灯片
  

  Figure 4  (a) Coordination environment of the Cd²⁺ ion in CP 4 with an ellipsoid probability level of 50%; (b) 2D layer constructed by dia and Cd²⁺ in 4, where DMSO molecules are shown in space-filling mode; (c) 1D tubes along the b-axis formed between adjacent layers in 4

  Symmetry code: A: 2-x, 1-y, 1-z.

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  Figure 5  (a) Coordination environment of the Zn²⁺ ion in CP 5 with an ellipsoid probability level of 50%; (b) Infinite 1D chain in 5

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  Figure 6  PXRD patterns for complexes 1-5

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  Figure 7  Fluorescent emissions for CPs 1-5 and ligands dip and dia

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  Table 1.  Crystal structure data of CPs 1-5

  Parameter	1	2	3	4	5
  Formula	C60H64Cd2N8O16	C64H56Cd2N8O8	C46H42Cl2N10NiO2	C44H44CdN10O10S2	C22H14Cl2N4Zn
  Formula weight	1 377.99	1 289.96	896.50	1 049.41	470.64
  Crystal system	Monoclinic	Monoclinic	Triclinic	Triclinic	Monoclinic
  Space group	P21/c	P21	P1	P1	P21/c
  a/nm	1.421 90(9)	0.794 90(3)	0.885 50(3)	0.877 41(7)	0.902 69(4)
  b/nm	2.533 52(16)	2.241 04(9)	1. 195 78(4)	1. 109 6(1)	1.645 63(7)
  c/nm	0.751 50(5)	1.828 50(6)	1. 197 35(4)	1.239 7(1)	1.349 68(7)
  α/(°)			111. 152(1)	82.682(3)
  β/(°)	94.481(2)	97.208(2)	100.401(1)	83.491(3)	101.777(2)
  γ/(°)			100. 175(1)	88.435(3)
  V/nm3	2.698 9(3)	3.231 6(2)	1.121 85(7)	1. 189 3(1)	1.962 7(1)
  Z	2	2	1	1	4
  F(000)	1 408	1 312	466	538	952
  μ/mm-1	0.872	0.731	0.601	0.614	1.540
  Dc/(g·cm-3)	1.696	1.474	1.327	1.465	1.593
  Rint	0.097 6	0.048 5	0.056 0	0.049 6	0.067 7
  GOF on F2	1.079	0.977	1.065	1.062	1.027
  R1 [I > 2σ(I)]	0.084 1	0.033 1	0.047 0	0.030 9	0.060 9
  wR2 [I > 2σ(I)]	0.191 7	0.071 0	0.138 0	0.084 9	0.173 2

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