English

• 1. INTRODUCTION

  The programming of multinuclear metal clusters remained a charming research area in the matter of coordination and material chemistry^[1]. This was mainly attributed to the engaging structure diversity and the proverbially application as functional materials in areas of catalysis, conductivity, porosity, luminescence, magnetism, spin-transition and non-linear optics^[2-9]. Although the assembly of multinuclear metal clusters had made great progress in recent years, the enthusiasm for the construction of multinuclear metal clusters was not decreased. There were many restricted factors such as metal ions, nature of organic ligands, reaction temperature, pH value of the solution and so on^[10-13]. In addition, hydrogen bonds and π-π stacking interactions all made great contributions to the construction of fascinating structures for multinuclear metal clusters by connecting low-dimensional motifs into higher-dimensional supramolecular frameworks^[14]. Therefore, the self-assembly of multinuclear metal clusters was a long-term mission and still had many sealed challenges for us. Furthermore, how to design and select a multi-functional ligand was the core factor for the synthesis of various frameworks for multinuclear metal clusters.

  In recent years, rare examples of copper(Ⅱ) complex with 2-(1H-pyrazol-3-yl)pyridine (HL) had been reported up to now^[15-18], while multinuclear copper(Ⅱ) clusters with this ligand were not found in the record literature. HL had three underlying bonding sites consisting of three N atoms from pyrazole and pyridine rings when it was fully deprotonated. Consequently, the coordination modes of HL were diffusely studied as a multifunctional ligand. Meanwhile, copper (Ⅱ) complexes emitted strong attraction owing to the elastic coordination sphere of Cu (Ⅱ) ion and the universal applications of its conjugation in miscellaneous fields such as magnetism, biology and medicine^[19-21].

  Inspired by the above explored points to continue our recent research, 2-(1H-pyrazol-3-yl)pyridine (HL) was selected as a ligand to react with two metal salts, finally obtaining a novel tetranuclear copper cluster. Furthermore, the thermostability and solid state fluorescence properties were investigated.

  2. EXPERIMENTAL

  2.1 Materials and physical measurements

  All the chemicals and solvents were commercially available and used as received without further purification. Elemental analyses for carbon, hydrogen, and nitrogen atoms were carried out on a Perkin-Elmer 240C elemental analyzer. IR spectrum was performed on a Nicolet 5700 spectrophotometer in the range of 4000~400 cm^-1 using KBr pellets. Thermo-gravimetric analysis (TGA) was measured on a Synchronous thermal analyzer under N₂ atmosphere at a heating rate of 10 ℃/min. Luminescence spectrum was investigated with a Horiba Fluoromax-4 fluorescence spectrophotometer.

  2.2 Synthesis of [Cu₄(μ-L)₆Cl₂]

  A mixture of HL (0.4 mmol, 0.0581 g), TbCl₃·6H₂O (0.2 mmol, 0.0747 g), CuI (0.1 mmol, 0.0191 g) and DMF (15 mL) was stirred in a 50 mL beaker for 15 min. And then triethylamine (28 μL) was dropwise added into the mixture. Finally, it was poured into a Teflon-lined stainless-steel autoclave (25 mL) and then heated at 160 ℃ for 48 h. The green block crystals were gathered after the final mixture was cooled to room temperature at rate of 10 ℃/h. Yield: 43% (based on HL). Anal. Calcd. (%) for C₂₄H₁₈ClCu₂N₉ (M_r = 595.01): C, 48.47; H, 3.03; N, 22.21. Found (%): C, 49.15; H, 3.36; N, 23.14. IR (KBr, cm^-1): 3444 (s), 1663 (m), 1616 (s), 1598 (s), 1458 (m), 1430 (m), 1362 (m), 1159 (w), 1140 (m), 1088 (w), 758 (m), 716 (w), 702 (w), 641(w).

  2.3 X-ray crystal structural determination

  A green single crystal of complex 1 with about dimensions of 0.38mm × 0.32mm × 0.25mm was selected and glued to a glass fiber. The diffraction data were collected on Rigaku SCX with graphite-monochromatic Mo-Kα radiation (λ = 0.71073 Å) by using the ω-θ scan method in the range of 3.41≤θ≤26.37º at room temperature. A total of 9712 reflec-tions were collected, including 3017 independent ones (R_int = 0.0404). The structure was solved by direct methods and refined by full-matrix least-squares on F² using SHELXL-2014^[22]. The empirical absorption correction was applied with the program Bruker FRAMBO. All non-hydrogen atoms were refined anisotropically. All hydrogen atoms were positioned geometrically and refined as a riding model. Selected bond distances and bond angles of complex 1 are listed in Table 1. Hydrogen bond lengths and bond angles are given in Table 2.

  Table 1

  

  Table 1.  Selected Bond Lengths (Å) and Bond Angles (°) for Complex 1

  DownLoad: CSV

  Bond	Dist.		Bond	Dist.
  Cu(1)–N(1)	2.081(4)		Cu(1)–N(2)	1.974(4)
  Cu(1)–N(7)	2.317(4)		Cu(1)–N(8)	1.968(4)
  Cu(2)–N(3)	1.961(5)		Cu(2)–N(4)	2.052(5)
  Cu(2)–N(5)	2.038(4)		Cu(1)–N(6)	1.988(4)
  Cu(2)–N(9A)	2.123(4)		Cu(2)–C(l1)	2.3509(16)
  Angle	(°)		Angle	(°)
  N(1)–Cu(1)–N(7)	84.46(16)		N(2)–Cu(1)–N(6)	97.46(17)
  N(2)–Cu(1)–N(1)	80.30(17)		N(2)–Cu(1)–N(7)	104.86(16)
  N(3)–Cu(2)–N(4)	174.02(19)		N(3)–Cu(2)–N(9A)	95.50(19)
  N(3)–Cu(2)–N(5)	95.90(18)		N(3)–Cu(2)–C(l1)	92.05(13)
  N(4)–Cu(2)–C(l1)	89.39(14)		N(4)–Cu(2)–N(9A)	89.62(18)
  N(5)–Cu(2)–N(4)	79.21(18)		N(5)–Cu(2)–N(9A)	112.93(16)
  N(5)–Cu(2)–C(l1)	138.14(12)		N(8)–Cu(1)–N(7)	75.82(16)
  N(8)–Cu(1)–N(2)	170.87(18)		N(8)–Cu(1)–N(6)	91.39(17)
  N(8)–Cu(1)–N(1)	90.74(17)		N(9A)–Cu(2)–C(l1)	107.06(13)
  Symmetry code: A: –x, –y, –z

  Table 2

  

  Table 2.  Hydrogen Bond Lengths (Å) and Bond Angles (°) for Complex 1

  DownLoad: CSV

  D–H...A	d(D–H)	d(H...A)	d(D...A)	∠(DHA)
  C(24)–H(24)...Cl(1)b	0.93	2.85	3.609(6)	140
  C(19)–H(19)...Cl(1)a	0.93	2.87	3.649(9)	142
  Symmetry codes: a: –x, –y, –z; b: x, y, z+1

  3. RESULTS AND DISCUSSION

  3.1 Crystal structure of complex [Cu₄(μ-L)₆Cl₂]

  X-ray single-crystal diffraction confirmed complex 1 crystallized in triclinic system with P$ \overline 1 $ space group. The asymmetric unit included three deprotonated HLs, one Cl^- ion and two crystallographically isolated Cu center. Cu(1) and Cu (2) had slight distorted square planar and square pyramidal geometries, respectively. As shown in Fig. 1, complex 1 had a centrosymmetric parallel grid-like structure. In this tetranuclear unit, six HL were all deprotonated and acted as a terdentate chelating-bridging linkage, while two Cl^- ions adopted a terminal coordination mode to meet the bond valence sum for four Cu²⁺ ions. Interestingly, there were two approximately planar binuclear units [Cu₂(μ-L)₃Cl] in 1 and each unit was a six-membered ring consisting of Cu(1)–N(2)–N(3)–Cu(2)–N(5)–N(6). The distance for two Cu(Ⅱ) centers was 3.9929(11) Å, which was longer than the previously reported Cu···Cu distances^[23] but was little shorter than the other records^[24]. And the two additional deprotonated HLs linked these two parallel binuclear units into the tetranuclear core structure with the distances for the adjacent nonbonding Cu(1)···Cu(2A) and Cu(1)···Cu(1A) to be 3.7310(16) and 4.3507(14) Å, respectively (symmetry code: A: –x, –y, –z). The bond lengths of Cu–N fell into the range of 1.961(5)~2.317(4) Å, which were close to the reported values^[25]. The Cu–Cl bond length was 2.3509(16) Å, similar to the reported ones^[26]. Furthermore, adjacent [Cu₄(μ-L)₆Cl₂] cores were connected into a one-dimensional chain (Fig. 2) via plentiful weak non-classical C(24)–H(24)···Cl^b hydrogen bonds, which had also been observed^{[27, 28]}. The contiguous chains were assembled into a 2D network (Fig. 3) by abundant C(19)–H(19)···Cl^a hydrogen bonds (symmetry codes: a: –x, –y, –z; b: x, y, z+1). In complex 1, there were many π-π stacking interactions, but we here only discussed one for understanding them more clearly. As displayed in Fig. 4, one pyridine ring (N(4), C(9)~C(13)) in the tetranuclear unit was nearly parallel to another one in its neighboring cores with a ring-to-ring distance of 3.859(3) Å, indicating a strong π-π stacking interaction between them. All of these strong π-π stacking interactions were responsible for the assembly of a 3D supramolecular network.

  Figure 1

  

  Figure 1.  ORTEP view of 1 showing atoms at 30% probability ellipsoids. Hydrogen atoms were omitted for clarity (Symmetry code: a: –x, –y, –z)

  DownLoad: Full-Size Img PowerPoint

  Figure 2

  

  Figure 2.  A one-dimensional chain structure for complex 1 by plentiful non-classical C(24)–H(24)^…Cl^b hydrogen bonds (Symmetry code: b: x, y, z+1)

  DownLoad: Full-Size Img PowerPoint

  Figure 3

  

  Figure 3.  2D network of complex 1 assembled by C(19)-H(19)⋅⋅⋅Cl^a (symmetry code: a: –x, –y, –z)

  DownLoad: Full-Size Img PowerPoint

  Figure 4

  

  Figure 4.  3D supramolecular network constructed by π-π interactions

  DownLoad: Full-Size Img PowerPoint

  Figure 5

  

  Figure 5.  TGA curve of complex 1

  DownLoad: Full-Size Img PowerPoint

  3.2 Thermogravimetric analysis

  The thermal behavior of complex 1 was investigated by thermogravimetric analysis under a nitrogen atmosphere at a heating rate of 10 ℃/min from room temperature to 800 ℃. The TGA curve of complex 1 indicated no obvious weight loss from room temperature to 300 ℃. There was a platform below 300 ℃. After that, the framework started to collapse above 300 ℃, forecasted that 1 revealed fine thermostability.

  3.3 Fluorescence property

  As displayed in Fig. 6, the fluorescence of complex 1 and the homologous free ligand HL was investigated in the solid state at room temperature. HL showed that the typical emission peak was 471 nm under 310 nm excitation, while a blue luminescent emission band for complex 1 was exhibited with the maximum at 430 nm upon 350 nm. It should be pointed out that complex 1 showed blue-shift by 41 nm and displayed stronger emission as compared to the HL ligand, which might be attributed to the large scope of conjugated system because the HL ligand was a π-conjugated organic molecule and the formation of cluster structure improved the intra-ligand π-π* transitions^[29]. Furthermore, this pheno-menon might be briefly assigned to ligand-to-metal charge transfer (LMCT)^[30].

  Figure 6

  

  Figure 6.  Solid-state fluorescent emission spectra of free HL and complex 1

  DownLoad: Full-Size Img PowerPoint

  4. CONCLUSION

  In summary, a novel tetranuclear copper cluster [Cu₄(μ-L)₆Cl₂] was obtained via the reaction of 2-(1H-pyra-zol-3-yl) pyridine and metal salts under hydrothermal conditions and structurally characterized by IR, single-rystal X-ray diffraction and so on. In complex 1, the tetranuclear core structure was connected into a 2D network via plentiful weak non-classical C–H^…Cl hydrogen bonds and further assembled into a 3D supramolecular network by week π-π stacking interaction between pyridine rings. Furthermore, complex 1 had excellent thermostability and stronger fluorescent emission as compared to the HL ligand.

  
  
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• 

  Figure 1  ORTEP view of 1 showing atoms at 30% probability ellipsoids. Hydrogen atoms were omitted for clarity (Symmetry code: a: –x, –y, –z)

  下载: 全尺寸图片 幻灯片
  

  Figure 2  A one-dimensional chain structure for complex 1 by plentiful non-classical C(24)–H(24)^…Cl^b hydrogen bonds (Symmetry code: b: x, y, z+1)

  下载: 全尺寸图片 幻灯片
  

  Figure 3  2D network of complex 1 assembled by C(19)-H(19)⋅⋅⋅Cl^a (symmetry code: a: –x, –y, –z)

  下载: 全尺寸图片 幻灯片
  

  Figure 4  3D supramolecular network constructed by π-π interactions

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  Figure 5  TGA curve of complex 1

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  Figure 6  Solid-state fluorescent emission spectra of free HL and complex 1

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  Table 1.  Selected Bond Lengths (Å) and Bond Angles (°) for Complex 1

  Bond	Dist.		Bond	Dist.
  Cu(1)–N(1)	2.081(4)		Cu(1)–N(2)	1.974(4)
  Cu(1)–N(7)	2.317(4)		Cu(1)–N(8)	1.968(4)
  Cu(2)–N(3)	1.961(5)		Cu(2)–N(4)	2.052(5)
  Cu(2)–N(5)	2.038(4)		Cu(1)–N(6)	1.988(4)
  Cu(2)–N(9A)	2.123(4)		Cu(2)–C(l1)	2.3509(16)
  Angle	(°)		Angle	(°)
  N(1)–Cu(1)–N(7)	84.46(16)		N(2)–Cu(1)–N(6)	97.46(17)
  N(2)–Cu(1)–N(1)	80.30(17)		N(2)–Cu(1)–N(7)	104.86(16)
  N(3)–Cu(2)–N(4)	174.02(19)		N(3)–Cu(2)–N(9A)	95.50(19)
  N(3)–Cu(2)–N(5)	95.90(18)		N(3)–Cu(2)–C(l1)	92.05(13)
  N(4)–Cu(2)–C(l1)	89.39(14)		N(4)–Cu(2)–N(9A)	89.62(18)
  N(5)–Cu(2)–N(4)	79.21(18)		N(5)–Cu(2)–N(9A)	112.93(16)
  N(5)–Cu(2)–C(l1)	138.14(12)		N(8)–Cu(1)–N(7)	75.82(16)
  N(8)–Cu(1)–N(2)	170.87(18)		N(8)–Cu(1)–N(6)	91.39(17)
  N(8)–Cu(1)–N(1)	90.74(17)		N(9A)–Cu(2)–C(l1)	107.06(13)
  Symmetry code: A: –x, –y, –z

  下载: 导出CSV

  Table 2.  Hydrogen Bond Lengths (Å) and Bond Angles (°) for Complex 1

  D–H...A	d(D–H)	d(H...A)	d(D...A)	∠(DHA)
  C(24)–H(24)...Cl(1)b	0.93	2.85	3.609(6)	140
  C(19)–H(19)...Cl(1)a	0.93	2.87	3.649(9)	142
  Symmetry codes: a: –x, –y, –z; b: x, y, z+1

  下载: 导出CSV
•