[N-ethyl-4,4'-bipyridinium][ZnX4] (X=Cl or Br) with N-ethyl-4,4'-bipyridinium Generated In Situ: Syntheses, Structures, Fluorescence and TDDFT Calculations

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a. Institute of Applied Chemistry, School of Chemistry and Chemical Engineering, Jiangxi Province Key Laboratory of Coordination Chemistry, Jinggangshan University, Ji'an, Jiangxi 343009, China;
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b. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China

Corresponding author: CHEN Wen-Tong,
Received Date: 23 December 2013
Available Online: 16 January 2014
Fund Project: This project was supported by the NNSF of China (21361013) (21361013) the NSF of Jiangxi Province (20132BAB203010, 20114BAB203028) (20132BAB203010, 20114BAB203028) the open foundation (No. 20130014) of the State Key Laboratory of Structural Chemistry, and the science and technology project of Jiangxi Provincial Department of Education (GJJ13555) (No. 20130014)

Two new zinc bipyridinium compounds, [N-ethyl-4,4'-bipyridinium][ZnX₄] (X=Cl (1) or Br (2)) with N-ethyl-4,4'-bipyridinium generated in situ, have been synthesized through solvothermal reactions and structurally characterized by single-crystal X-ray diffraction analyses. Both compounds are isostructural and crystallize in the P2₁/c space group of monoclinic system. Compound 1: a=8.4397(5), b=21.988(1), c=8.8777(5) Å, β=106.490(1)°, V=1579.7(2) Å³, C₁₂H₁₅Cl₄N₂Zn, M_r=394.43, Z=4, D_c=1.658 g/cm³, S=1.068, μ(MoKα)=2.218 mm^-1, F(000)=796, R=0.0295 and wR=0.0766. Compound 2: a=8.4154(6), b=22.844(2), c=9.0308(7) Å, β=106.026(1)°, V=1668.6(2) Å³, C₁₂H₁₅Br₄N₂Zn, M_r=572.27, Z=4, D_c=2.278 g/cm³, S=1.033, μ(MoKα)=11.038 mm^-1, F(000)=1084, R=0.0427 and wR=0.1175. Both of them are characteristic of an isolated structure with the zinc atoms locating at a tetrahedral environment. In both compounds, the N-ethyl-4,4'-bipyridinium²⁺ cations and ZnX₄^2- anions interconnect together via hydrogen bonding interactions to construct a three-dimensional (3-D) supramolecular framework. Fluorescent studies reveal that both compounds exhibit a strong emission in the green region. In combination with the theoretical calculations, we can draw a conclusion that the emissions should result from ligand-toligand charge-transfer (LLCT) transition.

[N-ethyl-4,4'-bipyridinium][ZnX4] (X=Cl or Br) with N-ethyl-4,4'-bipyridinium Generated In Situ: Syntheses, Structures, Fluorescence and TDDFT Calculations

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