Citation: GONG Ya-Qiong, GAO Jin-Wei, MI Tao-Qing. Self-assembly of a Mixed-valence Cu(I)/Cu(II) Coordination Polymer Derived from a Conformationally Flexible Tripodal Phosphoric Trimide Ligand[J]. Chinese Journal of Structural Chemistry, ;2016, 35(5): 747-752. doi: 10.14102/j.cnki.0254-5861.2011-0916 shu

Self-assembly of a Mixed-valence Cu(I)/Cu(II) Coordination Polymer Derived from a Conformationally Flexible Tripodal Phosphoric Trimide Ligand

GONG Ya-Qiong ^a,b,, ,
GAO Jin-Wei ^a,b ,
MI Tao-Qing ^a,b

a.
a. Industry and Ecology Institute, North University of China, Taiyuan 030051, China;
b.
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: GONG Ya-Qiong,
Received Date: 28 June 2015
Available Online: 2 November 2015
Fund Project: This project was supported by the NNSFC (No. 21301170) (No. 21301170)

Reaction of a tripodal ligand, N,N',N"-tris(3-pyridinyl) phosphoric trimide (TPPA) and CuBr₂·2H₂O result in the assembly of a new polymeric copper coordination polymer, which was characterized by single-crystal diffraction, infrared spectroscopy and elemental analysis. The polymer crystallizes in the triclinic system, space group P1 with a = 9.0964(5), b = 10.2592, c = 10.5822(8) Å, V = 933.01(9) Å³, Z = 2, C₃₀H₂₄Br₄Cu₃N₁₂O₂P₂, M_r = 985.02, D_c = 1.753 g/cm³, F(000) = 4072 and μ(MoKα) = 0.746 mm^-1. The final R and wR are 0.0588 and 0.1329 for 4260 observed reflections with I> 2s(I). Cu(I) is tetrahedrally coordinated and Cu(II) center adopts square planar coordination geometry. Because of the flexibility of the TPPA ligands, the pyridyl rings rotate though a certain angle and three pyridyl rings on the same TPPA rotate by about 45° with respect to the central P=O groups. TPPA ligand acts as a tridentate ligand and is coordinated with three metal centers with its pyridyl donors to form a 2D-sheet like structure, and it is further connected by N–H…O and N–H…Br, resulting in a 3D network packing. Oxidation states of the metal center have been determined by bond valence sum calculation.
- copper,
- phosphoric trimide,
- mixed-valence complex,
- crystal structure
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