Synthesis,Structure and Luminescent Properties of Polymeric Copper(Ⅰ) Halide Complexes Bearing Phosphine and N-donor Bridging Ligands

Three polymeric copper（Ⅰ） halide complexes beating phosphine and N-donor bridging ligands, [（PPh3）2Cu2（μ-Br）2（μ-4,4＇-bipy）]∞ 1 （bipy = bipyridine）, [（PPh3）2Cu2（μ-Br）2（μ- bpe）]∞ 2 （bpe = trans-1,2-bis（4-pyridyl）ethene） and [（PPh3）2Cu2（μ-Cl）2（μ-bpe）]∞ 3, were synthesized by the multilayer diffusion method, and the structures were refined by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic, space group P1^- with a = 9.122（3）, b = 9.322（3）, c = 13.201（4） A, α = 106.440（4）, β= 105.965（5）, γ= 94.167（5）°, V = 1021.3（6） A^3, Mr= 967.62, Z = 1, De= 1.573 g/cm^3, F（000） = 486, μ = 3.111 mm^-1, the final R = 0.0383 and ωR = 0.0960 for 2792 observed reflections （I 〉 2σ（I））. Complex 2 crystallizes in triclinic, space group P1^- with a = 9.420（3）, b = 10.209（4）, c = 12.407（4） A, α = 104.136（6）, β = 108.132（5）, γ= 95.338（6）°, V = 1081.0（7） A^3, Mr= 496.83, Z = 2, Dc= 1.526 g/cm^3, F（000） = 500, μ = 2.941 mm^-1, the final R = 0.0445 and ωR = 0.1117 for 3251 observed reflections （I 〉 2σ（I））. Complex 3 crystallizes in triclinic, space group P1^- with a = 8.32（1）, b = 11.53（2）, c = 13.94（3） A, α = 109.57（3）, β= 93.85（3）, γ= 97.28（3）°, V= 1242（4） A^3, Mr= 1074.59, Z = 1, Dc = 1.436 g/cm^3, F（000） = 548, μ = 1.279 mm^-1, the final R = 0.0786 and ωR = 0.1586 for 2266 observed reflections （I 〉 2σ（I））. The complexes exhibit intensive solid-state photoluminescence tentatively assigned to an admixture of triplet intraligand （IL） and metal-to-ligand charge-transfer （MLCT） excited state.

二个新颖的一维聚合物{(PyH)_3[Cu_3Br_6]}_∞和{(γ-MePyH)_2[Cu_2Br_4]}_∞的合成和晶体结构(英文)

Reactions of CuBr with equimolar PyHBr or γ MePyHBr afforded two novel one dimensional bromocuprate? polymers {(PyH)3}∞ (1) and {(γ MePyH)2}∞ (2), respectively. Both 1 and 2 were characterized by IR, elemental analysis, and X ray crystallography. Crystal data for 1: monoclinic, space group P21/n, a=0.93262(12)nm, b=1.3497(2)nm, c=1.9149(2)nm, β =93.465(7)° , V=2.4060(5)nm3, Z=4. Crystal data for 2: orthorhombic, space group Pbcm, a=0.8659(4)nm, b=1.5669(6)nm, c=1.2849(5)nm, V=1.7432(2)nm3, Z=4. The structure of 1 has a unique helical chain composed of units and μ bromide anions while that of 2 shows a linear chain consisted of [Cu2(μ Br)2] units bridged by pairs of μ Br atoms. CCDC: 1, 208412; 2, 208413.

二维异核铜-钠配位聚合物的合成和晶体结构(英文)

合成了铜-钠混合金属配位聚合物[(CuL)2(CH3OO)Na(H2O)4]2(简写为1)并进行了元素分析和单晶X射线衍射分析,L为{2-(2′-酚基)-Δ2-噻唑-4-羧酸}。晶体结构分析表明配合物形成Cu4Na2的六核混合金属大环。相邻的Cu4Na2环之间通过进一步的配位作用连结成包含更大的Cu8Na4大环的二维网状结构。该晶体属于三斜晶系P墿空间群,晶胞参数分别为:a=1.0777(4)nm,b=1.5221(6)nm,c=1.6994(6)nm,α=84.58(1)°,β=76.31(1)°,γ=89.97(1)°,V=2.696(2)nm3,Z=2,Mr=1447.26,dc=1.783 g.cm-3,T=293(2)K,μ=1.816 mm-1,F(000)=1472,R1=0.0794,wR2=0.1819[I>2σ(I)].