Synthesis and structural characterization of luminescent gold(I) derivatives with an unsymmetric diphosphine
Synthesis and structural characterization of luminescent gold(I) derivatives with an unsymmetric diphosphine
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DOI：
10.1039/b309116c
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发表时间：
2003-01-01
影响因子：
4
通讯作者：
Villaverde, N
中科院分区：
文献类型：
--
作者：
Bardají, M;Jones, PG;Villaverde, N
我们合成了一系列不对称双膦单桥金（Ⅰ）衍生物[（AuX）（2）（μ-（PPr_2CH_2PPh_2）-Pr_1）]（X = Cl，Br，I，C_6F_5，S_2CN（CH_2Ph）（2））和单核金（Ⅲ）配合物[Au（C_6F_5）（3）（（PPr_2CH_2PPh_2）-Pr_1）]。X射线衍射研究表明，对于X = Cl、Br和C6 F5，分子内金（I）-金（I）相互作用分别为3.4179（2）、3.1660（2）和3.0926（3）埃。五氟苯基衍生物在室温下以固态发射445 nm;该化合物和卤代衍生物在低温下发射440 - 486 nm范围内的光。我们还合成了双桥双环[Au_2X_2（mu-（PPr_2CH_2 PPh_2）-Pr_i）（2）]（X = Cl，Br，I）和[Au-2（mu-（PPr_2CH_2 PPh_2）-Pr_i）（2）] A（2）（A = CF_3SO_3，ClO_4）。碘衍生物的晶体结构显示T形几何形状的三配位金中心，金-金距离为2.9931（6）埃，金-碘距离为3.0999（6）埃，而三氟甲磺酸酯衍生物显示二配位金中心，金-金距离为2.9838（5）埃。所有衍生物在可见光范围内都有很强的光致发光，在298 K和77 K的最大发射波长分别在480 ~ 513 nm和459 ~ 508 nm之间。发射能量和金-金距离没有直接关系。
We have synthesised a series of mono-bridged digold(I) derivatives with an unsymmetric diphosphine, namely, [(AuX)(2)(mu-(PPr2CH2PPh2)-Pr-i)] (X = Cl, Br, I, C6F5, S2CN(CH2Ph)(2)) and the mononuclear gold(III) complex [Au(C6F5)(3)((PPr2CH2PPh2)-Pr-i)]. X-ray diffraction studies show intramolecular gold(I) - gold(I) interactions of 3.4179(2), 3.1660(2) and 3.0926(3) Angstrom, respectively, for X = Cl, Br and C6F5. The pentafluorophenyl derivative emits at 445 nm at room temperature in the solid state; this compound and the halo-derivatives are emissive at low temperature in the range 440 - 486 nm. We have also prepared doubly-bridged diauracycles, namely, [Au2X2(mu- (PPr2CH2PPh2)-Pr-i)(2)] (X = Cl, Br, I) and [Au-2(mu- (PPr2CH2PPh2)-Pr-i)(2)] A(2) (A = CF3SO3, ClO4). The crystal structure of the iodo derivative displays three-coordinated gold centres in a T-shaped geometry, with a gold - gold distance of 2.9931(6) Angstrom and a gold - iodo distance of 3.0999(6) Angstrom, whilst the triflate derivative displays di-coordinated gold centres and a gold - gold distance of 2.9838(5) Angstrom. All the derivatives are intensely photoluminescent in the visible range, with the emission maxima between 480 and 513 nm at 298 K and 459 - 508 nm at 77 K. The emission energies and the gold - gold distances are not directly related.