Fernández Eduardo J, López-de-Luzuriaga José M, Monge Miguel, Olmos M Elena, Puelles Raquel C, Laguna Antonio, Mohamed Ahmed A, Fackler John P
Departamento de Química, Universidad de La Rioja, Grupo de Síntesis Química de La Rioja, UA-CSIC, Madre de Dios 51, E-26004 Logroño, Spain.
Inorg Chem. 2008 Sep 15;47(18):8069-76. doi: 10.1021/ic800452w. Epub 2008 Aug 9.
The vapochromic behaviors of {Ag2L2[Au(C6F5)2]2}n (L = Et2O (1), Me2CO (2), THF (3), CH3CN (4)) were studied. {Ag2L2[Au(C6F5)2]2}n (L = Et2O (1)) was synthesized by the reaction of [Bu4N][Au(C6F5)2] with AgOClO3 in 1:1 molar ratio in CH2Cl2/Et2O (1:2). 1 was used as starting material with THF to form {Ag2L2[Au(C6F5)2]2}n (L = THF (3)). 3 crystallizes in the monoclinic space group C2/c and consists of tetranuclear units linked together via aurophilic contacts resulting in the formation of a 1D polymer that runs parallel to the crystallographic z axis. The gold(I) atoms are linearly coordinated to two pentafluorophenyl groups and display additional Au...Ag close contacts within the tetranuclear units with distances of 2.7582(3) and 2.7709(3) A. Each silver(I) center is bonded to the two oxygen atoms of the THF molecules with a Ag-O bond distance of 2.307(3) A. TGA analysis showed that 1 loses two molecules of the coordinated solvent per molecular unit (1st one: 75-100 degrees, second one: 150-175 degrees C), whereas 2, 3, and 4 lose both volatile organic compounds (VOCs) and fluorinated ligands in a less well defined manner. Each complex loses both the fluorinated ligands and the VOCs by a temperature of about 325 degrees C to give a 1:1 gold/silver product. X-ray powder diffraction studies confirm that the reaction of vapors of VOCs with 1 in the solid state produce complete substitution of the ether molecules by the new VOC. The VOCs are replaced in the order CH3CN > Me2CO > THF > Et2O, with the ether being the easiest to replace. {Ag2(Et2O)2[Au(C6F5)2]2}n and {Ag2(THF)2[Au(C6F5)2]2} n both luminesce at room temperature and at 77 K in the solid state. Emission maxima are independent of the excitation wavelength used below about 500 nm. Emission maxima are obtained at 585 nm (ether) and 544 nm (THF) at room temperature and at 605 nm (ether) and 567 nm (THF) at 77 K.
研究了{Ag2L2[Au(C6F5)2]2}n（L = 二乙醚 (1)、丙酮 (2)、四氢呋喃 (3)、乙腈 (4)）的气致变色行为。{Ag2L2[Au(C6F5)2]2}n（L = 二乙醚 (1)）通过[Bu4N][Au(C6F5)2]与AgOClO3以1:1摩尔比在二氯甲烷/二乙醚（1:2）中反应合成。以1为原料与四氢呋喃反应形成{Ag2L2[Au(C6F5)2]2}n（L = 四氢呋喃 (3)）。3结晶于单斜空间群C2/c，由通过亲金相互作用连接在一起的四核单元组成，形成平行于晶体学z轴的一维聚合物。金(I)原子与两个五氟苯基呈线性配位，并在四核单元内显示额外的Au…Ag近距离接触，距离为2.7582(3) 和2.7709(3) Å。每个银(I)中心与四氢呋喃分子的两个氧原子键合，Ag - O键长为2.307(3) Å。热重分析表明，1每个分子单元失去两个配位溶剂分子（第一个：75 - 100℃，第二个：150 - 175℃），而2、3和4以不太明确的方式同时失去挥发性有机化合物（VOCs）和氟化配体。每个配合物在约325℃时失去氟化配体和VOCs，生成1:1的金/银产物。X射线粉末衍射研究证实，固态下VOCs蒸气与1的反应使醚分子完全被新的VOC取代。VOCs按乙腈 > 丙酮 > 四氢呋喃 > 二乙醚的顺序被取代，其中醚最容易被取代。{Ag2(二乙醚)2[Au(C6F5)2]2}n和{Ag2(四氢呋喃)2[Au(C6F5)2]2}n在室温及77 K固态下均发光。发射最大值与低于约500 nm使用的激发波长无关。室温下在585 nm（醚）和544 nm（四氢呋喃）处获得发射最大值，77 K时在605 nm（醚）和567 nm（四氢呋喃）处获得发射最大值。
