Rausch Janek, Lorenz Volker, Hrib Cristian G, Frettlöh Vanessa, Adlung Matthias, Wickleder Claudia, Hilfert Liane, Jones Peter G, Edelmann Frank T
Chemisches Institut der Otto-von-Guericke-Universität Magdeburg , Universitätsplatz 2, 39106 Magdeburg, Germany.
Inorg Chem. 2014 Nov 3;53(21):11662-74. doi: 10.1021/ic501837x. Epub 2014 Oct 20.
This contribution presents a full account of a structurally diverse class of heterometallic europium disiloxanediolates. The synthetic protocol involves in situ metalation of (HO)SiPh2OSiPh2(OH) (1) with either (n)BuLi or KN(SiMe3)2 followed by treatment with EuCl3 in suitable solvents such as 1,2-dimethoxyethane (DME) or tetrahydrofuran (THF). Reaction of EuCl3 with 2 equiv of (LiO)SiPh2OSiPh2(OLi) in DME afforded the Eu(III) bis(disiloxanediolate) "ate" complex [{(Ph2SiO)2O}2{Li(DME)}3]EuCl2 (2), which upon attempted reduction with Zn gave the tris(disiloxanediolate) [{(Ph2SiO)2O}3{Li(DME)}3]Eu (3). Treatment of EuCl3 with (LiO)SiPh2OSiPh2(OLi) in a molar ratio of 1:2 yielded both the ate complex [{(Ph2SiO)2O}3Li{Li(THF)2}{Li(THF)}]EuCl·Li(THF)3 (4) and the LiCl-free europium(III) complex [{(Ph2SiO)2O}2{Li(THF)2}2]EuCl (5). Compound 5 was found to exhibit a brilliant red triboluminescence. When (KO)SiPh2OSiPh2(OK) was used as starting material in a 3:1 reaction with EuCl3, the Eu(III) tris(disiloxanediolate) [{(Ph2SiO)2O}3{K(DME)}3]Eu (6) was isolated. Attempted ligand transfer between 5 and (DAD(Dipp))2Ba(DME) (DAD(Dipp) = N,N'-bis(2,6-diisopropylphenyl)-1,4-diaza-1,3-butadiene) afforded the unique mixed-valent Eu(III)/Eu(II) disiloxanediolate cluster [(Ph2SiO)2O]6Eu(II)4Eu(III)2Li4O2Cl2 (7). All new complexes were structurally characterized by X-ray diffraction. Photoluminescence studies were carried out for complex 5 showing an excellent color quality, due to the strong (5)D0→(7)F2 transition, but a weak antenna effect.
本论文全面介绍了一类结构多样的异金属二硅氧烷二醇铕化合物。合成方法包括用正丁基锂或双（三甲基硅基）胺基钾对（HO）SiPh2OSiPh2（OH）（1）进行原位金属化，然后在合适的溶剂如1,2 - 二甲氧基乙烷（DME）或四氢呋喃（THF）中用EuCl3处理。EuCl3与2当量的（LiO）SiPh2OSiPh2（OLi）在DME中反应得到铕（III）双（二硅氧烷二醇）“酸根”配合物[{(Ph2SiO)2O}2{Li(DME)}3]EuCl2（2），用锌尝试还原该配合物得到三（二硅氧烷二醇）配合物[{(Ph2SiO)2O}3{Li(DME)}3]Eu（3）。EuCl3与（LiO）SiPh2OSiPh2（OLi）以1:2的摩尔比反应，得到酸根配合物[{(Ph2SiO)2O}3Li{Li(THF)2}{Li(THF)}]EuCl·Li(THF)3（4）和无LiCl的铕（III）配合物[{(Ph2SiO)2O}2{Li(THF)2}2]EuCl（5）。发现化合物5呈现出明亮的红色摩擦发光。当（KO）SiPh2OSiPh2（OK）作为起始原料与EuCl3以3:1的比例反应时，分离得到铕（III）三（二硅氧烷二醇）配合物[{(Ph2SiO)2O}3{K(DME)}3]Eu（6）。尝试在5和（DAD（Dipp））2Ba（DME）（DAD（Dipp） = N，N'-双（2,6 - 二异丙基苯基）-1,4 - 二氮杂 - 1,3 - 丁二烯）之间进行配体转移，得到了独特的混合价态Eu（III）/Eu（II）二硅氧烷二醇簇合物[(Ph2SiO)2O]6Eu（II）4Eu（III）2Li4O2Cl2（7）。所有新配合物都通过X射线衍射进行了结构表征。对配合物5进行了光致发光研究，由于其强烈的（5）D0→（7）F2跃迁，显示出优异的颜色质量，但天线效应较弱。
