Structure and emission studies of dimorphic crystals of [PtBr_2(5,5'-bis(CF_3CH_2OCH_2)-2,2'-bpy)] (1)

Norman Lu; Lauren M. Hight; David R. McMillin; Jyun-Wei Jhuo; Wei-Cheng Chung; Kwan-Yu Lin; Yuh-Sheng Wen; Ling-Kang Liu

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Structure and emission studies of dimorphic crystals of [PtBr_2(5,5'-bis(CF_3CH_2OCH_2)-2,2'-bpy)] (1)

机译：[PtBr_2（5,5'-bis（CF_3CH_2OCH_2）-2,2'-bpy）]的双晶晶体的结构和发射研究（1）

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The yellow (1y) and orange (1o) crystalline polymorphs of [PtBr_2(5,5'-bis(CF_3CH_2OCH_2)-2,2'-bipyridine)] exhibit surprisingly short nearest neighbour Pt?Pt separations of 3.526 ? and 3.590 ?, respectively, at 295 K. Both distances are much shorter than those found in structures of the unsubstituted [PtBr_2(2,2'- bipyridine)] analogue. Consistent with a linear chain structure in 1o and dimer formation in 1y, both solids exhibit emission spectra shifted to much longer wavelengths than that exhibited by the monomer in a low-temperature glass. Furthermore, the emission spectra of 1o and 1y shift to even longer wavelengths as the temperature decreases and the Pt?Pt separations contract. Till now delocalized emission of this type has been considered to be restricted to [PtCl_2(diimine)] systems and implausible in PtBr_2-containing analogues for steric reasons. Ironically, in the system at hand the bulky 5,5'-substituents apparently promote delocalization of the emission by forming a network of hydrogen-bonding-like C-H?F-C interactions that help shape the packing.

机译：[PtBr_2（5,5'-bis（CF_3CH_2OCH_2）-2,2'-联吡啶）]的黄色（1y）和橙色（1o）结晶多晶型物表现出令人惊讶的短近邻Pt？Pt间距3.526？分别在295K和3.590Ω。两个距离都比未取代的[PtBr_2（2,2'-联吡啶）]类似物的结构中的距离短。与1o的线性链结构和1y的二聚体形成相一致，两种固体的发射光谱都移到了比低温玻璃中单体所显示的更长的波长处。此外，随着温度的降低和Pt→Pt间距的缩小，1o和1y的发射光谱会移动到更长的波长。到目前为止，由于空间原因，这种类型的离域发射一直被认为仅限于[PtCl_2（diimine）]系统，并且在含PtBr_2的类似物中是难以置信的。具有讽刺意味的是，在现有系统中，庞大的5,5'-取代基显然通过形成有助于形成堆积的类似于氢键的C-H2F-C相互作用网络而促进了发射的离域化。

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《Dalton transactions: An international journal of inorganic chemistry》 |2014年第5期|共8页
作者
Norman Lu; Lauren M. Hight; David R. McMillin; Jyun-Wei Jhuo; Wei-Cheng Chung; Kwan-Yu Lin; Yuh-Sheng Wen; Ling-Kang Liu;
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正文语种 eng
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Structure; emission; dimorphic;

机译：结构;发射;二态;

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Structure and emission studies of dimorphic crystals of [PtBr_2(5,5'-bis(CF_3CH_2OCH_2)-2,2'-bpy)] (1)

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