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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Synthesis and characterization of platinum(ii) di-ynes and poly-ynes incorporating ethylenedioxythiophene (EDOT) spacers in the backbone
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Synthesis and characterization of platinum(ii) di-ynes and poly-ynes incorporating ethylenedioxythiophene (EDOT) spacers in the backbone

机译：骨架中结合了乙二氧基噻吩（EDOT）间隔基的铂（ii）二炔和聚炔的合成与表征

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摘要

A series of trimethylsilyl-protected di-alkynes incorporating 3,4-ethylenedioxythiophene (EDOT) linker groups Me3Si-CC-R-CC- SiMe_3 (R = ethylenedioxythiophene-3,4-diyl 1a, 2,2′-bis-3,4- ethylenedioxythiophene-5,5′-diyl 2a, 2,2′,5′,2′′- ter-3,4-ethylenedioxythiophene-5,5′′-diyl 3a) and the corresponding terminal di-alkynes, H-CC-R-CC-H 1b-2b has been synthesized and characterized and the single crystal X-ray structure of 1a has been determined. CuI-catalyzed dehydrohalogenation reaction between trans-[(Ph)(Et_3P) _2PtCl] and the terminal di-alkynes 1b-2b in ~iPr _2NH/CH_2Cl_2 (2:1 mole ratio) gives the Pt(ii) di-ynes trans-[(Et_3P)_2(Ph)Pt-CC-R-CC-Pt(Ph)(Et _3P)_2] 1M-2M while the dehydrohalogenation polycondensation reaction between trans-[(~nBu_3P)_2PtCl _2] and 1b-2b (1:1 mole ratio) under similar reaction conditions affords the Pt(ii) poly-ynes trans-[Pt(P~nBu_3) _2-CC-R-CC-]_n1P-2P. The di-ynes and poly-ynes have been characterized spectroscopically and, for 1M and 2M, by single-crystal X-ray which confirms the "rigid rod" di-yne backbone. The materials possess excellent thermal stability, are soluble in common organic solvents and readily cast into thin films. Optical absorption spectroscopic measurements reveal that the EDOT spacers create stronger donor-acceptor interactions between the platinum(ii) centres and conjugated ligands along the rigid backbone of the organometallic polymers compared to the related non-fused and fused oligothiophene spacers.
机译：一系列三甲基甲硅烷基保护的二炔烃，其中掺入3,4-乙二氧基噻吩（EDOT）接头基团Me3Si-CC-R-CC-SiMe_3（R =乙二氧基噻吩-3,4-二基1a，2,2'-bis-3 4-亚乙基二氧噻吩-5,5'-二基2a，2,2'，5'，2''-ter-3,4-亚乙基二氧噻吩-5,5''-二基3a）和相应的末端二炔烃，H -CC-R-CC-H 1b-2b已经合成并表征，并且1a的单晶X射线结构已经确定。在〜iPr _2NH / CH_2Cl_2中（摩尔比为2：1），反式[[（Ph）（Et_3P）_2PtCl]与末端二炔1b-2b之间的CuI催化的脱卤化氢反应得到了Pt（ii）二炔反式- [（Et_3P）_2（Ph）Pt-CC-R-CC-Pt（Ph）（Et _3P）_2] 1M-2M，而反式[[〜nBu_3P）_2PtCl _2]与1b-2b之间的脱卤化氢缩聚反应（在相似的反应条件下以1∶1的摩尔比得到Pt（ii）聚炔-反式-[Pt（P〜nBu_3）_2-CC-R-CC-] _ n1P-2P。对二炔和聚炔进行了光谱学表征，对于1M和2M，通过单晶X射线表征了“刚性棒”二炔骨架。该材料具有出色的热稳定性，可溶于常见的有机溶剂，并易于流延成薄膜。光学吸收光谱法测量表明，与相关的非熔融和熔融寡聚噻吩间隔物相比，EDOT间隔物沿着有机金属聚合物的刚性骨架在铂（ii）中心和共轭配体之间产生了更强的供体-受体相互作用。

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