Synthesis and characterization of platinum(II) di-ynes and poly-ynes incorporating ethylenedioxythiophene (EDOT) spacers in the backbone.
Synthesis and characterization of platinum(II) di-ynes and poly-ynes incorporating ethylenedioxythiophene (EDOT) spacers in the backbone.
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DOI：
10.1039/c1dt11010a
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发表时间：
2011-09
影响因子：
4
通讯作者：
Muhammad S. Khan;Mohammed K. Al-Suti;Hakkikulla H Shah;Said Al-Humaimi;Fathiya R Al-Battashi;Jens K. Bjernemose;L. Male;P. Raithby;Ning Zhang;A. Köhler;J. Warren
中科院分区：
文献类型：
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作者：
Muhammad S. Khan;Mohammed K. Al-Suti;Hakkikulla H Shah;Said Al-Humaimi;Fathiya R Al-Battashi;Jens K. Bjernemose;L. Male;P. Raithby;Ning Zhang;A. Köhler;J. Warren
一系列引入3，4-亚乙基二氧噻吩（EDOT）连接基团Me（3）的三甲基甲硅烷基保护的二炔（R =亚乙基二氧噻吩-3，4-二基1a，2，2 ′-双-3，4-亚乙基二氧噻吩-5，5 ′-二基2a，2，2 ′，5 ′，2 ″-三-3，4-亚乙基二氧噻吩-5，5 ″-二基3a）和相应的末端二炔，合成并表征了H-C-C-R-C-C-H 1b-2b，测定了1a的单晶X-射线结构。CuI催化的反式-[（Ph）]之间的脱卤化氢反应（Et（3）P）（2）PtCl]和（i）Pr（2）NH/CH（2）Cl（2）中的末端二炔1b-2b（二）1摩尔比）得到Pt（II）二炔反式-[（Et（3）P）（2）（Ph）Pt-C C-R-C C-Pt（Ph）（Et（3）P）（2）] 1 M-2 M之间的脱卤化氢缩聚反应，而trans-[（（n）Bu（3）P）（2）PtCl（2）]与1b-2b（1：1摩尔比）在相似的反应条件下合成了反式-[Pt（P（n）Bu（3））（2）-C = C-R-C = C-]（n）1 P-2 P。二炔和多炔的特征在于光谱，并为1 M和2 M，通过单晶X-射线，证实了“刚性棒”二炔骨架。该材料具有优异的热稳定性，可溶于常见的有机溶剂，并易于流延成薄膜。光学吸收光谱测量表明，EDOT间隔创建更强的供体-受体之间的相互作用的铂（II）中心和共轭配体沿着的刚性骨架的有机金属聚合物相比，相关的非稠合和稠合寡聚噻吩间隔。
A series of trimethylsilyl-protected di-alkynes incorporating 3,4-ethylenedioxythiophene (EDOT) linker groups Me(3)Si-C≡C-R-C≡C-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-C≡C-R-C≡C-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(3)P)(2)PtCl] and the terminal di-alkynes 1b-2b in (i)Pr(2)NH/CH(2)Cl(2) (2:1 mole ratio) gives the Pt(II) di-ynes trans-[(Et(3)P)(2)(Ph)Pt-C≡C-R-C≡C-Pt(Ph)(Et(3)P)(2)] 1M-2M while the dehydrohalogenation polycondensation reaction between trans-[((n)Bu(3)P)(2)PtCl(2)] and 1b-2b (1:1 mole ratio) under similar reaction conditions affords the Pt(II) poly-ynes trans-[Pt(P(n)Bu(3))(2)-C≡C-R-C≡C-](n)1P-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.