Diferrocenes Bridged by a Geminal Diethynylethene Scaffold with Varying Pendant Substituents: Electronic Interactions in Cross-Conjugated System,Organometallics

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Diferrocenes Bridged by a Geminal Diethynylethene Scaffold with Varying Pendant Substituents: Electronic Interactions in Cross-Conjugated System
Organometallics ( IF 2.5 ) Pub Date : 2017-10-27 00:00:00 , DOI: 10.1021/acs.organomet.7b00686
Yang Fan ₁ , Hua-Min Li ₁ , Guo-Dong Zou ₁ , Xu Zhang ₂ , Ying-Le Pan ₁ , Ke-Ke Cao ₁ , Meng-Li Zhang ₁ , Pei-Lin Ma ₁ , Hai-Ting Lu ₁

Affiliation

A series of geminal diethynylethene (gem-DEE) bridged diferrocenyl compounds with varying pendant substituents at the side chain, including xanthene, thioxanthene, dibenzo[a,d]cycloheptene, and fluorene, is reported with the aim of exploring electronic interactions in the cross-conjugated system. The compounds 9-[bis(ferrocenylethynyl)methylene]-9H-xanthene (1), 9-[bis(ferrocenylethynyl)methylene]-9H-thioxanthene (2), 5-[bis(ferrocenylethynyl)methylene]-5H-dibenzo[a,d]cycloheptene (3), and 9-[bis(ferrocenylethynyl)methylene]-9H-fluorene (4) were synthesized and characterized by using spectroscopic methods and single-crystal X-ray diffraction analyses. Electrochemical measurements using the weakly coordinating electrolyte Na[B{C₆H₃(3,5-CF₃)₂}₄] reveal the moderate electronic coupling between the ferrocenyl (Fc) termini. Hush analysis of the intervalence charge-transfer (IVCT) bands for the monocation species is suggestive of the weakly coupled Robin–Day class II mixed-valence compounds. DFT and TDDFT calculations suggest that the low-energy transitions of these compounds mainly involve a metal to ligand charge transfer (MLCT) transition from the iron center of ferrocenyl termini to the pendant substituent.

中文翻译：

双歧二茂铁与不同的侧链取代基的双戊二烯骨架架桥：交叉共轭系统中的电子相互作用。

据报道，一系列双季戊二烯（gem -DEE）桥联的二铁茂铁化合物在侧链上具有不同的侧基取代基，包括，吨，噻吨，二苯并[ a，d ]环庚烯和芴，旨在探索十字架中的电子相互作用。共轭体系。化合物9- [双（ferrocenylethynyl）亚甲基] -9- ħ呫吨（1），9- [双（ferrocenylethynyl）亚甲基] -9- ħ -thioxanthene（2），5- [双（ferrocenylethynyl）亚甲基] -5 ħ -二苯并[ a，d ]环庚烯（3）和9- [双（二茂铁基乙炔基）亚甲基] -9 H通过光谱法和单晶X射线衍射分析合成了-芴（4）并进行了表征。使用弱配位电解质Na [B {C ₆ H ₃（3,5-CF ₃）₂ } ₄ ]进行的电化学测量显示，二茂铁基（Fc）末端之间存在中等程度的电子偶联。对单阳离子物种的间隔电荷转移（IVCT）谱带进行静默分析表明，Robin-Day II类混合价化合物弱耦合。DFT和TDDFT计算表明，这些化合物的低能跃迁主要涉及从二茂铁基末端的铁中心到侧基取代基的金属到配体的电荷转移（MLCT）跃迁。

更新日期：2017-10-27

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