State Key Laboratory Breeding Base of Photocatalysis, Fuzhou University, Fuzhou 350002, China.
Dalton Trans. 2012 Aug 28;41(36):11000-8. doi: 10.1039/c2dt31091k.
Two novel alkynyl-bridged symmetric bis-tridentate ligands 1,2-bis(1'-[4'-(2,2':6',2''-terpyridinyl)]ferrocenyl)ethyne (3a; tpy-Fc-C[triple bond]C-Fc-tpy; Fc = ferrocenyl; tpy = terpyridyl) and 1,4-bis(1'-[4'-(2,2':6',2''-terpyridinyl)]ferrocenyl)-1,3-butadiyne (3b; tpy-Fc-C[triple bond]C-C[triple bond]C-Fc-tpy) and their Ru(2+) complexes 6a and 6b have been synthesized and characterized by cyclic voltammetry, UV-vis and luminescence spectroscopy, and in the case of 3b by single-crystal X-ray diffraction. Cyclic voltammograms of both compounds, 3a and 3b, display two severely overlapping ferrocene-based oxidative peaks with only one reductive peak. The redox behavior of 6a and 6b is dominated by the Ru(2+)/Ru(3+) redox couple (E(1/2) from 1.33 to 1.34 V), the Fe(2+)/Fe(3+) redox couples (E(1/2) from 0.46 to 0.80 V), and the tpy/tpy(-)/tpy(2-) redox couples (E(1/2) from -1.19 to -1.48 V). The UV-vis spectra of 6a and 6b show absorption bands assigned to the (1)[(d(π)(Fe))(6)] → (1)[(d(π)(Fe))(5)(π*(tpy)(Ru))(1)] MMLCT transition at ~555 nm. Complexes and are luminescent in H(2)O-CH(3)CN (4 : 1, v/v) solution at room temperature, and 6b exhibits the strongest luminescence intensity (λ(max)(em): 710 nm, Φ(em): 2.28 × 10(-4), τ: 358 ns) relative to analogous ferrocene-based bis(terpyridine) Ru(II) complexes reported so far.
两种新型炔基桥联对称双三齿配体 1,2-双(1'-[4'-(2,2':6',2''-三联吡啶基)]二茂铁基)乙炔(3a;tpy-Fc-C[三键]C-Fc-tpy;Fc=二茂铁基;tpy=三联吡啶基)和 1,4-双(1'-[4'-(2,2':6',2''-三联吡啶基)]二茂铁基)-1,3-丁二炔(3b;tpy-Fc-C[三键]C-C[三键]C-Fc-tpy)及其 Ru(2+)配合物 6a 和 6b 已通过循环伏安法、紫外可见光谱和发光光谱进行了合成和表征，对于 3b 还通过单晶 X 射线衍射进行了表征。化合物 3a 和 3b 的循环伏安图均显示出两个严重重叠的基于二茂铁的氧化峰，仅存在一个还原峰。6a 和 6b 的氧化还原行为主要由 Ru(2+)/Ru(3+)氧化还原对(E(1/2)从 1.33 到 1.34 V)、Fe(2+)/Fe(3+)氧化还原对(E(1/2)从 0.46 到 0.80 V)和 tpy/tpy(-)/tpy(2-)氧化还原对(E(1/2)从-1.19 到-1.48 V)控制。6a 和 6b 的紫外可见光谱显示出归因于(1)[(d(π)(Fe))(6)]→(1)[(d(π)(Fe))(5)(π*(tpy)(Ru))(1)] MMLCT 跃迁的吸收带，在~555 nm 处。配合物在室温下在 H(2)O-CH(3)CN(4:1，v/v)溶液中发光，并且相对于迄今报道的类似的基于二茂铁的双(三联吡啶)Ru(II)配合物，6b 表现出最强的发光强度(λ(max)(em):710nm，Φ(em):2.28×10(-4)，τ:358 ns)。
