基于半夹心Cp*Rh单元的超分子桥环和螺环化合物的构筑策略

A synthetic strategy of organometallic supramolecular bridged compounds and spirocyclic compounds featuring half-sandwich Cp*Rh units

桥环和螺环化合物是有机化学中常用的概念而在其他领域鲜有提及。在本研究中,我们将桥环和螺环的概念拓展至超分子化学领域中并提出了相应的构筑策略。在刚性直线型配体中引入额外的螯合位点,通过配位驱动、分步组装的方法合成了复杂的3个有机金属超分子桥环化合物[(Cp*Rh)_(6)(μ-η^(2)-η^(2)-C_(2)O_(4))_(2)(μ-C_(2)O_(4))(L^(A))_(2)](OTf)_(6)(1)、[(Cp*Rh)_(6)(dhbq)_(2)(pyrazine)(L^(A))_(2)](OTf)_8(2)和[(Cp*Rh)_(6)(tpphz)_(2)(bpea)(L^(A))_(2)](OTf)_(12)(3),以及一个超分子螺环化合物(Cp*Rh)_(12)(bibzim)_(3)Ru(L^(A))_(3)(L^(B))_(3)](OTf)_(10)(PF_(6))_(4)(4),其中L^(A)=3,3'-di(pyridin-4-yl)-2,2'-bipyridine,OTf^(-)=CF_(3)SO_(3)^(-),dhbq=2,5-dihydroxy-1,4-benzoquinone,tpphz=tetrapyrido[3,2-a∶2',3'-c∶3″,2″-h∶2′″,3′″-j]phenazine,bpea=1,2-di(pyridin-4-yl)ethane,bibzim=2,2'-bisbenzimidazole,L^(B)=4,4'-di(pyridin-4-yl)-1,1'-biphenyl。并通过单晶X射线衍射的方法一一表征了它们的单晶结构。

Bridged and spirocyclic compounds are common concepts in the pure organic field.Herein,we extend these concepts to supramolecular chemistry and a synthetic strategy is exhibited.Three supramolecular bridged compounds[(Cp*Rh)_(6)(μ-η^(2)-η^(2)-C_(2)O_(4))_(2)(μ-C_(2)O_(4))(L~A)_(2)](OTf)_(6)(1),[(Cp*Rh)_(6)(dhbq)_(2)(pyrazine)(L~A)_(2)](OTf)_8(2),and[(Cp*Rh)_(6)(tpphz)_(2)(bpea)(L~A)_(2)](OTf)_(12)(3),and a spirocyclic compound (Cp*Rh)_(12)(bibzim)_(3)Ru(L~A)_(3)(L^(B))_(3)](OTf)_(10)(PF_(6))_(4)(4),where L~A=3,3'-di(pyridin-4-yl)-2,2'-bipyridine,OTf^(-)=CF_(3)SO_(3)^(-),dhbq=2,5-dihydroxy-1,4-benzoquinone,tpphz=tetrapyrido[3,2-a∶2',3'-c∶3",2"-h∶2′″,3′″-j]phenazine,bpea=1,2-di(pyridin-4-yl)ethane,bibzim=2,2'-bisbenzimidazole,L^(B)=4,4'-di(pyridin-4-yl)-1,1'-biphenyl,were obtained by introducing of additional chelating sites in rigid linear ligand through coordination-driven stepwise chemical self-assembly method and were characterized by single crystal X-ray diffraction method.CCDC:2296510,1;2296511,2;2296512,3;2296513,4.