钌铂异核配合物的双光子性能研究
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- 英文论文题名：Study on the Two-photon Absorption Ability of a Heterometallic Heptnuclear Ru-Pt Complex
- 论文作者：施鹏飞 ; 姜琴
- 英文论文作者：Pengfei Shi ; Qin Jiang ; Department of Chemistry ; Huaihai Institute of Technology
- 年：2016
- 作者机构：淮海工学院;
- 论文关键词：双光子 ; 异多核配合物
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第二十七分会：光化学
- 语种：中文
- 分类号：O641.4
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第二十七分会 ; 光化学
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：271k
- 原文格式：D
- 会议级别：全国
摘要
前期报道的七核配合物Ru Pt6-A(Fig.1-a)具有良好的双光子吸收性能1,与相应的单核钌配合物相比其双光子吸收截面值增大了4倍。本文采用共轭体系更大的bbpe(4,4’-Bis[(E)-2-(4-pyridyl)vinyl]-2,2′-bipyridiine)作为RuII的配体,采用Pt{N,C,N}取代外围的铂配位单元Pt{N,N,N},设计合成了配合物Ru Pt6-B(Fig.1-b)。X-ray单晶衍射数据显示配合物Ru Pt6-B结构中的配体bbpe比Ru Pt6-A中的配体qpy(4,4’:2’,2’’:4’’,4’’’-quaterpyridine)具有更好的平面性,Pt{N,C,N}配位平面与bbpe末端的吡啶平面的夹角也小于Pt{N,N,N}与qpy末端吡啶平面的二面角。Ru Pt6-B的双光子吸收界面值比Ru Pt6-A大大增强,这不仅是因为Pt{N,N,C}的发光性能要显著强于Pt{N,N,N}2,还可能与配合物中异多核金属之间存在更为有效的相互作用有关。Ru Pt6-B中配体的分子平面性以及大共轭体系有利于RuII和PtII之间的电子传递,异多核效应协同增强了配合物的双光子性能。
In the previous work we reported a heptnuclear complex RuPt6-A(shown in Fig.1-a) and its TPA cross-section value increased 4 times when compared with its RuII core-unit. Here a novel Ru-Pt complex was designed and synthesized, by using bbpe(4,4'-Bis[(E)-2-(4-pyridyl)vinyl]-2,2′-bipyridiine) as the ligand and replacing the peripheral Pt{N,N,N} with Pt{N,C,N}. The X-ray diffraction crystallography data indicated that the bbpe displayed better coplanarity in the crystal structure of Ru Pt6-B than the qpy(4,4':2',2'':4'',4'''-quaterpyridine) in Ru Pt6-A does, the dihedral angle between the Pt{N, C, N} and outer pyridine ring was smaller than that of Pt{N, N, N}/pyridine. Ru Pt6-B showed greatly enhanced TPA cross-section than Ru Pt6-A, not only because the emission property of Pt{N, C, N} was superior to that of Pt{N,N,N}, the contribution from the efective interactions between the Ru II and Pt II centers in the heterometallic complex should also be considered. The coplanarity and extended π-conjugation system facilitates the electron transfer between the heterometallic center, which can "boost" the TPA property through the cooperative enhancement effect.
In the previous work we reported a heptnuclear complex RuPt6-A(shown in Fig.1-a) and its TPA cross-section value increased 4 times when compared with its RuII core-unit. Here a novel Ru-Pt complex was designed and synthesized, by using bbpe(4,4'-Bis[(E)-2-(4-pyridyl)vinyl]-2,2′-bipyridiine) as the ligand and replacing the peripheral Pt{N,N,N} with Pt{N,C,N}. The X-ray diffraction crystallography data indicated that the bbpe displayed better coplanarity in the crystal structure of Ru Pt6-B than the qpy(4,4':2',2'':4'',4'''-quaterpyridine) in Ru Pt6-A does, the dihedral angle between the Pt{N, C, N} and outer pyridine ring was smaller than that of Pt{N, N, N}/pyridine. Ru Pt6-B showed greatly enhanced TPA cross-section than Ru Pt6-A, not only because the emission property of Pt{N, C, N} was superior to that of Pt{N,N,N}, the contribution from the efective interactions between the Ru II and Pt II centers in the heterometallic complex should also be considered. The coplanarity and extended π-conjugation system facilitates the electron transfer between the heterometallic center, which can "boost" the TPA property through the cooperative enhancement effect.
引文
[1]Shi,P.F.,Coe,B.J.,Sa?nchez,S.,Wang,D.Q.,Tian,Y.P.,Nyk,M.,Samoc,M.Inorg.Chem.2015,54:11450
[2]Botchway,S.W.,Charnley,M.,Haycock,J.W.,Parker,A.W.,Rochester,D.L.,Weinstein,J.A.,Williams,J.A.G.PNAS,2008,105,16071
[2]Botchway,S.W.,Charnley,M.,Haycock,J.W.,Parker,A.W.,Rochester,D.L.,Weinstein,J.A.,Williams,J.A.G.PNAS,2008,105,16071