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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Ultrafast Energy Migration in Platinum(II) Diimine Complexes Bearing Pyrenylacetylide Chromophores
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Ultrafast Energy Migration in Platinum(II) Diimine Complexes Bearing Pyrenylacetylide Chromophores

机译：含P基乙炔发色团的铂（II）二亚胺络合物中的超快能量迁移

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The ultrafast excited-state dynamics of three structurally related platinum(II) complexes has been investigated using femtosecond transient absorption spectrometry in 2-methyltetrahydrofuran (MTHF).Previous work has shown that Pt(dbbpy)(Cident toC-Ph)_2 (dbbpy is 4,4'-di(tert-butyl)-2,2'-bipyridine and Cident toC-Ph is ethynylbenzene) has a lowest metal-to-ligand charge transfer (~3MLCT) excited state,while the multichromophoric Pt(dbbpy)-(Cident toC-pyrene)_2 (Cident toC-pyrene is 1-ethynylpyrene) contains the MLCT state,but possesses a lowest intraligand (~3IL) excited state localized on one of the Cident toC-pyrenyl units (Pomestchenko,I.E.;Luman,C.R.;Hissler,M.;Ziessel,R.;Castellano,F.N.Inorg.Chem.2003,42,1394-96).trans-Pt(PBu_3)_2(Cident toC-pyrene)_2 serves as a model system that provides a good representation of the Cident toC-pyrene-localized ~3IL state in a Pt(II) complex lacking the MLCT excited state.Following 400 nm excitation,the formation of the ~3MLCT excited state in Pt(dbbpy)(Cident toC-Ph)_2 is complete within 200+-40 fs,and intersystem crossing to the ~3IL excited state in trans-Pt(PBu_3)_2(Cident toC-pyrene)_2 occurs with a time constant of 5.4+-0.2 ps.Selective excitation into the low-energy MLCT bands in Pt(dbbpy)(Cident toC-pyrene)_2 (lambda_(ex)=480 nm) leads to the formation of the ~3IL excited state in 240+-40 fs,suggesting ultrafast wire-like energy migration in this molecule.The kinetic data suggest that the presence of the MLCT states in Pt(dbbpy)(Cident toC-pyrene)_2 markedly accelerates the formation of the triplet state of the pendant pyrenylacetylide ligand.In essence,the triplet sensitization process is kinetically faster than pure intersystem crossing in trans-Pt(PBu_3)_2(Cident toC-pyrene)_2 as well as vibrational relaxation in the MLCT excited state of Pt(dbbpy)(Cident toC-Ph)_2.These results are potentially important for the design of chromophores intended to reach their lowest excited state on subpicosecond time scales and advocate the likelihood of wire-like behavior in triplet-triplet energy transfer.
机译：使用飞秒瞬态吸收光谱法在2-甲基四氢呋喃（MTHF）中研究了三种结构相关的铂（II）配合物的超快激发态动力学。先前的研究表明Pt（dbbpy）（Cident toC-Ph）_2（dbbpy is 4,4'-二（叔丁基）-2,2'-联吡啶，C-Ph为乙炔基苯）的金属-配体电荷转移（〜3MLCT）激发态最低，而多色Pt（dbbpy） -（Cident toC-pyrene）_2（Cident toC-pyrene是1-ethynylpyrene）包含MLCT状态，但具有最低的配体（〜3IL）激发态，位于一个Cident toC-pyrenyl单元中（Pomestchenko，IE; Luman ，CR; Hissler，M。; Ziessel，R。; Castellano，FNInorg.Chem.2003,42,1394-96）.trans-Pt（PBu_3）_2（Cident toC-pyrene）_2用作提供在没有MLCT激发态的Pt（II）络合物中C到C-py定位的〜3IL态的事件的良好表示。在400 nm激发之后，在Pt中形成〜3MLCT激发态（dbbpy）（C-Ph-Cident）_2的入射在200 + -40 fs内完成，并且在trans-Pt（PBu_3）_2（C-pyrene）_2发生跨系统跃迁到〜3IL激发态的时间常数为5.4 + -0.2 ps。对Pt（dbbpy）（C-pyrene入射）_2（lambda_（ex）= 480 nm）的低能MLCT波段的选择性激发导致在240 + -40处形成〜3IL激发态动力学数据表明，Pt（dbbpy）（Cute toC-pyrene）_2中MLCT状态的存在显着促进了pyr基乙炔侧基配体的三重态的形成。从本质上讲，三重态敏化过程在动力学上比在反式Pt（PBu_3）_2（Cute toC-pyrene）_2中纯的系统间穿越以及在Pt（dbbpy）（Cident toC-Ph）的MLCT激发态下的振动松弛快_2。这些结果对于发色团的设计潜在重要，该发色团旨在在亚皮秒级的时间尺度和advo上达到其最低激发态确定三重态-三重态能量传递中类似导线行为的可能性。

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