Directly Coupled Versus Spectator Linkers on Diimine PtII Acetylides-Change the Structure, Keep the Function?
Directly Coupled Versus Spectator Linkers on Diimine PtII Acetylides-Change the Structure, Keep the Function?
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二亚胺 PtII 乙酰化物上的直接偶联与旁观连接基 - 改变结构，保留功能？
DOI：
10.1002/chem.201703989
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发表时间：
2017
期刊：
影响因子：
--
通讯作者：
Archer SA
中科院分区：
文献类型：
--
作者：
Archer SA
用锚定基团修饰集光单元以用于表面附着通常会损害光利用特性。在此，开发了一系列[供体-受体-锚]铂（II）二亚胺（双）乙炔化物，以便系统地比较受保护的锚定基团的连接的共轭模式与电子去耦模式对光捕获单元的光物理性质的影响。第一个例子的“去耦”膦酸二亚胺铂II配合物的报道，和他们的性能进行了比较和对比的羧酸盐类似物研究的多样性的方法。超快时间分辨红外光谱和瞬态吸收光谱显示，所有配合物都具有电荷转移（CT）最低激发态，寿命在2至14 ns之间。 CT状态的振动签名和动力学进行了鉴定，电子状态和它们的振动起源的分配是由TDDFT计算辅助。超快能量再分配伴随着结构的变化被直接捕获在CT状态。电子基态和CT激发态的结构之间的显着差异，以及在复合物轴承直接连接或电子去耦锚定基团的结构重组的差异，被发现。这项工作表明，通过饱和间隔物将锚定基团与光捕获核解耦是一种简单的方法，可以将联合收割机表面附着与高还原电位和光吸收单元的CT激发态的十倍长寿命相结合，并保留光捕获应用所必需的电子转移光反应性。
Modification of light‐harvesting units with anchoring groups for surface attachment often compromises light‐harnessing properties. Herein, a series of [donor–acceptor–anchor] platinum(II) diimine (bis‐)acetylides was developed in order to systematically compare the effect of conjugated versus electronically decoupled modes of attachment of protected anchoring groups on the photophysical properties of light‐harvesting units. The first examples of “decoupled” phosphonate diimine PtIIcomplexes are reported, and their properties are compared and contrasted to those of carboxylate analogues studied by a diversity of methods. Ultrafast time‐resolved IR and transient absorption spectroscopy revealed that all complexes have a charge‐transfer (CT) lowest excited state with lifetimes between 2 and 14 ns. Vibrational signatures and dynamics of CT states were identified; the assignment of electronic states and their vibrational origin was aided by TDDFT calculations. Ultrafast energy redistribution accompanied by structural changes was directly captured in the CT states. A significant difference between the structures of the electronic ground and CT excited states, as well as differences in the structural reorganisation in the complexes bearing directly attached or electronically decoupled anchoring groups, was discovered. This work demonstrates that decoupling of the anchoring group from the light‐harvesting core by a saturated spacer is an easy approach to combine surface attachment with high reduction potential and ten times longer lifetime of the CT excited state of the light‐absorbing unit, and retain electron‐transfer photoreactivity essential for light‐harvesting applications.
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