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首页> 外文期刊>Chemistry: A European journal >Push-Pull Porphyrins via b-Pyrrole Functionalization: Evidence of Excited State Events Leading to High-Potential Charge-Separated States
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Push-Pull Porphyrins via b-Pyrrole Functionalization: Evidence of Excited State Events Leading to High-Potential Charge-Separated States

机译：通过B-Pyrrole功能化推拉卟啉：兴奋状态事件的证据，导致高潜在的电荷分离状态

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摘要

A new set of free-base and zinc(II)-metallated, βpyrrole- functionalized unsymmetrical push-pull porphyrins were designed and synthesized via β-mono- and dibrominated tetraphenylporphyrins using Sonogashira cross-coupling reactions. The ability of donors and acceptors on the push- pull porphyrins to produce high-potential charge separated states was investigated. The porphyrins were functionalized at the opposite β,β'-pyrrole positions of porphyrin ring bearing triphenylamine push groups and naphthalimide pull groups. Systematic studies involving optical absorption, steady-state and time-resolved emission revealed existence of intramolecular type interactions both in the ground and excited states. The push-pull nature of the molecular systems was supported by frontier orbitals generated on optimized structures, wherein delocalization of HOMO over the push group and LUMO over the pull group connecting the porphyrin π-system was witnessed. Electrochemical studies were performed to visualize the effect of push and pull groups on the overall redox potentials of the porphyrins. Spectroelectrochemical studies combined with frontier orbitals helped in characterizing the one-electron oxidized and reduced porphyrins. Finally, by performing transient absorption studies in polar benzonitrile, the ability of push-pull porphyrins to produce charge-separated states upon photoexcitation was confirmed and the measured rates were in the range of 10~9 s~(-1). The lifetime of the final charge separated state was around 5 ns. This study ascertains the importance of push-pull porphyrins in solar energy conversion and diverse optoelectronic applications, for which high-potential charge-separated states are warranted.
机译：使用Sonogashira交叉偶联反应，设计和合成了一组新的自由基和锌（II）制备的βPyrOle-官能化的非对称推拉卟啉。研究了供体和受体对推拉卟啉产生高潜能电荷分离状态的能力。卟啉在卟啉环轴承三苯胺推动基团和萘胺拉动组的相对β，β'-吡咯位置官能化。涉及光学吸收，稳态和时间分离的排放的系统研究显示地面和激发态中的分子内型相互作用。通过在优化结构上产生的前轨道支撑分子系统的推挽性质，其中，目睹了连接卟啉π-系统的拉杆上的按钮和Lumo上的同性恋的分层化。进行电化学研究以可视化推拉组对卟啉整体氧化还原电位的影响。光谱电化学研究与边界轨道相结合，有助于表征单电子氧化和降低的卟啉。最后，通过在极性苄腈中进行瞬态吸收研究，确认了推挽卟啉在光透镜上产生电荷分离状态的能力，并且测量的速率在10〜9 s〜（-1）的范围内。最终电荷分离状态的寿命约为5 ns。本研究确定了推拉卟啉在太阳能转换和多样化的光电应用中的重要性，需要高潜能的电荷分离状态。

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