Selective Excited-State Dynamics in a Unique Set of Rationally Designed Ni Porphyrins

Selective Excited-State Dynamics in a Unique Set of Rationally Designed Ni Porphyrins
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一组独特的合理设计的镍卟啉的选择性激发态动力学

DOI:
10.1021/acs.jpcc.9b05413
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发表时间:
2019
期刊:
The Journal of Physical Chemistry C
影响因子:
--
通讯作者:
Zhang, Jian
Zhang, Jian
中科院分区:
--
文献类型:
--
作者:
Pattengale, Brian;Liu, Qiuhua;Hu, Wenhui;Yang, Sizhuo;He, Peilei;Tender, Sir Lawrence;Wang, Yingqi;Zhang, Xiaoyi;Zhou, Zaichun;Zhang, Jian

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在这项工作中,我们报告了一类独特的镍卟啉的设计和光物理性质,其中大环中间位置的叔丁基苯取代基通过带有烷基连接体的醚连接。这不仅导致大环永久锁定的ruf畸变,而且还能够通过改变烷基连接体的长度来设计畸变程度,从而解决了长期困扰卟啉光物理界的特定结构畸变的不确定性的复杂性。使用先进的时间分辨光学和 X 射线吸收光谱,我们观察到激发态弛豫路径的可调性取决于畸变程度,并表征了相关的瞬态中间结构。这些发现为研究非平面卟啉的各种激发态特性提供了一条新途径。
In this work, we report the design and photophysical properties of a unique class of Ni porphyrins, in which thetert-butyl benzene substituents at the meso positions of the macrocycle were tethered by ethers with alkyl linkers. This not only results in the permanently lockedrufdistortion of the macrocycle but also enables the engineering of the degree of distortion through varying the length of alkyl linkers, which addressed the complication of uncertainty in the specific structural distortions that has long plagued the porphyrin photophysical community. Using advanced time-resolved optical and X-ray absorption spectroscopy, we observed tunability in the excited-state relaxation pathway depending on the degree of distortion and characterized the associated transient intermediate structure. These findings provide a new avenue to afford accessibility to a wide range of excited-state properties in nonplanar porphyrins.
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发表时间: 2005-11-24
影响因子: 2.9
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