The Impact of Axial Ligation on the Excited State Dynamics of Cobalt(II) Phthalocyanine
The Impact of Axial Ligation on the Excited State Dynamics of Cobalt(II) Phthalocyanine
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DOI：
10.1016/j.jpap.2022.100132
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发表时间：
2022-06
影响因子：
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通讯作者：
Wenhui Hu;Denan Wang;Qiushi Ma;Benjamin J. Reinhart;Xiaoyi Zhang;Jie Huang
中科院分区：
文献类型：
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作者：
Wenhui Hu;Denan Wang;Qiushi Ma;Benjamin J. Reinhart;Xiaoyi Zhang;Jie Huang
本文采用X射线吸收光谱(XAS)、瞬时吸收光谱(TA)和密度泛函理论(DFT)计算相结合的方法，研究了轴向配位对钴(CoPc)分子激发态动力学的影响。X-射线光电子能谱(XAS)确证了以吡啶为溶剂形成六配位Co中心，导致其Q带跃迁较弱配位溶剂(DMF)显著蓝移。密度泛函理论计算进一步支持了这一点，预言了两个吡啶分子的轴向配位导致Q带蓝移。更有趣的是，利用TA光谱，我们观察到了一个新的中间态的形成，这可能是由于光激发时吡啶与CoPc进一步轴向连接，导致CoPc激发态的猝灭和寿命的缩短。
In this work, we report the effect of axial ligation on the excited state dynamics of Cobalt phthalocyanines (CoPc) using the combination of X-ray absorption spectroscopy (XAS), transient absorption (TA) spectroscopy, and density functional theory (DFT) calculation. The formation of six coordinated Co center was unambiguously confirmed by XAS when pyridine was used as the solvent, which leads to the prominent blue shift of its Q-band transition with respect to that in weak-ligating solvent (DMF). This is further supported by DFT calculation, which predicted that axial coordination by two pyridine molecules leads to blue shift of Q band. More interestingly, using TA spectroscopy, we observed the formation of a new intermediated state, which is likely due to the further axial ligation of pyridine to CoPc upon photoexcitation, resulting in the quenching of the CoPc excited state and shorter lifetime.