Anionic Fluorinated Zn-porphyrin Combined with Cationic Endohedral Li-fullerene for Long-Lived Photoinduced Charge Separation with Low Energy Loss
Anionic Fluorinated Zn-porphyrin Combined with Cationic Endohedral Li-fullerene for Long-Lived Photoinduced Charge Separation with Low Energy Loss
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阴离子氟化锌卟啉与阳离子内嵌锂富勒烯相结合，实现低能量损失的长寿命光致电荷分离
DOI：
10.1021/acs.jpcb.0c10450
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Ohkubo Kei
中科院分区：
文献类型：
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作者：
Miwa Kazuhira;Aoyagi Shinobu;Sasamori Takahiro;Ueno Hiroshi;Okada Hiroshi;Ohkubo Kei
本文报道了一种锌卟啉(anionicmeso-tetrakis(4-carboxymethylthio-2，3，5，6-tetrafluorophenyl))与阳离子锂内面体[60]富勒烯(Li+@C60)形成超分子配合物。由较大的结合常数与较强的静电吸引形成的超分子ZnTF4PPTC4-/Li+@C60通过光致电子转移产生长寿命、低能量损失的电荷分离(CS)态。具有高氧化电位的阴离子氟化锌卟啉减少了电荷分离的能量损失，提高了CS态的能级。电化学法测得CS态的能级为0.94 eV，远高于0.55 eV的阴离子四(磺基苯基)锌卟啉超分子络合物的能级。时间分辨瞬时吸收光谱表明，在乙腈和氯苯的二元溶剂中，ZnTF4PPTC4-/Li+@C60产生了寿命为0.29ms的长寿命CS态。CS态的寿命与苯甲腈中的ZnTPPS4-/Li+@C60相当。
Here we report an anionicmeso-tetrakis(4-carboxymethylthio-2,3,5,6-tetrafluorophenyl) zinc porphyrin (ZnTF4PPTC4–) to form a supramolecular complex with a cationic lithium endohedral [60]fullerene (Li+@C60). The supramolecular ZnTF4PPTC4–/Li+@C60complex formed by strong electrostatic attraction with a large binding constant generates a long-lived charge-separated (CS) state with low energy loss by photoinduced electron transfer from ZnTF4PPTC4–to Li+@C60. The anionic fluorinated zinc porphyrin with high oxidation potential reduces the energy loss associated with the charge separation and enhances the energy level of the CS state. The energy level of the CS state determined by electrochemical measurements is at 0.94 eV, which is much higher than that of a similar supramolecular complex using an anionicmeso-tetrakis(sulfonatophenyl) zinc porphyrin (ZnTPPS4–) at 0.55 eV. Time-resolved transient absorption spectroscopy demonstrates that ZnTF4PPTC4–/Li+@C60generates a long-lived CS state with a lifetime of 0.29 ms in a binary solvent of acetonitrile and chlorobenzene. The lifetime of the CS state is comparable to that of ZnTPPS4–/Li+@C60in benzonitrile.