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DOE OSTI · 1974380

Shape-persistent phthalocyanine cages

Hu, Yiming·Huang, Shaoda·Wayment, Lacey J.·Wu, Jingyi·Xu, Qiucheng·Chang, Tieyan·Chen, Ying-Pin·Li, Xiaonian·Andi, Babak·Chen, Hongxuan·Jin, Yinghua·Zhu, Han·Du, Mingliang·Lu, Shuanglong·Zhang, Wei
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Abstract

Phthalocyanine (Pc), an electro-redox active moiety, has many attractive properties stemming from its large aromatic system and ability to act as a catalyst in electrochemical reactions, such as the CO 2 reduction reaction (CO 2 RR). However, due to the synthetic challenge related to geometric requirements and poor solubility (strong aggregation), discrete shape-persistent cages consisting of site-isolated, readily accessible Pc moieties have not been available. Here, we report the synthesis of Zn- and Ni-metallated Pc-based molecular cages via one-step dynamic spiroborate linkage formation in high yields. The ZnPc cage structure is unambiguously elucidated at the atomic level by single-crystal X-ray diffraction. Moreover, owing to the site-isolated redox-active metal centers, readily accessible intrinsic cavity, and shape-persistent backbone, the Ni-metallated Pc (NiPc) cage exhibits high catalytic efficiency, selectivity, and stability, superior to the non-caged control molecules in electrocatalytic CO 2 RR.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY59 BASIC BIOLOGICAL SCIENCESCO2 reductiondynamic spiroborate chemistryorganic molecular cagephthalocyaninesite-isolated

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Hu, Yiming, Huang, Shaoda, Wayment, Lacey J., Wu, Jingyi, Xu, Qiucheng, Chang, Tieyan, Chen, Ying-Pin, Li, Xiaonian, Andi, Babak, Chen, Hongxuan, Jin, Yinghua, Zhu, Han, Du, Mingliang, Lu, Shuanglong, Zhang, Wei. 2023-02-07. Shape-persistent phthalocyanine cages. https://doi.org/10.1016/j.xcrp.2023.101285

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