Binary ionic porphyrin self-assembly: Structures, and electronic and light-harvesting properties
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oduction Crystalline solids self-assembled from anionic and cationic porphyrins have received significant attention in nanoscience and nanotechnology.1–3 Their tunable optical and electronic properties and their tailorable size and shape structures with molecular design provide an opportunity to control optoelectronic properties and device performance.4 These structures show great promise for a variety of applications, including sensors,5 energy-conversion and storage devices,6 and lightharvesting energy materials for solar and other renewable energy systems.7 Porphyrins, which can be found in nature (e.g., chlorophyll), represent a class of conjugated organic molecules that possess unique planar, rigid molecular geometries, various metals (e.g., Cu, Zn, and Sn) that sit in the center of the ring for a metal porphyrin, and substituents (e.g., phenoxy and phenylcarboxy). These structurally and functionally resemble natural photosynthetic and enzymatic chromophores, which are parts of a molecule that are responsible for its color.8 Porphyrins are attractive building blocks for self-assembled nanomaterials through noncovalent interactions, such as van der Waals forces, hydrogen bonding, aromatic π–π stacking,
and axial coordination. Porphyrin assemblies are extensively being studied as promising organic photocatalytic, electronic, and biochemical phototherapy materials. Self-assembled, porphyrin crystalline solids can be obtained by ionic, surfactant-assisted, phase-transfer self-assembly methods as well as other synthetic methods.9–12 Here, we focus on the concept of binary ionic porphyrin self-assembly. This article summarizes the ionized forms of porphyrin, ultraviolet (UV)–visible optical absorption, and electronic and optoelectronic properties. Crystalline solid porphyrins self-assembled as photocatalytic organic semiconductors are also discussed, including the ability of photocatalytic reduction of metal complexes and deposition of metals onto their outer surfaces, photoreduction of H2O to H2, and the potential for light-driven CO2-reduction catalysis with the aid of a soluble sacrificial electron donor (ED) under visible light.
Ionized forms of porphyrin Binary ionic porphyrin self-assembly (ISA) is a method that uses binary, oppositely charged porphyrin ions to construct crystalline solids with defined size and morphology through electrostatic interactions and other noncovalent interactions,
Yong Zhong, Key Laboratory for Special Functional Materials, Ministry of Education, Henan University, China; [email protected] Jiefei Wang, International Joint Center for Biomedical Innovation, Henan University, China; [email protected] Yongming Tian, Angstrom Thin Film Technologies LLC, USA; [email protected] doi:10.1557/mrs.2019.40
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