Cooperative self-assembly of porphyrins and derivatives
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tion Porphyrins and their derivatives with well-defined size and chemistry are essential building blocks for the synthesis of active nanostructured materials for various applications, including light harvesting, photocatalytic synthesis, and water splitting.1–8 It has been shown that efficient electron or energy transport relies not only on intermolecular forces (such as hydrogen bonding, and π–π stacking), but also on ordered intermolecular arrangements, morphology, and dimension control.8–18 For example, the formation of ordered porphyrin nanoparticles with spatial control or axial porphyrin arrangement leads to significantly better photocatalytic activity.17,19–22 Thus, the potential of these materials is directly connected to the ability to control and engineer well-defined material structures, including size, shape, dimension, and spatial or axial intermolecular arrangements, which drives extensive synthetic efforts. Earlier studies on the formation of porphyrin arrays23–25 were limited to two-dimensional arrays with ill-defined material morphology and without long range order. Threedimensional (3D) porphyrin assemblies have been demonstrated through solid-state synthesis.26 However, the resulting materials exhibited uncontrolled external morphology and
structure dimensions. Recently, multichromophoric arrays and dendrimers were elegantly synthesized as antennas, and their photophysics were investigated.18,27,28 However, the complex multistep syntheses needed generally make it difficult for reproducibility and the engineering of material structure and properties, which hinders practical applications. More recently, efforts have been made to direct the synthesis of onedimensional (1D) nanostructures. For example, 1D porphyrin arrays were synthesized through electrostatic interactions and ionic self-assembly (see also the Zhong et al. article in this issue).29–32 Despite these recent advances, methods to engineer the assembly of porphyrins into well-defined 1D–3D nanostructures as model materials for the fundamental understanding of chemical and physical properties are still limited. Technologies to leverage the structural advantages of individual porphyrins amenable to energy-storage applications remain a significant challenge. Key factors such as molecular arrangement, types of noncovalent interactions, and shape have been demonstrated to be critical within specific 1D–3D nanostructures for charge and energy transfer. In this article, the cooperative selfassembly method will be discussed as a way to use amphiphilic surfactants and block copolymers to form “micelle-like”
Wenbo Wei, Key Laboratory for Special Functional Materials, National and Local Joint Engineering Research Center for High-Efficiency Display and Lighting Technology, School of Materials Science and Engineering, and Collaborative Innovation Center of Nano Functional Materials and Applications, Henan University, China; [email protected] Jiajie Sun, Department of Physics and Electronics, Henan University, China; [email protected] Hongyou
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