Band engineering in two-dimensional porphyrin- and phthalocyanine-based covalent organic frameworks: insight from molecular design

doi:10.1007/s44275-024-00007-y

Moore and More ›› 2025, Vol. 1 ›› Issue (1): 26-39.DOI: 10.1007/s44275-024-00007-y

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Band engineering in two-dimensional porphyrin- and phthalocyanine-based covalent organic frameworks: insight from molecular design

Xiaojuan Ni, Jean-Luc Brédas

Department of Chemistry and Biochemistry, The University of Arizona, Tucson, AZ, 85721-0041, USA

Received:2024-04-02 Revised:2024-05-17 Accepted:2024-05-22 Online:2024-07-04 Published:2024-07-04
Contact: Xiaojuan Ni,E-mail:xjni@arizona.edu;Jean-Luc Brédas,E-mail:jlbredas@arizona.edu
Supported by:
This work was supported by the College of Science at the University of Arizona.

Band engineering in two-dimensional porphyrin- and phthalocyanine-based covalent organic frameworks: insight from molecular design

Xiaojuan Ni, Jean-Luc Brédas

Department of Chemistry and Biochemistry, The University of Arizona, Tucson, AZ, 85721-0041, USA

通讯作者: Xiaojuan Ni,E-mail:xjni@arizona.edu;Jean-Luc Brédas,E-mail:jlbredas@arizona.edu
作者简介:Xiaojuan Ni Xiaojuan Ni currently is a Post-doctoral Research Associate in Chemistry and Biochemistry at The University of Arizona, working with Professor Jean-Luc Bredas. ′ She graduated with Bachelor’s (2010) and Master’s (2013) degrees in Chemical Engineering and Materials Science from Dalian University of Technology, China. She received her Ph.D. in Materials Science and Engineering from the University of Utah (2020) with the mentorship of Professor Feng Liu. Her research focuses on investigating the geometric, electronic, magnetic, and topological properties of organic frameworks and p-conjugated polymers. Additionally, she explores the ground- and excited-state characteristics of hybrid organic-inorganic perovskites, with a specific emphasis on their potential applications in optoelectronics.
Jean-Luc Brédas JeanLuc Brédas received his B.Sc. (1976) and Ph.D. (1979) degrees from University of Namur, Belgium. In 1988, he was appointed Professor at the University of Mons, Belgium, where he established the Laboratory for Chemistry of Novel Materials. While keeping an “Extraordinary Professorship” appointment in Mons, he joined The University of Arizona in 1999. In 2003, he moved to the Georgia Institute of Technology where he became Regents’ Professor of Chemistry and Biochemistry and held the Vasser-Woolley and Georgia Research Alliance Chair in Molecular Design. Between 2014 and 2016, he joined King Abdullah University of Science and Technology (KAUST) as a Distinguished Professor and served as Director of the KAUST Solar & Photovoltaics Engineering Research Center. He returned to Georgia Tech in 2017 before moving back to The University of Arizona in 2020 where he is currently Regents Professor in Department of Chemistry and Biochemistry.
Jean-Luc Brédas is an elected Member of the International Academy of Quantum Molecular Science, the Royal Academy of Belgium, and the European Academy of Sciences. Recent honors include the 2013 American Physical Society David Adler Lectureship Award in the field of Materials Physics, the 2016 American Chemical Society Award in the Chemistry of Materials, the 2019 Alexander von Humboldt Research Award, the 2020 Materials Research Society Materials Theory Award, and the 2021 Centenary Prize of the Royal Society of Chemistry. He is an Honorary Professor of the Institute of Chemistry of the Chinese Academy of Sciences and holds an Adjunct Professorship at the Georgia Institute of Technology. He was Editor for Chemistry of Materials, published by the American Chemical Society, between 2008 and 2021; since June 2022, he serves as Scientific Editor for Materials Horizons, the flagship materials journal of the Royal Society of Chemistry. He has published over 1 200 scientific articles, which have garnered nearly 140 000 citations (h-index: 170) according to Google Scholar.
基金资助:
This work was supported by the College of Science at the University of Arizona.

Abstract

Abstract: Two-dimensional covalent organic frameworks (2D COFs) represent an emerging class of crystalline polymeric networks, characterized by their tunable architectures and porosity, synthetic adaptability, and interesting optical, magnetic, and electrical properties. The incorporation of porphyrin (Por) or phthalocyanine (Pc) core units into 2D COFs provides an ideal platform for exploring the relationship between the COF geometric structure and its electronic properties in the case of tetragonal symmetry. In this work, on the basis of tight-binding models and density functional theory calculations, we describe the generic types of electronic band structures that can arise in tetragonal COFs. Three tetragonal lattice symmetries are examined: the basic square lattice, the Lieb lattice, and the checkerboard lattice. The potential topological characteristics of each lattice are explored. The Por-/Pc-based COFs exhibit characteristic band dispersions that are directly linked to their lattice symmetries and the nature of the frontier molecular orbitals of their building units. We show that the band dispersions in these COFs can be tailored by choosing specific symmetries of the molecular building units and/or by modulating the relative energies of the core and linker units. These strategies can be extended to a wide array of COFs, offering an effective approach to engineering their electronic properties.

Key words: Covalent organic frameworks, Porphyrin, Phthalocyanine, Electronic band structures, Molecular design

摘要： Two-dimensional covalent organic frameworks (2D COFs) represent an emerging class of crystalline polymeric networks, characterized by their tunable architectures and porosity, synthetic adaptability, and interesting optical, magnetic, and electrical properties. The incorporation of porphyrin (Por) or phthalocyanine (Pc) core units into 2D COFs provides an ideal platform for exploring the relationship between the COF geometric structure and its electronic properties in the case of tetragonal symmetry. In this work, on the basis of tight-binding models and density functional theory calculations, we describe the generic types of electronic band structures that can arise in tetragonal COFs. Three tetragonal lattice symmetries are examined: the basic square lattice, the Lieb lattice, and the checkerboard lattice. The potential topological characteristics of each lattice are explored. The Por-/Pc-based COFs exhibit characteristic band dispersions that are directly linked to their lattice symmetries and the nature of the frontier molecular orbitals of their building units. We show that the band dispersions in these COFs can be tailored by choosing specific symmetries of the molecular building units and/or by modulating the relative energies of the core and linker units. These strategies can be extended to a wide array of COFs, offering an effective approach to engineering their electronic properties.

关键词: Covalent organic frameworks, Porphyrin, Phthalocyanine, Electronic band structures, Molecular design

Xiaojuan Ni, Jean-Luc Brédas. Band engineering in two-dimensional porphyrin- and phthalocyanine-based covalent organic frameworks: insight from molecular design[J]. Moore and More, 2025, 1(1): 26-39.

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Band engineering in two-dimensional porphyrin- and phthalocyanine-based covalent organic frameworks: insight from molecular design

Band engineering in two-dimensional porphyrin- and phthalocyanine-based covalent organic frameworks: insight from molecular design

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