title: Creation of Superheterojunction Polymers via Direct Polycondensation: Segregated and Bicontinuous Donor-Acceptor π-Columnar Arrays in Covalent Organic Frameworks for Long-Lived Charge Separation.
abstract: By developing metallophthalocyanines and diimides as electron-donating and -accepting building blocks, herein, we report the construction of new electron donor-acceptor covalent organic frameworks (COFs) with periodically ordered electron donor and acceptor π-columnar arrays via direct polycondensation reactions. X-ray diffraction measurements in conjunction with structural simulations resolved that the resulting frameworks consist of metallophthalocyanine and diimide columns, which are ordered in a segregated yet bicontinuous manner to form built-in periodic π-arrays. In the frameworks, each metallophthalocyanine donor and diimide acceptor units are exactly linked and interfaced, leading to the generation of superheterojunctions-a new type of heterojunction machinery, for photoinduced electron transfer and charge separation. We show that this polycondensation method is widely applicable to various metallophthalocyanines and diimides as demonstrated by the combination of copper, nickel, and zinc phthalocyanine donors with pyrommellitic diimide, naphthalene diimide, and perylene diimide acceptors. By using time-resolved transient absorption spectroscopy and electron spin resonance, we demonstrated that the COFs enable long-lived charge separation, whereas the metal species, the class of acceptors, and the local geometry between donor and acceptor units play roles in determining the photochemical dynamics. The results provide insights into photoelectric COFs and demonstrate their enormous potential for charge separation and photoenergy conversions.
authors.affiliation: †Department of Materials Molecular Science, Institute for Molecular Science, National Institutes of Natural Sciences, 5-1 Higashiyama, Myodaiji, Okazaki, Aichi 444-8787, Japan.
authors.forename: Shangbin
authors.initials: S
authors.lastname: Jin
authors.affiliation: ⊥Department of Material and Life Science, Graduate School of Engineering, Osaka University, ALCA, JST, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan.
authors.forename: Mustafa
authors.initials: M
authors.lastname: Supur
authors.affiliation: ‡WPI-Research Initiative-Institute of Transformative Bio-Molecules and Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8602, Japan.
authors.forename: Matthew
authors.initials: M
authors.lastname: Addicoat
authors.affiliation: §Institute for Research Promotion Center for Instrumental Analysis, Niigata University, 8050 Ikarashi, 2 Nocho, Niigata, Niigata 950-2181, Japan.
authors.forename: Ko
authors.initials: K
authors.lastname: Furukawa
authors.affiliation: †Department of Materials Molecular Science, Institute for Molecular Science, National Institutes of Natural Sciences, 5-1 Higashiyama, Myodaiji, Okazaki, Aichi 444-8787, Japan.|¶College of Materials Science and Engineering, Beijing Institute of Technology, Zhongguancun south street 5, Beijing 100081, China.
authors.forename: Long
authors.initials: L
authors.lastname: Chen
authors.affiliation: †Department of Materials Molecular Science, Institute for Molecular Science, National Institutes of Natural Sciences, 5-1 Higashiyama, Myodaiji, Okazaki, Aichi 444-8787, Japan.
authors.forename: Toshikazu
authors.initials: T
authors.lastname: Nakamura
authors.affiliation: ⊥Department of Material and Life Science, Graduate School of Engineering, Osaka University, ALCA, JST, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan.
authors.forename: Shunichi
authors.initials: S
authors.lastname: Fukuzumi
authors.affiliation: ‡WPI-Research Initiative-Institute of Transformative Bio-Molecules and Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8602, Japan.
authors.forename: Stephan
authors.initials: S
authors.lastname: Irle
authors.affiliation: †Department of Materials Molecular Science, Institute for Molecular Science, National Institutes of Natural Sciences, 5-1 Higashiyama, Myodaiji, Okazaki, Aichi 444-8787, Japan.
authors.forename: Donglin
authors.initials: D
authors.lastname: Jiang
mesh_terms: D004583:Electrons; D007094:Imides / Q000737:chemistry*; D007211:Indoles / Q000737:chemistry*; D054833:Isoindoles; D008670:Metals / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D009281:Naphthalenes / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010569:Perylene / Q000031:analogs & derivatives* / Q000737:chemistry; D011108:Polymers / Q000737:chemistry*; D014961:X-Ray Diffraction
chemical_list: D007094:Imides; D007211:Indoles; D054833:Isoindoles; D008670:Metals; D009281:Naphthalenes; D009942:Organometallic Compounds; D011108:Polymers; C521332:perylenediimide; C542131:naphthalenediimide; D010569:Perylene; C013647:phthalocyanine