Triply N‐Confused Hexaphyrins(1.1.1.1.1.0) Synthesized From N‐Confused Hexaphyrin(2.1.1.1.1.1): Aromaticity Modulation, Metal Coordination, and Photothermal Conversion
Abstract
ABSTRACT Antiaromatic compounds exhibit intriguing structures, reactivity, and physicochemical properties. To address the challenge in developing stable antiaromatic porphyrinoids, a vinylene bridge and an α,β′‐linked pyrrole unit were used to synthesize a 28π Möbius aromatic N‐confused oxohexaphyrin(2.1.1.1.1.1) ( 1 ). Subsequent oxidative C β –C β fusion afforded a stable Hückel antiaromatic formally triply N‐confused oxohexaphyrin(1.1.1.1.1.0) ( 2 ) as a hybrid of 24 and 28π systems with two peripheral NH moieties, enabling further C–N fusion with the adjacent C 6 F 5 moiety under basic conditions to yield the corresponding N‐confused dioxohexaphyrin(1.1.1.1.1.0) ( 3 ), which shows Hückel antiaromaticity with a modulated circuit. Coordination of various metals within the distinct coordination cavities afforded two mono‐rhenium complexes 3‐Re‐1 (NNη 2 ‐coordinated) and 3‐Re‐2 (NNO‐coordinated) along with a mono‐Pd complex 3‐Pd‐1 (CNNO‐coordinated) with modulated antiaromaticity. On this basis, the heterobimetallic complex 3‐O‐Pd‐Re was synthesized with the conjugation and antiaromaticity disrupted by further oxygenation. Notably, these compounds display distinctive near‐infrared (NIR) absorption, enabling pronounced photothermal conversion under 1064 nm laser irradiation with efficiencies up to 61.4%. This work composes an effective post‐fusion approach for developing multiply N‐confused porphyrinoids with tunable antiaromaticity and distinctive coordination properties to achieve efficient NIR photothermal conversion behavior.
Article Details
Authors (13)
Gaojie Zhu
Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering Shanghai Key Laboratory of Functional Materials Chemistry Feringa Nobel Prize Scientist Joint Research Center Frontiers Science Center for Materiobiology and Dynamic Chemistry Institute of Fine Chemicals School of Chemistry and Molecular Engineering East China University of Science and Technology Shanghai China
Zimei Ma
Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering Shanghai Key Laboratory of Functional Materials Chemistry Feringa Nobel Prize Scientist Joint Research Center Frontiers Science Center for Materiobiology and Dynamic Chemistry Institute of Fine Chemicals School of Chemistry and Molecular Engineering East China University of Science and Technology Shanghai China
Mingbo Zhou
Key Laboratory of Chemical Biology and Traditional Chinese Medicine, Ministry of Education of China, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province College of Chemistry and Chemical Engineering Hunan Normal University Changsha China
Hailong Wang
Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering
Shijun Li
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education
Rinat Nasibullin
Department of Science and Technology Institution Laboratory of Organic Electronics Linköping University Norrköping Sweden
Glib Baryshnikov
Laboratory of Organic Electronics, Department of Science and Technology
Chengjie Li
Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Shanghai Key Laboratory of Functional Materials Chemistry, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, State Key Laboratory of Bioreactor Engineering, Engineering Research Centre of Pharmaceutical Process Chemistry, Ministry of Education, Laboratory of Pharmaceutical Crystal Engineering & Technology, School of Pharmacy, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China
Hans Ågren
School of Chemistry and Chemical Engineering
Jianxin Song
Jianzhuang Jiang
Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering
Qizhao Li
Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Shanghai Key Laboratory of Functional Materials Chemistry, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, State Key Laboratory of Bioreactor Engineering, Engineering Research Centre of Pharmaceutical Process Chemistry, Ministry of Education, Laboratory of Pharmaceutical Crystal Engineering & Technology, School of Pharmacy, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China
Yongshu Xie
Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Shanghai Key Laboratory of Functional Materials Chemistry, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, State Key Laboratory of Bioreactor Engineering, Engineering Research Centre of Pharmaceutical Process Chemistry, Ministry of Education, Laboratory of Pharmaceutical Crystal Engineering & Technology, School of Pharmacy, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China