Redox‐Active Metal–Organic Frameworks: Highly Stable Charge‐Separated States through Strut/Guest‐to‐Strut Electron Transfer |
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Authors: | Nivedita Sikdar Dr. Kolleboyina Jayaramulu Dr. Venkayala Kiran Dr. K. Venkata Rao Prof. Srinivasan Sampath Prof. Subi J. George Prof. Tapas Kumar Maji |
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Affiliation: | 1. Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore‐560064 (India);2. Department of Inorganic and Physical Chemistry, Indian Institute of Science (IISc), Bangalore‐560012 (India);3. New Chemistry Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore‐560064 (India) |
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Abstract: | Molecular organization of donor and acceptor chromophores in self‐assembled materials is of paramount interest in the field of photovoltaics or mimicry of natural light‐harvesting systems. With this in mind, a redox‐active porous interpenetrated metal–organic framework (MOF), {[Cd(bpdc)(bpNDI)] ? 4.5 H2O ? DMF}n ( 1 ) has been constructed from a mixed chromophoric system. The μ‐oxo‐bridged secondary building unit, {Cd2(μ‐OCO)2}, guides the parallel alignment of bpNDI (N,N′‐di(4‐pyridyl)‐1,4,5,8‐naphthalenediimide) acceptor linkers, which are tethered with bpdc (bpdcH2=4,4′‐biphenyldicarboxylic acid) linkers of another entangled net in the framework, resulting in photochromic behaviour through inter‐net electron transfer. Encapsulation of electron‐donating aromatic molecules in the electron‐deficient channels of 1 leads to a perfect donor–acceptor co‐facial organization, resulting in long‐lived charge‐separated states of bpNDI. Furthermore, 1 and guest encapsulated species are characterised through electrochemical studies for understanding of their redox properties. |
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Keywords: | electron transfer host– guest systems metal– organic frameworks photochromism redox‐active systems |
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