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Redox‐Active Metal–Organic Frameworks: Highly Stable Charge‐Separated States through Strut/Guest‐to‐Strut Electron Transfer
Author(s) -
Sikdar Nivedita,
Jayaramulu Kolleboyina,
Kiran Venkayala,
Rao K. Venkata,
Sampath Srinivasan,
George Subi J.,
Maji Tapas Kumar
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201501614
Subject(s) - redox , electron transfer , photochromism , electrochemistry , chemistry , acceptor , chromophore , electron acceptor , metal organic framework , photochemistry , molecule , metal , electron donor , crystallography , nanotechnology , materials science , catalysis , electrode , inorganic chemistry , organic chemistry , adsorption , physics , condensed matter physics
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 H 2 O ⋅ DMF} n ( 1 ) has been constructed from a mixed chromophoric system. The μ‐oxo‐bridged secondary building unit, {Cd 2 (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 (bpdcH 2 =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.