title: Redox-Active Metal-Organic Frameworks: Highly Stable Charge-Separated States through Strut/Guest-to-Strut Electron Transfer.
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 H2 O⋅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.
authors.affiliation: Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore-560064 (India).
authors.forename: Nivedita
authors.initials: N
authors.lastname: Sikdar
authors.affiliation: Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore-560064 (India).
authors.forename: Kolleboyina
authors.initials: K
authors.lastname: Jayaramulu
authors.affiliation: Department of Inorganic and Physical Chemistry, Indian Institute of Science (IISc), Bangalore-560012 (India).
authors.forename: Venkayala
authors.initials: V
authors.lastname: Kiran
authors.affiliation: New Chemistry Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore-560064 (India).
authors.forename: K Venkata
authors.initials: KV
authors.lastname: Rao
authors.affiliation: Department of Inorganic and Physical Chemistry, Indian Institute of Science (IISc), Bangalore-560012 (India).
authors.forename: Srinivasan
authors.initials: S
authors.lastname: Sampath
authors.affiliation: New Chemistry Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore-560064 (India). george@jncasr.ac.in.
authors.forename: Subi J
authors.initials: SJ
authors.lastname: George
authors.affiliation: Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore-560064 (India). tmaji@jncasr.ac.in.|New Chemistry Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore-560064 (India). tmaji@jncasr.ac.in.
authors.forename: Tapas Kumar
authors.initials: TK
authors.lastname: Maji
keywords: electron transfer; host-guest systems; metal-organic frameworks; photochromism; redox-active systems