Redox-active metal-organic frameworks constructed using novel rylene diimides

Ogar, Joseph Ochocheowoni (2021) Redox-active metal-organic frameworks constructed using novel rylene diimides. PhD thesis, University of Nottingham.

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The synthesis and characterisation of three rylene diimides – N,N’-bis(2,6-diisopropyl-4-(pyridin-4-yl)phenyl)-1,4,5,8-naphthalenetetracarboxydiimide (DPPNDI), N,N’-bis(dinicotinic acid)-1,4,5,8-naphthalenetetracarboxydiimide (DNNDI) and N,N’-bis(2,6-diisopropyl-4-(pyridin-4-yl)phenyl)-3,4:9,10-perylenetetracarboxydiimide (DPPPDI) are reported here alongside the metal-organic frameworks (MOFs) prepared with them. Another linker used in this study is the widely studied N,N’-di-(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide or DPNDI. Each of the materials contains a redox-active functionalised naphthalenediimide (NDI) or perylenediimide (PDI). A total of 14 MOFs (1 – 14) are reported herein. The frameworks 1 – 7 were constructed using either DPNDI/DPPNDI or DPPPDI (acting as pillars) in conjunction with carboxylate linkers (acting as sheets) all of which are coordinated to either a Co2+ or Ni2+ centre. Frameworks 8 – 14 were constructed utilising DNNDI linker and seven lanthanides (Lanthanide = Dy 8, Ce 9, Pr 10, Gd 11, Ho 12, La 13 and Nd 14). The MOFs were all made by a straight-forward solvothermal method and characterised using SCXRD, PXRD, TGA ancyclic voltammetry and Uv-Vis spectroscopy. All the frameworks containing DPNDI, DPPNDI or DPPPDI 2 – 7 are two-fold interpenetrated except 1 which is non-interpenetrated. In terms of dimensionality, 1 and 6 is two-dimensional all the other materials are three-dimensional. The secondary building units (SBUs) are {[M(k2-O2NO)]2(μ2-O2CR)2} paddle wheel SBU for 1, M2(μ2-O2CR)4 paddle-wheel SBU for 2 – 7 and M-O-C rod SBUs with MO8 polyhedra for 8 – 14. Host-guest experiments involving the encapsulation of molecular ferrocene are also reported. The solid state electrochemistry of all the MOFs indicate that the electrochemical behaviours of the rylene linker were exhibited by the MOFs constructed from them. Due to the presence of the redox-active ligands, these MOFs hold great potential for the entrapment of other electron-rich species which can in turn lead to new and exciting chemical properties.

Item Type: Thesis (University of Nottingham only) (PhD)
Supervisors: Champness, Neil R.
Amabilino, David
Keywords: Redox-active, Metal-organic frameworks, Novel rylene diimides
Subjects: Q Science > QD Chemistry
Faculties/Schools: UK Campuses > Faculty of Science > School of Chemistry
Item ID: 67121
Depositing User: Ogar, Joseph
Date Deposited: 08 Dec 2021 04:40
Last Modified: 08 Dec 2022 04:30

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