Copper-Bipyridine Grid Frameworks Incorporating Redox-Active Tetrathiafulvalene: Structures And Supercapacitance

Redox active tetrathiafulvalene (TTF) and its derivatives when used as electrode additives have exhibited improved energy efficiency and sustainability in batteries. However, the structure-property relationship has not been investigated in detail until very recently. In this work, three redox-active TTF compounds were synthesized, and formulated as [Cu(HL)(2)(bpa)(2)](n) (1), [Cu(bpe)(2)(H2O)(2)](n)center dot 2n(HL)center dot nMeOH center dot nH(2)O (2), and [Cu(bpp)(2)(H2O)(2)](n)center dot 2n(HL) (3) (L = dimethylthio-tetrathiafulvalene-bicarboxylate) for this work. The effects of conjugated state and spacer length of the linkers on structural assembly and band gap as well as the interactions of TTF-TTF/TTF-bpy are discussed. Compound 1 is a bpa and HL co-coordinated 1D Cu(ii) polymer. Compounds 2 and 3 are 2D Cu(ii)-bipyridine (4,4) MOFs incorporating HL (1(-)) as free anion columns. The photocurrent density of 2 is larger than those of 1 and 3 due to a strong charge transfer from TTF to bpe in compound 2. The supercapacitance performances of these compounds were evaluated by cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) techniques. The results revealed that the 2D MOF structures of 2 and 3 are beneficial for good specific capacitance values (C-sp). This work revealed the structure-property relationships of TTF derivatives for use as electrode active materials in energy transfer and storage.