RMIT University
Browse

Systematic Approach to the Synthesis of Cobaltocenium Salts with Reduced Forms of TCNQF 4 : Two [Cp 2 Co](TCNQF 4 ) Polymorphs and [Cp 2 Co]Li(TCNQF 4 )

journal contribution
posted on 2024-11-02, 20:18 authored by Jinzhen Lu, Ruchika OjhaRuchika Ojha, Alan Bond, Lisandra Martin
Three new crystallographically characterized compounds were prepared in high yield from reactions between [Cp 2 Co]PF 6 (Cp = cyclopentadiene) and lithium salts of the radical anion of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (TCNQF 41- ) or the dianionic TCNQF 42- . The two [Cp 2 Co]TCNQF 4 compounds (1 and 2) with 1:1 stoichiometry were found to be polymorphic, α and β. Remarkably, the syntheses only differed by the presence of a small amount of neutral TCNQF 4 in the case of polymorph β (2). The role of the TCNQF 4 has been rationalized on the basis of a transient intermediate, postulated as [Cp 2 Co](TCNQF 4 ) 2 . Compound 3 contains TCNQF 42- and crystallized as [Cp 2 Co]Li(TCNQF 4 ). This material highlights a novel coordination mode for the Li + cation that participated in the formation of a metal-organic framework accommodating the [Cp 2 Co] + cation. All complexes were comprehensively characterized by Fourier transform infrared spectroscopy, UV-vis spectroscopy, and electrochemistry. Polymorph β (2) has a conductivity of 5.8 × 10 -4 S cm -1 , which lies well within the semiconductor range. Previous work in this area employed redox chemistry based on the reaction of cobaltocene or ferrocene with neutral TCNQ. The introduction of metathesis reactions enhances the synthetic flexibility enabling a systematic approach to new materials.

History

Journal

Crystal Growth and Design

Volume

19

Issue

5

Start page

2712

End page

2722

Total pages

11

Publisher

American Chemical Society

Place published

United States of America

Language

English

Copyright

© 2019 American Chemical Society

Former Identifier

2006117076

Esploro creation date

2022-09-15

Usage metrics

    Scholarly Works

    Keywords

    Exports

    RefWorks
    BibTeX
    Ref. manager
    Endnote
    DataCite
    NLM
    DC