Electrochemically-induced TCNQ/Mn[TCNQ]2(H2O)2 (TCNQ = 7,7,8,8- Tetracyanoquinodimethane) solid-solid interconversion: Two voltammetrically distinct processes that allow selective generation of nanofiber or nanorod network morphologies

Nafady, A, Bond, A and O'Mullane, A 2009, 'Electrochemically-induced TCNQ/Mn[TCNQ]2(H2O)2 (TCNQ = 7,7,8,8- Tetracyanoquinodimethane) solid-solid interconversion: Two voltammetrically distinct processes that allow selective generation of nanofiber or nanorod network morphologies', Inorganic Chemistry, vol. 48, pp. 9258-9270.


Document type: Journal Article
Collection: Journal Articles

Title Electrochemically-induced TCNQ/Mn[TCNQ]2(H2O)2 (TCNQ = 7,7,8,8- Tetracyanoquinodimethane) solid-solid interconversion: Two voltammetrically distinct processes that allow selective generation of nanofiber or nanorod network morphologies
Author(s) Nafady, A
Bond, A
O'Mullane, A
Year 2009
Journal name Inorganic Chemistry
Volume number 48
Start page 9258
End page 9270
Total pages 13
Publisher American Chemical Society
Abstract Unlike the case with other divalent transition metal M[TCNQ](2)(H(2)O)(2) (M = Fe, Co, Ni) analogues, the electrochemically induced solid-solid phase interconversion of TCNQ microcrystals (TCNQ = 7,7,8,8-tetracyanoquinodimethane) to Mn[TCNQ](2)(H(2)O)(2) occurs via two voltammetrically distinct, time dependent processes that generate the coordination polymer in nanofiber or rod-like morphologies. Careful manipulation of the voltammetric scan rate, electrolysis time, Mn(2+)((aq)) concentration, and the method of electrode modification with solid TCNQ allows selective generation of either morphology. Detailed ex situ spectroscopic (IR, Raman), scanning electron microscopy (SEM), and X-ray powder diffraction (XRD) characterization clearly establish that differences in the electrochemically synthesized Mn-TCNQ material are confined to morphology. Generation of the nanofiber form is proposed to take place rapidly via formation and reduction of a Mn-stabilized anionic dimer intermediate, [(Mn(2+))(TCNQ-TCNQ)(2)(*-)], formed as a result of radical-substrate coupling between TCNQ(*-) and neutral TCNQ, accompanied by ingress of Mn(2+) ions from the aqueous solution at the triple phase TCNQ/electrode/electrolyte boundary. In contrast, formation of the nanorod form is much slower and is postulated to arise from disproportionation of the [(Mn(2+))(TCNQ-TCNQ)(*-)(2)] intermediate. Thus, identification of the time dependent pathways via the solid-solid state electrochemical approach allows the crystal size of the Mn[TCNQ](2)(H(2)O)(2) material to be tuned and provides new mechanistic insights into the formation of different morphologies.
Subject Electrochemistry
DOI - identifier 10.1021/ic9011394
Copyright notice 2009 American Chemical Society
ISSN 0020-1669
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