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Hybrid CuTCNQ/AgTCNQ Metal‐Organic Charge Transfer Complexes via Galvanic Replacement vs Corrosion‐Recrystallization
Author(s) -
Pearson Andrew,
Ramanathan Rajesh,
O'Mullane Anthony P.,
Bansal Vipul
Publication year - 2014
Publication title -
advanced functional materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 6.069
H-Index - 322
eISSN - 1616-3028
pISSN - 1616-301X
DOI - 10.1002/adfm.201402320
Subject(s) - materials science , galvanic cell , acetonitrile , hybrid material , aqueous solution , organic semiconductor , recrystallization (geology) , metal , tetracyanoquinodimethane , electrochemistry , chemical engineering , nanotechnology , semiconductor , organic chemistry , molecule , chemistry , electrode , metallurgy , paleontology , optoelectronics , engineering , biology
This study reports a hybrid of two metal‐organic semiconductors that are based on organic charge transfer complexes of 7,7,8,8‐tetracyanoquinodimethane (TCNQ). It is shown that the spontaneous reaction between semiconducting microrods of CuTCNQ with Ag + ions leads to the formation of a CuTCNQ/AgTCNQ hybrid, both in aqueous solution and acetonitrile, albeit with completely different reaction mechanisms. In an aqueous environment, the reaction proceeds by a complex galvanic replacement (GR) mechanism, wherein in addition to AgTCNQ nanowires, Ag 0 nanoparticles and Cu(OH) 2 crystals decorate the surface of CuTCNQ microrods. Conversely, in acetonitrile, a GR mechanism is found to be thermodynamically unfavorable and instead a corrosion‐recrystallization mechanism leads to the decoration of CuTCNQ microrods with AgTCNQ nanoplates, resulting in a pure CuTCNQ/AgTCNQ hybrid metal‐organic charge transfer complex. While hybrids of two different inorganic semiconductors are regularly reported, this report pioneers the formation of a hybrid involving two metal‐organic semiconductors that will expand the scope of TCNQ‐based charge transfer complexes for improved catalysis, sensing, electronics, and biological applications.