Conductive casting films based on an octasilicate-core dendrimer containing the mixed-valence state TCNQ on the periphery

An octasilicate (OS)-core dendrimer terminated with imidazolium–7,7,8,8-tetracyanoquiodimethane (TCNQ) anion radicals (OS-mimTCNQ) was synthesized from an OS-core dendrimer having alkyl bromides as terminal groups (OS-mimBr) via anion exchange reaction with lithium TCNQ salt (LiTCNQ) in water. Conductive films were prepared by casting mixtures of OS-mimTCNQ with the neutral TCNQ in acetonitrile on glass substrates. Although the casting film of OS-mimTCNQ showed low conductivity (<10−6 S cm−1), the casting films showed relatively high electron conductivity. In particular, the casting film with the same feed molar ratio between the neutral TCNQ and the terminated imidazolium moiety (OS-CT1.0) showed the highest conductivity (5.4 × 10−2 S cm−1). The stacking structure with the mixed-valence state of TCNQ in these casting films was confirmed by UV-vis-NIR spectra. The grazing incidence X-ray diffraction (GI-XD) of OS-CT1.0 showed an anisotropic pattern, indicating that the OS-core dendrimer arranged in the direction of the out-of-plane.

[1]  K. Naka,et al.  Single component transparent free‐standing films based on polyhedral octasilicate‐core dendrimers bearing carbazole terminal groups and their emission properties , 2016 .

[2]  K. Naka,et al.  Syntheses of biphenyl‐terminated polyhedral oligomeric octasilicate‐core dendrimers and their single‐component optical transparent free‐standing thermoplastic films , 2015 .

[3]  V. Starodub,et al.  Radical anion salts and charge transfer complexes based on tetracyanoquinodimethane and other strong -electron acceptors , 2014 .

[4]  R. Shinke,et al.  Synthesis of imidazolium salt-terminated poly(amidoamine)-typed POSS-core dendrimers and their solution and bulk properties , 2014 .

[5]  K. Naka,et al.  Effect of tertiary aliphatic amines on self-assembly of TCNQ in mixed-valence state , 2013 .

[6]  Anthony P O'Mullane,et al.  Effect of imidazolium-based ionic liquids on the nanoscale morphology of CuTCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane) metal-organic semiconductors. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[7]  A. Bond,et al.  Synthesis, Physical Properties, Structural, and Electrochemical Characterization of Methimidazolium and Imidazolium-based Tetracyanoquinodimethane Anion Radical Salts , 2011 .

[8]  S. Schricker,et al.  Synthesis and Characterization of Inorganic-Organic Hybrid Materials Derived from Polysilsesquioxanes (POSS) , 2010 .

[9]  P. D. Lickiss,et al.  Recent developments in the chemistry of cubic polyhedral oligosilsesquioxanes. , 2010, Chemical reviews.

[10]  A. Mudring,et al.  Synthesis, structure, and physico-optical properties of manganate(II)-based ionic liquids. , 2010, Chemistry.

[11]  R. Clérac,et al.  Glassy Magnets Composed of Metals Coordinated to 7,7,8,8-tetracyanoquinodimethane: M(TCNQ)2 (M = Mn, Fe, Co, Ni)† , 2003 .

[12]  G. Stevens,et al.  Two conductive phases of 1,3-dimethylimidazolium-(TCNQ)2 complex salt , 1996 .

[13]  Y. Ozaki,et al.  Structure and Degree of Charge Transfer of Simple and Complex Cyanine-TCNQ Anion Radical Salts Studied by Resonance Raman and Infrared Spectroscopy , 1995 .

[14]  T. Welton,et al.  1:1 Imidazolium 7,7',8,8'-Tetracyano-p-quinodimethanide ([TCNQ].bul.-) Salts: Substituent Control of Solid-State Architecture , 1994 .

[15]  M. Kryszewski,et al.  Charge transfer complexes and salts of ionenes , 1994 .

[16]  S. Pons,et al.  An Infrared Spectroelectrochemical Investigation of the Ion Pairing Reactions of the Anions and Dianions of TCNE and TCNQ , 1987 .

[17]  S. Nespurek,et al.  Physical properties of the TCNQ salts with 1-methyl-3-alkylimidazolium derivatives , 1987 .

[18]  J. Torrance The difference between metallic and insulating salts of tetracyanoquinodimethone (TCNQ): how to design an organic metal , 1979 .

[19]  W. Mahler,et al.  Substituted Quinodimethans. II. Anion-radical Derivatives and Complexes of 7,7,8,8-Tetracyanoquinodimethan , 1962 .