Electrochromism of Electropolymerized Metallophthalocyanines

In this paper, metallophthalocyanines (MPcs; M = 2H+ (H2Pc); Ni2+ (NiPc) and Cu2+ (CuPc)) bearing electropolymerizable amino substituents were easily and controllably electropolymerized on the working electrodes as thin solid films and electrochromic properties of these films were studied in detail with the various electrochemical, in-situ spectroelectrochemical and in-situ electrocolorimetric analysis methods. Although H2Pc and CuPc showed reasonable electrochromic features, NiPc illustrated excellent electrochromic responses with the fast response times, high optic contrast and better optical and coulombic stabilities. Although, monomeric H2Pc, NiPc, and CuPc did not behave as electrochromic materials, surprisingly the electropolymerized films of these complexes illustrated electrochemically triggered color changes between cyan and yellow or red colors. H2Pc is the first example of the metal free phthalocyanine, whose electropolymerized film behaved as an anodic coloring material. © 2013 The Electrochemical Society. [DOI: 10.1149/2.002403jes] All rights reserved.

[1]  C. Tanyeli,et al.  Electrochromic properties of a novel low band gap conductive copolymer , 2007 .

[2]  R. Mortimer,et al.  9.13 – Metal Complexes as Dyes for Optical Data Storage and Electrochromic Materials , 2003 .

[3]  D. Sokaras,et al.  Origin of electrochromism in high-performing nanocomposite nickel oxide. , 2013, ACS applied materials & interfaces.

[4]  B. Salih,et al.  Synthesis and electrochemical, electrochromic and electrical properties of novel s-triazine bridged trinuclear Zn(II), Cu(II) and Lu(III) and a tris double-decker Lu(III) phthalocyanines , 2011 .

[5]  Maria Luz Rodriguez-Mendez,et al.  Nanostructured thin films based on phthalocyanines: electrochromic displays and sensors , 2009 .

[6]  A. Koca,et al.  3,4-Ethylenedioxythiophene substituted phthalocyanines , 2011 .

[7]  L. Gaffo,et al.  Electrochromic and redox properties of Langmuir–Blodgett films of ytterbium bisphthalocyanine , 2001 .

[8]  O. Sato.  Electrochromism and electrochemical magnetism in Ni–Fe Prussian blue , 2007 .

[9]  D. R. Clarke,et al.  Annual Review of Materials Research. Materials science of biological systems , 2011 .

[10]  John R. Reynolds,et al.  Electrochromic organic and polymeric materials for display applications , 2006, Displays.

[11]  A. Koca,et al.  Synthesis and electrochemical properties of a double-decker lutetium(III) phthalocyanine bearing electropolymerizable substituents on non-peripheral positions , 2014 .

[12]  L. G. Tomilova,et al.  Electrochemical and electrochromic properties of rare-earth metal diphthalocyanine complexes , 2001 .

[13]  Debajyoti Mondal,et al.  Improved reversibility of color changes in electrochromic Ni–Al layered double hydroxide films in presence of electroactive anions , 2012 .

[14]  Gunnar A. Niklasson,et al.  Electrochromism in nickel oxide films containing Mg, Al, Si, V, Zr, Nb, Ag, or Ta , 2004 .

[15]  P. Patil,et al.  Electrochromism in spray deposited iridium oxide thin films , 2005 .

[16]  I. Chambrier,et al.  108 – Phthalocyanine Thin Films: Deposition and Structural Studies , 2003 .

[17]  G. Wallace,et al.  Ion effects in REDOX cycling of conducting polymer based electrochromic materials , 2010 .

[18]  P. Monk,et al.  Pulsed electrolysis enhancement of electrochromism in viologen systems: Influence of comproportionation reactions , 1993 .

[19]  L. Toppare,et al.  Green to highly transmissive switching multicolored electrochromes: Ferrocene pendant group effect on electrochromic properties , 2011 .

[20]  P. Somani,et al.  Electrochromic materials and devices: present and future , 2003, Materials Chemistry and Physics.

[21]  A. Koca,et al.  Synthesis, characterization, electrochemical and spectroelectrochemical properties of metal-free and metallophthalocyanines bearing electropolymerizable dimethylamine groups , 2013 .

[22]  L. Aras,et al.  Electropolymerization of a new 4‐(2,5‐Di‐2‐thiophen‐2‐yl‐pyrrol‐1‐yl)‐tetra substituted nickel phthalocyanine derivative , 2011 .

[23]  Cheng Haifeng,et al.  Multicolor electrochromism of low‐bandgap copolymers based on pyrrole and 3,4‐ethylenedioxythiophene: Fine‐tuning colors through feed ratio , 2013 .

[24]  Cheng Haifeng,et al.  Tricolor electrochromism of PEDOT film electrodeposited in mixed solution of boron trifluoride diethyl etherate and tetrahydrofuran: Hypsochromic effect , 2013 .

[25]  B. Salih,et al.  Synthesis, Characterization, Nonlinear Absorption and Electrochromic Properties of Double-Decker Octakis(mercaptopropylisobutyl-POSS)phthalocyaninatolanthanide(III) Complexes , 2008 .

[26]  N. Kobayashi,et al.  Recent progress in phthalocyanine chemistry: Synthesis and characterization , 2006 .

[27]  A. Koca,et al.  Electrochemistry and spectroelectrochemistry of tert-butylcalix[4]arene bridged bis double-decker lutetium(III) phthalocyanine, Lu2Pc4 and dimeric lutetium(III) phthalocyanine, Lu2Pc2(OAc)2 , 2007 .

[28]  Hui-min Wang,et al.  Novel organosoluble aromatic polyetheramides bearing triphenylamine moieties: synthesis, electrochemistry, and electrochromism , 2013, Journal of Polymer Research.