Raman changes induced by electrochemical oxidation of poly(triarylamine)s: toward a relationship between molecular structure modifications and charge generation.

Linear, alternating polymers of aromatic amines (p-phenylenediamine, bis(p-aminophenyl)amine, and diaminocarbazole) and either m-phenylene or 3,5-pyridine have been synthesized and characterized by electrochemical and spectroscopic means. The presence of radical cations in their electrochemically oxidized forms is manifested by new bands in the UV-vis-NIR spectra whose appearance can be correlated with reversible redox couples registered in the corresponding cyclic voltammograms at approximately the same potentials as well as with pronounced evolutions of their resonance Raman spectra. Detailed analysis of the Raman data gives information about the locations and the distribution of radical cations and spinless dication in the macromolecule. This approach can provide a new insight into the formation of high-spin states in these polymers.

[1]  A. Pron,et al.  Vibrational dynamics in dendridic oligoarylamines by Raman spectroscopy and incoherent inelastic neutron scattering. , 2014, The journal of physical chemistry. B.

[2]  A. Rajca,et al.  High-spin S = 2 ground state aminyl tetraradicals. , 2013, Journal of the American Chemical Society.

[3]  A. Pron,et al.  Polymers for electronics and spintronics. , 2013, Chemical Society reviews.

[4]  P. Gawryś,et al.  Tuning of ferromagnetic spin interactions in polymeric aromatic amines via modification of their π-conjugated system. , 2012, The journal of physical chemistry. B.

[5]  K. Shiraishi,et al.  Ladder oligo(m-aniline)s: derivatives of azaacenes with cross-conjugated π-systems. , 2012, The Journal of organic chemistry.

[6]  P. Baran,et al.  Magnetic properties of a doped linear polyarylamine bearing a high concentration of coupled spins (S = 1). , 2012, Physical chemistry chemical physics : PCCP.

[7]  A. Rajca,et al.  Triplet ground state derivative of aza-m-xylylene diradical with large singlet-triplet energy gap. , 2011, Journal of the American Chemical Society.

[8]  R. Bushby,et al.  Disjoint and coextensive amminium radical cations : a general problem in making amminium radical cation based high-spin polymers , 2007 .

[9]  M. Zagorska,et al.  High-spin radical cations of poly(m-p-anilines) and poly (m-p-p -anilines ) : Synthesis and spectroscopic properties , 2007 .

[10]  Yasukazu Hirao,et al.  Intramolecular charge transfer in a star-shaped oligoarylamine. , 2007, The journal of physical chemistry. A.

[11]  R. Bushby,et al.  Ferromagnetic spin-coupling 4,4″-through metaterphenyl: models for high-spin polymers , 2007 .

[12]  Sanjay Kumar,et al.  Infrared, Raman spectra and DFT calculations of chlorine substituted anilines , 2006 .

[13]  A. Rajca,et al.  Organic spin clusters: macrocyclic-macrocyclic polyarylmethyl polyradicals with very high spin S = 5-13. , 2004, Journal of the American Chemical Society.

[14]  A. Rajca,et al.  Organic spin clusters. A dendritic-macrocyclic poly(arylmethyl) polyradical with very high spin of S = 10 and its derivatives: synthesis, magnetic studies, and small-angle neutron scattering. , 2004, Journal of the American Chemical Society.

[15]  T. Michinobu,et al.  m-Phenylene-linked aromatic poly(aminium cationic radical)s: persistent high-spin organic polyradicals. , 2003, Organic letters.

[16]  H. Nishide,et al.  Ladderlike ferromagnetic spin coupling network on a pi-conjugated pendant polyradical. , 2003, Journal of the American Chemical Society.

[17]  A. Rajca.  From high-spin organic molecules to organic polymers with magnetic ordering. , 2002, Chemistry.

[18]  Kazuyoshi Tanaka,et al.  Facile synthesis, crystal structures, and high-spin cationic states of all-para-brominated oligo(N-phenyl-m-aniline)s. , 2002, The Journal of organic chemistry.

[19]  A. Rajca,et al.  Magnetic Ordering in an Organic Polymer , 2001, Science.

[20]  Y. Teki,et al.  Synthesis and characterization of poly(1,3-phenylene)-based polyradicals carrying cyclic aminoxyls , 2001 .

[21]  Janssen,et al.  Ferromagnetic spin alignment in head-to-tail coupled oligo(1, 4-phenyleneethynylene)s and Oligo(1,4-phenylenevinylene)s bearing pendant p-phenylenediamine radical cations , 2000, The Journal of organic chemistry.

[22]  Y. Teki,et al.  Synthesis and Characterization of Poly(1,3-phenylene)-Based Polyradical Carrying Cyclic Nitroxides. Observation of Ferromagnetic Interaction , 1999 .

[23]  Richard H. Friend,et al.  Electronic structure of conjugated polymers: consequences of electron}lattice coupling , 1999 .

[24]  J. Hartwig,et al.  PALLADIUM-CATALYZED SYNTHESIS OF PURE, REGIODEFINED POLYMERIC TRIARYLAMINES , 1999 .

[25]  T. Michinobu,et al.  Robust Triplet Molecule: Cationic Diradical of 3,4‘-Bis(diphenylamino)stilbene , 1999 .

[26]  A. Rajca,et al.  Very high-spin organic polymer: π-Conjugated hydrocarbon network with average spin of S ≥ 40 [2] , 1999 .

[27]  S. Lefrant,et al.  RRS characterization of selected oligomers of polyaniline in situ spectroelectrochemical study , 1999 .

[28]  R. Janssen,et al.  High-Spin Cation Radicals of Meta−Para Aniline Oligomers , 1997 .

[29]  R. Bushby,et al.  Disjoint and coextensive diradical diions , 1997 .

[30]  R. Janssen,et al.  Stable Triplet-State Di(Cation Radicals) of a Meta−Para Aniline Oligomer by “Acid Doping” , 1996 .

[31]  A. MacDiarmid,et al.  Vibrational analysis of polyaniline: A comparative study of leucoemeraldine, emeraldine, and pernigraniline bases. , 1994, Physical review. B, Condensed matter.

[32]  A. Rajca,et al.  Organic Diradicals and Polyradicals: From Spin Coupling to Magnetism? , 1994 .

[33]  G. Berden,et al.  Spectroscopy on triphenylamine and its van der Waals complexes , 1992 .

[34]  V. Belsky,et al.  Structural investigation of the triaryl derivatives of the Group V elements. IX. Structure of triphenylamine, C18H15N , 1985 .

[35]  E. Bright Wilson,et al.  The Normal Modes and Frequencies of Vibration of the Regular Plane Hexagon Model of the Benzene Molecule , 1934 .