Twist glass transition in regioregulated poly(3-alkylthiophene)

The molecular structure and dynamics of regioregulated poly(3-butylthiophene) (P3BT), poly(3-hexylthiophene) (P3HT), and poly(3-dodecylthiophene) (P3DDT) were investigated using Fourier-transform infrared absorption (FTIR), solid-state $^{13}\mathrm{C}$ nuclear-magnetic resonance (NMR), and differential-scanning calorimetry (DSC) measurements. In the DSC measurements, the endothermic peak was obtained around $340\phantom{\rule{0.3em}{0ex}}\mathrm{K}$ in P3BT, and assigned to enthalpy relaxation that originated from the glass transition of the thiophene-ring twist in crystalline phase from results of FTIR, $^{13}\mathrm{C}$ cross-polarization and magic-angle spinning (CPMAS) NMR, $^{13}\mathrm{C}$ spin-lattice relaxation-time measurements, and centerband-only detection of exchange (CODEX) measurements. We defined this transition as a twist-glass transition, which is analogous to the plastic crystal--glassy crystal transition.

[1]  G. Hinze,et al.  2H nuclear magnetic resonance study of supercooled toluene: Slow and fast processes above and below the glass transition , 1996 .

[2]  H. Suga,et al.  Phase Changes in Crystalline and Glassy-Crystalline Cyclohexanol , 1968 .

[3]  A. Sokolov,et al.  Indications for a change of transport mechanism in supercooled liquids and the dynamics close and below Tg , 1994 .

[4]  David R. Nelson,et al.  Dislocation-mediated melting in two dimensions , 1979 .

[5]  Liu,et al.  Excitations in incommensurate biphenyl: Proton spin-lattice relaxation. , 1985, Physical review letters.

[6]  Graham Williams,et al.  Non-symmetrical dielectric relaxation behaviour arising from a simple empirical decay function , 1970 .

[7]  H. Zimmermann,et al.  Structural relaxation of the fragile glass-former propylene carbonate studied by nuclear magnetic resonance , 2000 .

[8]  D. Morton-Blake,et al.  ATOMISTIC INVESTIGATION OF THERMOCHROMISM IN A POLY(3-ALKYLTHIOPHENE) , 1997 .

[9]  R. Rieke,et al.  The first regioregular head-to-tail poly(3-hexylthiophene-2,5-diyl) and a regiorandom isopolymer: nickel versus palladium catalysis of 2(5)-bromo-5(2)-(bromozincio)-3-hexylthiophene polymerization , 1992 .

[10]  H. G. Zachmann,et al.  Glass transition temperature of copolyesters of PET, PEN and PHB as determined by dynamic mechanical analysis , 1991 .

[11]  Kazuhiro Tsuji,et al.  New Finding of Glassy Liquid Crystal – a Non-equilibrium State of Cholesteryl Hydrogen Phthalate , 1971 .

[12]  Martin Goldstein,et al.  Viscous Liquids and the Glass Transition. II. Secondary Relaxations in Glasses of Rigid Molecules , 1970 .

[13]  L. Carpentier,et al.  Nuclear magnetic resonance and dielectric investigations of molecular motions in a glassy crystal: the mixed compound (CN-adm)0.75(Cl-adm)0.25. , 2005, The Journal of chemical physics.

[14]  K. Park,et al.  Order−Disorder Transition in the Electroactive Polymer Poly(3-dodecylthiophene) , 1997 .

[15]  David R. Nelson,et al.  Theory of Two-Dimensional Melting , 1978 .

[16]  Valerio Causin,et al.  Crystallization and Melting Behavior of Poly(3-butylthiophene), Poly(3-octylthiophene), and Poly(3-dodecylthiophene) , 2005 .

[17]  Kenichiro Iwasaki,et al.  Conformational changes of poly(3-alkylthiophene)s with temperature and pressure , 1994 .

[18]  Thermochromism in polyalkylthiophenes: Molecular aspects from vibrational spectroscopy , 1991 .

[19]  W. R. Salaneck,et al.  Thermochromic and solvatochromic effects in poly(3-hexylthiophene) , 1988 .

[20]  W. Graupner,et al.  Planarity of para Hexaphenyl , 1999 .

[21]  Peter Pulay,et al.  Efficient implementation of the gauge-independent atomic orbital method for NMR chemical shift calculations , 1990 .

[22]  R. Böhmer,et al.  Dynamics of supercooled liquids and glassy solids , 2001 .

[23]  R. Böhmer,et al.  Dynamical heterogeneity in α- and β-relaxations of glass forming liquids as seen by deuteron NMR , 2000 .

[24]  S. Holdcroft,et al.  A Phenomenological Model for Predicting Thermochromism of Regioregular and Nonregioregular Poly(3-alkylthiophenes) , 1996 .

[25]  Dynamics of the quasiordered structure in the regioregulatedπ-conjugated polymer poly(4-methylthiazole-2,5-diyl) , 2004, cond-mat/0412419.

[26]  Stephen D. Jacobs,et al.  Novel Glassy Nematic Liquid Crystals for Non‐destructive Rewritable Optical Memory and Photonic Switching , 2003 .

[27]  A. Campo,et al.  Amorphous‐Smectic Glassy Main‐Chain LCPs, 1. Poly(ether esters) Derived from Hydroxybibenzoic Acid and (R,S)‐ and (R)‐2‐Methylpropane‐1,3‐diol , 2002 .

[28]  Jacob Schaefer,et al.  Magic-angle spinning and polarization transfer in proton-enhanced NMR , 1977 .

[29]  Tian-an Chen,et al.  Polyalkylthiophenes with the smallest bandgap and the highest intrinsic conductivity , 1993 .

[30]  A. Bolognesi,et al.  Structural and thermal behavior of poly(3-octylthiophene): a DSC, 13C MAS NMR, XRD, photoluminescence, and Raman scattering study , 2001 .

[31]  G. Barbarella,et al.  13C‐CPMAS NMR characterization and molecular dynamics of oligothiophenes in the solid state , 1996 .

[32]  E. deAzevedo,et al.  Principles of centerband-only detection of exchange in solid-state nuclear magnetic resonance, and extension to four-time centerband-only detection of exchange , 2000 .

[33]  D. Thouless,et al.  Ordering, metastability and phase transitions in two-dimensional systems , 1973 .

[34]  H. Chihara,et al.  Proton Magnetic Relaxation Study of Phase Transition in Crystalline p-Terphenyl , 1982 .

[35]  A. J. Lovinger,et al.  Influence of molecular weight and regioregularity on the polymorphic behavior of poly(3-decylthiophenes) , 1997 .

[36]  R. D. Mccullough,et al.  Evidence of a Novel Side Chain Structure in Regioregular Poly(3-alkylthiophenes) , 1996 .

[37]  31P to 77Se cross polarization in β-P4Se3 , 1997 .

[38]  E. Purcell,et al.  Relaxation Effects in Nuclear Magnetic Resonance Absorption , 1948 .

[39]  A. P. Young,et al.  Melting and the vector Coulomb gas in two dimensions , 1979 .

[40]  Schilling,et al.  Ideal glass transitions for hard ellipsoids , 2000, Physical review. E, Statistical physics, plasmas, fluids, and related interdisciplinary topics.

[41]  R. Tycko.  Molecular dynamics, phase diagrams and electronic properties of fullerenes and alkali fullerides: insights from solid-state nuclear magnetic resonance spectroscopy. , 1994, Solid state nuclear magnetic resonance.

[42]  Tian-An Chen,et al.  Synthesis of Regioregular Head-to-Tail Poly[3-(alkylthio)thiophenes]. A Highly Electroconductive Polymer , 1995 .

[43]  R. Ditchfield,et al.  Self-consistent perturbation theory of diamagnetism , 1974 .

[44]  E. deAzevedo,et al.  Centerband-Only Detection of Exchange: Efficient Analysis of Dynamics in Solids by NMR , 1999 .

[45]  D. Torchia.  The measurement of proton-enhanced carbon-13 T1 values by a method which suppresses artifacts , 1978 .

[46]  S. Chen,et al.  Structure/properties of conjugated conductive polymers. 1. Neutral poly(3-alkythiophene)s , 1992 .