High‐Temperature and High‐Energy‐Density Dipolar Glass Polymers Based on Sulfonylated Poly(2,6‐dimethyl‐1,4‐phenylene oxide)

A new class of high‐temperature dipolar polymers based on sulfonylated poly(2,6‐dimethyl‐1,4‐phenylene oxide) (SO₂‐PPO) was synthesized by post‐polymer functionalization. Owing to the efficient rotation of highly polar methylsulfonyl side groups below the glass transition temperature (T_g≈220 °C), the dipolar polarization of these SO₂‐PPOs was enhanced, and thus the dielectric constant was high. Consequently, the discharge energy density reached up to 22 J cm^?3. Owing to its high T_g , the SO₂‐PPO₂₅ sample also exhibited a low dielectric loss. For example, the dissipation factor (tan δ) was 0.003, and the discharge efficiency at 800 MV m^?1 was 92 %. Therefore, these dipolar glass polymers are promising for high‐temperature, high‐energy‐density, and low‐loss electrical energy storage applications.     

Synthesis,crystal structure and properties of a quaternary oxide with a new structure type,BiGaTi4O11

A new quaternary oxide, BiGaTi₄O₁₁ (bismuth gallium tetratitanium undecaoxide), was prepared by heating a mixture of the binary oxides at 1373 K in air. BiGaTi₄O₁₁ melts at 1487 K and prismatic single crystals were obtained from a sample melted at 1523 K and solidified by furnace cooling. The structure of BiGaTi₄O₁₁ was analyzed using single‐crystal X‐ray diffraction to be of a new type that crystallized in the space group Cmcm. A Bi³⁺ site is coordinated by nine O^2? anions, and three oxygen‐coordinated octahedral sites are statistically occupied by Ga³⁺ and Ti⁴⁺ cations. A relative dielectric constant of 46 with a temperature coefficient of 57 ppm K^?1 in the temperature range 297–448 K was measured for a polycrystalline ceramic sample at 150 Hz–1 MHz with a dielectric loss tan δ of less than 0.01. Electrical resistivities measured at 1073 K by alternating‐current impedance spectroscopic and direct‐current methods were 1.16 × 10^?4 and 1.14 × 10^?4 S cm^?1, respectively, which indicates that electrons and/or holes were conduction carriers at high temperature. The optical band gap estimated by the results of diffuse reflectance analysis was 2.9–3.0 eV, while the band gap obtained from the activation energy for electrical conduction was 3.5 eV.     

Far-infrared reflectivity study in optically non-linear crystal of potassium pentaborate

A study of far-IR (5–400 cm⁻¹) reflectivity spectra of potassium pentaborate tetrahydrate (KB₅O₈·4H₂O) crystal has been performed in the temperature range 90–300 K. Frequencies of the lattice longitudinal optical and transverse optical modes, their intensities, dampings as well as oscillator strengths and induced dipole moments, have been determined for this compound at two temperatures (90 and 300 K). Estimations of low frequency dielectric parameters from IR reflectivity spectra allowed us to evaluate the room temperature dispersion properties of the dielectric function in a wide frequency range.     

Intramolecular and Intermolecular Magnetic Coupling Mechanism of a Dinuclear Copper(II) Complex

Abstract. A new dinuclear complex, [Cu₂(μ_{1, 3}‐NCS)₂(Ophen)₂(OH₂)₂], (HOphen = 1, 10‐phenanthrolin‐2‐ol) was synthesized and its crystal structure was determined by X‐ray crystallography. In the complex, the Cu^II ion assumes a distorted square pyramidal arrangement and the thiocyanate anion functions as bridged ligand and Ophen as capped ligand. The analysis of the crystal structure shows that there exists a π–π stacking interaction between the adjacent complexes. The theoretical calculations reveal that the magnetic coupling pathways from the thiocyanate anions bridge ligand and the π–π stacking magnetic coupling pathway resulted in the weak ferromagnetic interactions with 2J = 18.46 cm^–1 and 2J = 10.46 cm^–1, respectively. The calculations also display that the spin delocalization and the spin polarization occur in the bridge magnetic coupling system and the π–π stacking magnetic coupling system, and the magnetic coupling mechanism of the π–π stacking can be explained with McConnell I spin‐polarization mechanism. The fitting for the data of the variable‐temperature magnetic susceptibility with dinuclear Cu^II formula gave the magnetic coupling constant 2J = 2.84 cm^–1 and zJ′ = 0.03 cm^–1, in which the 2J = 2.84 cm^–1 is attributed to the magnetic coupling from the bridge dinuclear Cu^II unit and the zJ′ = 0.03 cm^–1 is ascribed to the π–π stacking magnetic coupling system. The study may benefit to understand the magnetic coupling mechanism of π–π stacking system.     

Molecular Dynamics,Phase Transition and Frequency‐Tuned Dielectric Switch of an Ionic Co‐Crystal

Dielectric switches that can be converted between high and low dielectric states by thermal stimuli have attracted much interest owing to their many potential applications. Currently one main drawback for practical application lies in the non‐tunability of their switch temperatures (T_S). We report here an ionic co‐crystal (Me₃NH)₄[Ni(NCS)₆] that contains a multiply rotatable Me₃NH⁺ ion and a solely rotatable one due to a more spacious supramolecular cage for the former one. This compound undergoes an isostructural order–disorder phase transition and it can function as a frequency‐tuned dielectric switch with highly adjustable T_S, which is further revealed by the variable‐temperature structure analyses and molecular dynamics simulations. In addition, the distinct arrangements and molecular dynamics of two coexisting Me₃NH⁺ ions confined in different lattice spaces as well as the notable offset effect on the promoting/hindering of dipolar reorientation after dielectric transition provide a rarely observed but fairly good model for understanding and modulating the dipole motion in crystalline environment.     

Molecular Dynamics,Phase Transition and Frequency‐Tuned Dielectric Switch of an Ionic Co‐Crystal

Dielectric switches that can be converted between high and low dielectric states by thermal stimuli have attracted much interest owing to their many potential applications. Currently one main drawback for practical application lies in the non‐tunability of their switch temperatures (T_S). We report here an ionic co‐crystal (Me₃NH)₄[Ni(NCS)₆] that contains a multiply rotatable Me₃NH⁺ ion and a solely rotatable one due to a more spacious supramolecular cage for the former one. This compound undergoes an isostructural order–disorder phase transition and it can function as a frequency‐tuned dielectric switch with highly adjustable T_S, which is further revealed by the variable‐temperature structure analyses and molecular dynamics simulations. In addition, the distinct arrangements and molecular dynamics of two coexisting Me₃NH⁺ ions confined in different lattice spaces as well as the notable offset effect on the promoting/hindering of dipolar reorientation after dielectric transition provide a rarely observed but fairly good model for understanding and modulating the dipole motion in crystalline environment.     

Thermal Expansion,Anharmonicity and Temperature‐Dependent Raman Spectra of Single‐ and Few‐Layer MoSe2 and WSe2

We report the temperature‐dependent Raman spectra of single‐ and few‐layer MoSe₂ and WSe₂ in the range 77–700 K. We observed linear variation in the peak positions and widths of the bands arising from contributions of anharmonicity and thermal expansion. After characterization using atomic force microscopy and high‐resolution transmission electron microscopy, the temperature coefficients of the Raman modes were determined. Interestingly, the temperature coefficient of the A²_2u mode is larger than that of the A_1g mode, the latter being much smaller than the corresponding temperature coefficients of the same mode in single‐layer MoS₂ and of the G band of graphene. The temperature coefficients of the two modes in single‐layer MoSe₂ are larger than those of the same modes in single‐layer WSe₂. We have estimated thermal expansion coefficients and temperature dependence of the vibrational frequencies of MoS₂ and MoSe₂ within a quasi‐harmonic approximation, with inputs from first‐principles calculations based on density functional theory. We show that the contrasting temperature dependence of the Raman‐active mode A_1g in MoS₂ and MoSe₂ arises essentially from the difference in their strain–phonon coupling.     

Two‐Photon Voltmeter for Measuring a Molecular Electric Field

We present a new approach for determining the strength of the dipolar solute‐induced reaction field, along with the ground‐ and excited‐state electrostatic dipole moments and polarizability of a solvated chromophore, using exclusively one‐photon and two‐photon absorption measurements. We verify the approach on two benchmark chromophores N,N‐dimethyl‐6‐propionyl‐2‐naphthylamine (prodan) and coumarin 153 (C153) in a series of toluene/dimethyl sulfoxide (DMSO) mixtures and find that the experimental values show good quantitative agreement with literature and our quantum‐chemical calculations. Our results indicate that the reaction field varies in a surprisingly broad range, 0–10⁷ V cm^?1, and that at close proximity, on the order of the chromophore radius, the effective dielectric constant of the solute–solvent system displays a unique functional dependence on the bulk dielectric constant, offering new insight into the close‐range molecular interaction.     

Three‐component,negative‐type,alkaline‐developable,thermally stable,and photosensitive polymer based on poly(2,6‐dihydroxy‐1,5‐naphthalene), a crosslinker,and a photoacid generator

A negative working and chemically amplified photosensitive polymer has been developed, which is based on poly(2,6‐dihydroxy‐1,5‐naphthalene) (PDHN), the crosslinker 4,4′‐methylenebis[2,6‐bis(hydroxymethyl)]phenol, and the photoacid generator (5‐propylsulfonyloxyimino‐5H‐thiophen‐2‐ylidene)‐(2‐methylphenyl)acetonitrile. PDHN, with a number‐average molecular weight of 25,000, was prepared by the oxidative coupling polymerization of 2,6‐dihydroxynaphthalene with di‐μ‐hydroxo‐bis[(N,N,N′,N′‐tetramethylethylenediamine)copper(II)] chloride in 2‐methoxyethanol at room temperature. The resulting PDHN showed a 5% weight loss temperature of 440 °C in nitrogen and a low dielectric constant of 2.82. The resist showed a sensitivity of 8.3 mJ cm^?2 and a contrast of 11 when it was exposed to 436‐nm light, followed by postexposure baking at 100 °C for 5 min and development with a 2.38 wt % aqueous tetramethylammonium hydroxide solution at 25 °C. A fine negative image featuring 10‐μm line‐and‐space patterns was obtained on a film 3 μm thick exposed to 10 mJ cm^?2 of ultraviolet light at 436 nm in the contact‐printed mode. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2235–2240, 2004     

Switchable Dielectric Phase Transition Triggered by Pendulum‐Like Motion in an Ionic Co‐crystal

Molecular‐based ionic co‐crystals, which have the merits of low‐cost/easy fabrication processes and flexible structure and functionality, have already exhibited tremendous potential in molecular memory switches and other electric devices. However, dipole (ON/OFF switching) triggering is a huge challenge. Here, we introduce a pendulum‐like dynamic strategy to induce the order–disorder transition of a co‐crystal [C₅H₇N₃Cl]₃[Sb₂Br₉] (compound 1 ). Here, the anion and cation act as a stator and a pendulum‐like rotor (the source of the dielectric switch), respectively. The temperature‐dependent dielectric and differential scanning calorimetry (DSC) analyses reveal that 1 undergoes a reversible phase transition, which stems from the order–disorder transition of the cations. The thermal ON/OFF switchable motions make 1 a promising candidate to promote the development of bulk crystals as artificial intelligent dielectric materials. In addition, the pendulum‐like molecular dynamics and distinct arrangements of two coexisting ions with a notable offset effect promotes/hinders dipolar reorientation after dielectric transition and provides a rarely observed but fairly useful and feasible strategy for understanding and modulating the dipole motion in crystalline electrically polarizable materials.     

Molecular relaxation of isotactic polystyrene: Real‐time dielectric spectroscopy and X‐ray scattering studies*

The molecular relaxation processes and structure of isotactic polystyrene (iPS) films were investigated with real‐time dielectric spectroscopy and simultaneous wide‐ and small‐angle X‐ray scattering. The purpose of this work was to explore the restrictions imposed on molecular mobility in the vicinity of the α relaxation (glass transition) for crystallized iPS. Isothermal cold crystallization at temperatures of T_c = 140 or 170 °C resulted in a sigmoidal increase of crystallinity with crystallization time. The glass‐transition temperature (T_g), determined calorimetrically, exhibited almost no increase during the first stage of crystal growth before impingement of spherulites. After impingement, the calorimetric T_g increased, suggesting that confinement effects occur in the latter stages of crystallization. For well‐crystallized samples, the radius of the cooperativity region decreased substantially as compared with the purely amorphous sample but was always smaller than the layer thickness of the mobile amorphous fraction. Dielectric experiments directly probed changes in the amorphous dipole mobility. The real‐time dielectric data were fitted to a Havriliak–Negami model, and the time dependence of the parameters describing the distribution of relaxation times and dielectric strength was obtained. The central dipolar relaxation time showed little variation before spherulite impingement but increased sharply during the second stage of crystal growth as confinement occurred. Vogel–Fulcher–Tammann analysis demonstrated that the dielectric reference temperature, corresponding to the onset of calorimetric T_g, did not vary for well‐crystallized samples. This observation agreed with a model in which constraints affect primarily the modes having longer relaxation times and thus broaden the glass‐transition relaxation process on the higher temperature side. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 777–789, 2004     

Superoxide Compounds of the Large Pseudo‐Alkali‐Metal Ions Tetramethylammonium, ‐Phosphonium,and ‐Arsonium

Compounds of the three large cations tetramethylammonium, tetramethylphosphonium, and tetramethylarsonium with the superoxide radical anion were synthesized by either metathesis or ion exchange in liquid ammonia. They were obtained from concentrated solutions as ammoniates in the form of long needle‐shaped single crystals. [N(CH₃)₄]‐(O₂)?3NH₃ crystallizes in the monoclinic crystal system, whereas the two compounds [E(CH₃)₄](O₂)?2NH₃ (E=P, As) are isostructural and belong to the orthorhombic crystal system. The cation–anion packing in all three crystal structures is related to the sodium chloride structure. All structures contain hydrogen bonds between the ammonia molecules and between ammonia and the superoxide. The solvent of crystallization was easily released from the crystals upon complete removal of the solvent from the reaction vessel, leading to polycrystalline samples. The Raman spectra of all three solvent‐free compounds show the symmetric stretching mode of the superoxide ion at about 1123 cm^?1. The desolvated [N(CH₃)₄](O₂) was investigated by powder X‐ray diffraction, and the crystal structure was solved by ab initio simulated annealing methods by using rigid‐body models of the constituent molecular ions. The superoxide ion shows rotational disorder. The magnetic susceptibility of tetramethylammonium superoxide follows the Curie–Weiss law with a high‐temperature effective magnetic moment of 1.66(3) μ_B and a paramagnetic Curie temperature of Θ=?13(6) K. Complementary electron paramagnetic resonance spectroscopy revealed that the average g factor is temperature‐dependent. It decreased from 2.15 at 10 K to 1.66 at 100 K, possibly due to the onset of rotational motion of the superoxide ion and in accordance with the lower‐than‐expected effective magnetic moment.     

Strong Coupling and Laser Action of Ladder‐Type Oligo(p‐phenylene)s in a Microcavity

We investigate the coupling of ladder‐type quarterphenyl to the photon modes of a dielectric ZrO_x/SiO_x microcavity at ultraviolet wavelengths. For a relatively long cavity (≈10 μm) with high‐reflectivity mirrors (0.998), optically pumped laser action is demonstrated in the weak‐coupling regime. We observe single‐mode operation with a threshold of 0.4 mJ cm^?2. Strong coupling is achieved by using a short λ/2 cavity. We find pronounced anti‐crossing features of the molecular (0,0) and (0,1) vibronic transitions and the cavity mode in angle‐dependent reflectivity measurements providing Rabi splittings of (90±10) meV. All these features occur spectrally resonant to the exciton transition of ZnO demonstrating the potential of ladder‐type oligo(p‐phenylene)s for the construction of inorganic/organic hybrid microcavities.     

Magnetic Properties of Mixed Ligand NiII2 and NiII4 Complexes Composed of Macrocyclic Hexaamine‐Dithiophenolato and Bridging Tetrazolato Ligands

The magnetic properties of the dinuclear and tetranuclear nickel(II) tetrazolato complexes [Ni₂L(RCN₄)][BPh₄] (R = H ( 4 ), Me ( 5 ), Ph ( 6 )) and [(Ni₂L)₂(1,4‐(CN₄)₂‐C₆H₄)][BPh₄]₂ ( 7 ), where (L)^2– represents a 24‐membered macrocyclic N₆S₂ supporting ligand, are reported. Analysis of temperature‐dependent magnetic susceptibility measurements over the temperature range from 2 to 300 K revealed the presence of weak ferromagnetic exchange interactions between the Ni^II ions in the binuclear [Ni₂L(μ‐L′)]⁺ subunits with magnetic exchange coupling constant values of J₁ = 13.5 cm^–1 for 4 , J₁ = 20.0 cm^–1 for 5 , J₁ = 19.2 cm^–1 for 6 , and J₁ = 15.2 cm^–1 for 7 ( H = –2JS₁S₂). The exchange coupling J₂ across the bistetrazolato bridge in 7 is less than 0.1 cm^–1, which suggests that no significant interdimer coupling occurs in this compound. The synthesis and crystal structure of the new complex 7 ·2MeCN is also reported.     

Studying the Origin of the Antiferromagnetic to Spin‐Canting Transition in the β‐p‐NCC6F4CNSSN. Molecular Magnet

The crystal structure of the spin‐canted antiferromagnet β‐p‐NCC₆F₄CNSSN^. at 12 K (reported in this work) was found to adopt the same orthorhombic space group as that previously determined at 160 K. The change in the magnetic properties of these two crystal structures has been rigorously studied by applying a first‐principles bottom‐up procedure above and below the magnetic transition temperature (36 K). Calculations of the magnetic exchange pathways on the 160 K structure reveal only one significant exchange coupling (J(d1)=?33.8 cm^?1), which generates a three‐dimensional diamond‐like magnetic topology within the crystal. The computed magnetic susceptibility, χ(T), which was determined by using this magnetic topology, quantitatively reproduces the experimental features observed above 36 K. Owing to the anisotropic contraction of the crystal lattice, both the geometry of the intermolecular contacts at 12 K and the microscopic J_AB radical–radical magnetic interactions change: the J(d1) radical–radical interaction becomes even more antiferromagnetic (?43.2 cm^?1) and two additional ferromagnetic interactions appear (+7.6 and +7.3 cm^?1). Consequently, the magnetic topologies of the 12 and 160 K structures differ: the 12 K magnetic topology exhibits two ferromagnetic sublattices that are antiferromagnetically coupled. The χ(T) curve, computed below 36 K at the limit of zero magnetic field by using the 12 K magnetic topology, reproduces the shape of the residual magnetic susceptibility (having subtracted the contribution to the magnetization arising from spin canting). The evolution of these two ferromagnetic J_AB contributions explains the change in the slope of the residual magnetic susceptibility in the low‐temperature region.     

Preface

The anisotropic rototranslational scattering spectra of nitrogen gas at high frequency up to 700 cm⁻¹ for several temperatures and from low densities are analyzed in terms of new site–site (M3SV) intermolecular potential and interaction-induced pair polarizability models, using quantum spectral shapes computations. Our theoretical calculations take into account multipole contributions from the mean value and anisotropy of the dipole–dipole polarizability tensor α, two independent components of the dipole–octopole polarizability tensor E and dipole–dipole–quadrupole hyperpolarizability tensor B. The high-frequency wings are discussed in terms of the collision-induced rotational Rayleigh effect and estimates for the dipole–octopole polarizability |E₄| are obtained and checked with recent ab initio theoretical value. Good comparison is found in the frequency range 0–400 cm⁻¹ between the theoretical and experimental spectra. When an exponential contribution [exp(−ν/ν₀)] with ν₀ = 425 cm⁻¹ is considered to model very short-range light scattering mechanisms at room temperature, good agreement is found over the whole frequency range.     

Efficient Solution‐Processed Bulk Heterojunction Solar Cells by Antiparallel Supramolecular Arrangement of Dipolar Donor–Acceptor Dyes

A series of dipolar donor–acceptor (D –A) chromophores with aminothiophene donor and different heterocyclic acceptor units is reported. By modulation of the acceptor strength, absorption bands over the whole visible spectrum are accessible as well as adjustment of the frontier molecular orbital levels. The performance of the chromophores in blends with fullerene acceptors in solution‐processed bulk heterojunction solar cells was studied and related to the molecular properties of the dyes. In particular, the effect of the large ground‐state dipole moments of these dyes was investigated by single crystal X‐ray analysis, which revealed antiparallel dimers, resulting in an annihilation of the dipole moments. This specific feature of supramolecular organization explains the excellent performance of merocyanine dyes in organic solar cells. With blends of HB366 :PC₇₁BM, the most efficient solar cell with a V_OC of 1.0 V, a J_SC of 10.2 mA cm⁻², and a power‐conversion efficiency of 4.5 % was achieved under standard AM1.5, 100 mW cm⁻² conditions. Under reduced lighting conditions, even higher efficiencies up to 5.1 % was obtained.     

Structure and Magnetic Properties of Two Lanthanide 1,4‐Phenylenediacetate Compounds

The reactions of Ln(NO₃)₃ with 1,4‐phenylenediacetic acid (H₂PDA) under hydrothermal conditions produced two isostructural lanthanide coordination polymers with the empirical formula [Ln₂(PDA)₃(H₂O)] · 2H₂O [Ln = Nd ( 1 ), Sm ( 2 )]. Single‐crystal X‐ray diffraction analyses revealed that both contain one‐dimensionalmetal carboxylato chains, which are further connected by the–CH₂C₆H₄CH₂– spacers of PDA^2– ligands to yield a three‐dimensional metal‐organic framework. Magnetic susceptibilities of 1 and 2 were measured. The experimental χ_mT value of both compounds decreases continuously with decreasing temperature over the whole temperature range. The best least‐squares fit of the experimental data of 1 to a theoretical equation in the temperature range of 70–300 K gives the zero‐field splitting parameter Δ = 2.21 cm^–1 and the magnetic interaction between the Nd^III ions 2zJ′ = –1.97 cm^–1, which indicates the presence of antiferromagnetic interaction between the Nd^III ions. The experimental χ_mT value of 2 at 2 K is much smaller than the expected value for two free Sm^III ions (⁶H_5/2, g = 2/7) in the ground state, indicating that an antiferromagnetic interaction possibly exists between Sm^III ions at low temperature. Fitting the magnetic data of 2 above 110 K based on an equation deduced from the Sm^III ion in a monomeric system with free‐ion approximation gave a spin‐orbit coupling parameter λ = 192(2) cm^–1     

Synthesis,crystal structure and magnetic properties of diaquabis(2,6‐diamino‐7H‐purin‐1‐ium‐κN9)bis(4,4′‐oxydibenzoato‐κO)cobalt(II) dihydrate

The title mononuclear Co^II complex, [Co(C₅H₇N₆)₂(C₁₄H₈O₅)₂(H₂O)₂]·2H₂O, has been synthesized and its crystal structure determined by X‐ray diffraction. The complex crystallizes in the triclinic space group P, with one formula unit per cell (Z = 1 and Z′ = ). It consists of a mononuclear unit with the Co^II ion on an inversion centre coordinated by two 2,6‐diamino‐7H‐purin‐1‐ium cations, two 4,4′‐oxydibenzoate anions (in a nonbridging κO‐monodentate coordination mode, which is less common for the anion in its Co^II complexes) and two water molecules, defining an octahedral environment around the metal atom. There is a rich assortment of nonbonding interactions, among which a strong N⁺—H…O⁻ bridge, with a short N…O distance of 2.5272 (18) Å, stands out, with the H atom ostensibly displaced away from its expected position at the donor side, towards the acceptor. The complex molecules assemble into a three‐dimensional hydrogen‐bonded network. A variable‐temperature magnetic study between 2 and 300 K reveals an orbital contribution to the magnetic moment and a weak antiferromagnetic interaction between Co^II centres as the temperature decreases. The model leads to the following values: A (crystal field strength) = 1.81, λ (spin‐orbit coupling) = −59.9 cm⁻¹, g (Landé factor) = 2.58 and zJ (exchange coupling) = −0.5 cm⁻¹.     

New P‐type of poly(4‐methoxy‐triphenylamine)s derived by coupling reactions: Synthesis,electrochromic behaviors,and hole mobility

Methoxy‐substituted poly(triphenylamine)s, poly‐4‐methoxytriphenylamine ( PMOTPA ), and poly‐N,N‐bis(4‐methoxyphenyl)‐N′,N′‐diphenyl‐p‐phenylenediamine ( PMOPD ), were synthesized from the nickel‐catalyzed Yamamoto and oxidative coupling reaction with FeCl₃. All synthesized polymers could be well characterized by ¹H and ¹³C NMR spectroscopy. These polymers possess good solubility in common organic solvent, thermal stability with relatively high glass‐transition temperatures (T_gs) in the range of 152–273 °C, 10% weight‐loss temperature in excess of 480 °C, and char yield at 800 °C higher than 79% under a nitrogen atmosphere. They were amorphous and showed bluish green light (430–487 nm) fluorescence with quantum efficiency up to 45–62% in NMP solution. The hole‐transporting and electrochromic properties are examined by electrochemical and spectroelectrochemical methods. All polymers exhibited reversible oxidation redox peaks and E_onset around 0.44–0.69 V versus Ag/AgCl and electrochromic characteristics with a color change under various applied potentials. The series of PMOTPA and PMOPD also showed p‐type characteristics, and the estimated hole mobility of O ‐ PMOTPA and Y ‐ PMOPD were up to 1.5 × 10^?4 and 5.6 × 10^?5 cm² V^?1 s^?1, respectively. The FET results indicate that the molecular weight, annealing temperature, and polymer structure could crucially affect the charge transporting ability. This study suggests that triphenylamine‐containing conjugated polymer is a multifunctional material for various optoelectronic device applications. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4037–4050, 2009