Synthesis and characterization of diphenylaminodiphenyl stryl based alternating copolymers

Diphenylaminobiphenylated stryl based alternating copolymers with phenyl or fluorene, which were expected to have a terphenylene vinylene backbone containing an (N,N‐diphenylamino)biphenyl pendant and a phenyl/fluorene/phenylene vinylene backbone containing an (N,N‐diphenylamino)biphenyl pendant, were synthesized by a Suzuki coupling reaction. The obtained copolymers were confirmed with various types of spectroscopy. The alternating copolymers showed good hole‐injection properties because of their low oxidation potential and good solubility and high thermal stability with a high glass‐transition temperature. The alternating copolymers showed blue emissions because of the adjusted conjugation lengths; the maximum wavelength was 460 nm for poly{4,4′‐biphenylene‐α‐[4″‐(N,N′‐diphenylamino)diphenyl]vinylene‐alt‐5‐(2′‐ethylhexyloxy)‐2‐methoxybenzene} and 487 nm for poly{4,4′‐biphenylene‐α‐[4″‐(N,N′‐diphenylamino)diphenyl] vinylene‐alt‐9,9‐dihexylfluorene}. The maximum brightness of indium tin oxide/poly(3,4‐ethylene dioxythiophene)/polymer/LiF/Al devices with poly{4,4′‐biphenylene‐α‐[4″‐(N,N′‐diphenylamino)diphenyl]vinylene‐alt‐5‐(2′‐ethylhexyloxy)‐2‐methoxybenzene} or poly{4,4′‐biphenylene‐α‐[4″‐(N,N′‐diphenylamino)diphenyl]vinylene‐alt‐9,9‐dihexylfluorene} as the emitting layer was 250 or 1000 cd/m², respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 341–347, 2007     

On the calculation of some mixed moments of aggregative characteristics of a homogeneous Markov chain for the polynomial scheme

Formulas are given for the calculation of some mixed moments of aggregative characteristics of a homogeneous Markov chain for the polynomial scheme. Translated fromStatisticheskie Metody Otsenivaniya i Proverki Gipotez, pp. 156–164, Perm, 1991.     

Asymptotic solutions of Fokker-Planck equations for nonlinear irreversible processes and generalized Onsager-Machlup theory

Fokker-Planck equations for nonlinear processes are solved asymptotically in the limit k→0 where k is the Boltzmann constant. It is shown that the leading asymptotic solutions for conditional (two-gate) distribution functions simply correspond to generalizations of the Onsager-Machlup theory to nonlinear processes. The asumptotic solution method used in the paper is similar to the well-known W.K.B. method in quantum mechanics. A stability criterion of nonlinear irreversible processes is also considered and compared with the Glansdorff-Prigogine stability criterion.     

Marked increase in the binding strength between the substrate and the covalently attached monolayers of zeolite microcrystals by lateral molecular cross-linking between the neighboring microcrystals

Monolayers of cubic zeolite microcrystals (1.7 x 1.7 x 1.7 and 0.3 x 0.3 x 0.3 mum3) were assembled on glass plates through imine- or urethane-linkages between the zeolite-tethered 3-aminopropyl (AP) groups and the glass-bound benzaldehyde or isocyanate groups, which were prepared by treating AP-tethering glass plates with a large excess of terephthaldicarboxaldehyde (TPDA) or 1,4-diisocyanatobutane (DICB), respectively, in toluene. The additional treatment of the monolayers of zeolite microcrystals with TPDA or DICB led to lateral molecular cross-linking between the neighboring, closely packed zeolite microcrystals in the monolayers through AP-TPDA-AP imine or AP-DICB-AP urethane linkages between the zeolite-tethered AP groups and the newly introduced TPDA or DICB, respectively. The comparison of the binding strengths between the glass substrates and the monolayers revealed that the molecular cross-linking leads to as much as 7- and 38-fold (by average) increase in the binding strength in the cases of 1.7 x 1.7 x 1.7 and 0.3 x 0.3 x 0.3 mum3 crystals, respectively. We predict that the effect of lateral cross-linking on the binding strength will further increase with further decreasing the size of the building blocks to nanoparticles and to molecules.     

Anion complexation. A ditriphenylphosphonium calix[4]arene derivative as a novel receptor for anions

A novel anionic receptor 2 consisting of a calix[4]arene bearing two alkytriphenylphosphonium has been prepared by two different procedures. The complexation occurred at the phosphonium sites probably due to electrostatic and/or π-anion forces.     

Synthesis and characterization of thiazolothiazole‐based polymers and their applications in polymer solar cells

A novel series of thiazolothiazole (Tz)‐based copolymers, poly[9,9‐didecylfluorene‐2,7‐diyl‐alt‐2,5‐bis‐(3‐hexylthiophene‐2‐yl)thiazolo[5,4‐d]thiazole] (P1), poly[9,9‐dioctyldibenzosilole‐2,7‐diyl‐alt‐2,5‐bis‐(3‐hexylthiophene‐2‐yl)thiazolo[5,4‐d]thiazole] (P2), and poly[4,4′‐bis(2‐ethylhexyl)‐dithieno[3,2‐b:2′,3′‐d]silole‐alt‐2,5‐bis‐(3‐hexylthiophene‐2‐yl)thiazolo[5,4‐d]thiazole] (P3), were synthesized for the use as donor materials in polymer solar cells (PSCs). The field‐effect carrier mobilities and the optical, electrochemical, and photovoltaic properties of the copolymers were investigated. The results suggest that the donor units in the copolymers significantly influenced the band gap, electronic energy levels, carrier mobilities, and photovoltaic properties of the copolymers. The band gaps of the copolymers were in the range of 1.80–2.14 eV. Under optimized conditions, the Tz‐based polymers showed power conversion efficiencies (PCEs) for the PSCs in the range of 2.23–2.75% under AM 1.5 illumination (100 mW/cm²). Among the three copolymers, P1, which contained a fluorene donor unit, showed a PCE of 2.75% with a short‐circuit current of 8.12 mA/cm², open circuit voltage of 0.86 V, and a fill factor (FF) of 0.39, under AM 1.5 illumination (100 mW/cm²). © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Preparation of cycloolefin copolymers of a bulky tricyclopentadiene

Copolymerizations of ethylene and tricyclopentadiene (TCPD) are realized without formation of a gel with a high activity (3–18 × 10⁶ g/molZr·h) using a catalytic system of [Ph₂C(Flu)(Cp)]ZrCl₂/MMAO. The monomer reactivity ratios, r_ethylene and r_TCPD, determined through the Fineman‐Ross plot, are 6.4 and 0.044, respectively, indicating that TCPD insertion is unfavorable, negligibly allowing the successive TCPD insertions. A significant higher glass transition temperature (T_g) is attained than those observed for other reported cycloolefin copolymers at the same cycloolefin content. A T_g as high as 214 °C is attainable at 41 mol % TCPD content. The remaining double bond can be hydrogenated to saturated hydrocarbon or converted to an epoxide group. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011