A modular approach to ferroelectric polymers with chemically tunable curie temperatures and dielectric constants

We present a modular approach toward poly(vinylidene fluoride)-based ferroelectric fluoropolymers with high dielectric constants. This strategy is based on a two-step reaction, including the copolymerization of vinylidene fluoride and chlorotrifluoroethylene and a subsequent hydrogenation reaction. The chemical structures and compositions of the resulting polymers can be precisely controlled, leading to tunable Curie temperatures and dielectric constants and a systematical study of structure-property correlations.     

Investigations of blends containing coil polymers and thermotropic main-chain polymers

Blends containing main-chain thermotropic, semiflexible polyesters and flexible-chain polymers (PC and PET) are investigated by calorimetry and microscopy. First results of studies about the mechanical behaviour by torsional pendulum are presented.     

A modular and divergent approach to spirocyclic pyrrolidines

An efficient three-step sequence to afford a valuable class of spirocyclic pyrrolidines is reported. A reductive cleavage/Horner–Wadsworth–Emmons cascade facilitates the spirocyclisation of a range of isoxazolines bearing a distal β-ketophosphonate. The spirocyclisation precursors are elaborated in a facile and modular fashion, via a [3 + 2]-cycloaddition followed by the condensation of a phosphonate ester, introducing multiple points of divergence. The synthetic utility of this protocol has been demonstrated in the synthesis of a broad family of 1-azaspiro[4,4]nonanes and in a concise formal synthesis of the natural product (±)-cephalotaxine.

A three-step, modular and divergent sequence accessing challenging spirocyclic pyrrolidines has been developed, featuring a novel reductive spirocyclization cascade.     

A straightforward modular approach to NLO-active beta-amino vinyl nitrothiophenes

Secondary amines add very efficiently to 2-ethynyl-5-nitrothiophene to give beta-amino vinyl nitrothiophenes, a novel class of push-pull chromophores. According to first HRS measurements these highly solvochromic compounds with relatively short dipole axes display remarkably high static first hyperpolarizabilities = 29-31 x 10(-)(30) esu.     

A modular approach to DNA-programmed self-assembly of macromolecular nanostructures

DNA-programmed organic reactions are new and powerful tools for assembling chemical compounds into predetermined complex structures and a brief review of their use is given. This approach is particular efficient for the selection and covalent coupling of multiple components. DNA-templated synthesis is used for polymerization of PNA tetramers and for copying of the connectivity information in DNA. Direct DNA-programmed multicomponent coupling of custom designed organic modules is described. The macromolecular structures obtained are highly conjugated potentially conducting nanoscaffolds. Some future developments in this area are discussed.     

X-ray investigation of combined main-chain/side-chain liquid-crystalline polymers

Structural investigations on six combined liquid-crystalline polymers using the X-ray technique are described. The measurements have allowed a characterization of the liquid-crystalline phases and have led to our first ideas about the phase structures. All mesogenic groups are arranged parallel to each other, the shortest segment in the main-chain or in the side-chain determines the smectic layer spacing. A modified designation for liquid-crystalline phases of high polymers is proposed.     

A modular approach toward block copolymers

A novel methodology for the formation of block copolymers has been developed that combines ring-opening metathesis polymerization (ROMP) with functional chain-transfer agents (CTAs) and self-assembly. Telechelic homopolymers of cyclooctene derivatives end-functionalized with hydrogen-bonding or metal-coordination sites are formed through the combination of ROMP with a corresponding functional CTA. These telechelic homopolymers are fashioned with a high control over molecular weight and without the need for post-polymerization procedures. The homopolymers undergo fast and efficient self-assembly with their complement homopolymer or small molecule analogue to form block-copolymer architectures. The block copolymers show equivalent association constants as their small molecule analogues described in the literature, regardless of size or nature of the complementary unit or the polymer side chain.     

The modular approach to ligand discovery

Identifying specific protein-ligand interactions is a long-standing problem in drug discovery and chemical biology, which is only exacerbated by the abundance of uncharacterized proteins revealed by genomics. Last month in Chemistry Biology, Sem et al. described a powerful technique for rapidly screening protein families for ligands.     

Morphology and strength of high performance main-chain liquid crystal polymers

The impact of chain-length on formation and properties of thermotropic LC-phases is described for poly(didocecyl-p-phenylene). Isotropic, biphasic or anisotropic melts are observed. The zero-shear viscosity scales as η≈︁M_w^2.9 in the isotropic and as η=M_w^3.2 in the anisotropic melt. If quenched from the LC-melt, the material exhibits a smectic superstructure dominated by disclinations. The same feature is seen with the poly(diacetylene) P-4BCMU crystallized from lyotropic solution. The LC-phase consists of lamellae the thickness of which scales with the extended chain length. Segregation of the chains allows the lamellae to adapt to the strain field in the vicinity of the core of the disclinations. A banded texture observed when the LC-phase is subject to shear is resolved by TEM as composed of periodically distorted stacks of lamellae. Small modifications of the chain structure by comonomers has a substantial impact on the mechanical properties. Introducing only 5 mol percent of comonomers with sterically assuming substituents into lyotropic poly(p-phenylene terephthalamide) improves the compressional strength (Elastica test) of fibers by 25 percent.     

Carbazole main-chain polymers for multifunctional materials: Synthesis and characterization

A series of α,ω-bis(3-formylcarbazolyl)alkane monomers have been prepared starting from carbazole and α,ω-dibromoalkane in two steps. Main-chain polymers with carbazole substituted with one acceptor group as the nonlinear optical (NLO) chromophores and photoconductive moieties were synthesized by the Knoevenagel polycondensation of α,ω-bis(3-formylcarbazolyl)alkane and 1,6-bis(cyanoacetoxy)hexane using 4-(N,N-dimethyl)pyridine (DMAP) as a base. This Knoevenagel polycondensation involved two stages: polycondensation was first carried out in tetrahydrofuran solution, and then polycondensation was allowed to continue in the solid-state after removal of solvent. All of these main-chain polymers characterized by spectroscopic methods and elemental analyses are soluble in common low boiling organic solvents, such as chloroform. These polymers were found to be amorphous with glass transition temperatures in the range of 94–117°C by differential scanning calorimetry. This two-stage polycondensation gave polymers with weight-average molecular weight in the range of 25,000–72,000 g/mol by gel permeation chromatography. The study of the nonlinear optical and photorefractive properties of these polymers is in progress. © 1996 John Wiley & Sons, Inc.     

A modular approach to the synthesis of 2,3,4-trisubstituted tetrahydrofurans

A highly diastereoselective Lewis acid-mediated [1,3] rearrangement of 1,3-dioxepins is the key step along a modular route to 2,3,4-trisubstituted tetrahydrofurans.     

A combinatorial approach to branched polymers’ statistics

At least ideally, a certain class of polymers presents itself as a collection (set) of connected components. Each of these components is a cycle of trees, that is branched polymers eventually rooted on a cycle. We derive (and study) an equilibrium statistical model that accounts for the main connectivity features of such structures, whose origin is to be found in combinatorial probability. Phase transition (gel–soltransition) is shown to occur when some internal control parameter crosses one (critical parameter). Various structural asymptotic results are shown to be available using singularity analysis. This revised version was published online in July 2006 with corrections to the Cover Date.     

A synergistic approach to the polydispersity of polymers

A scheme for calculating polydispersity coefficients of polymers during chain propagation in living polymerization is proposed on the basis of the synergistic approach (the master equation) with allowance for fluctuations in the number of free radicals at the stage of initiation. The molecular-mass-distribution function of living chains is calculated. The form of this function is shown to be dependent on the ratio between the constants of the elementary stages of chain initiation and propagation.     

A theoretical investigation of electron correlation and relaxation in organometallic polymers

The importance of many-body interactions beyond the mean-field approximation of the Hartree–Fock (HF ) self-consistent-field crystal orbital formalism is analyzed in one-dimensional (lD) transition-metal (3d) polymers with extended organic π ligands. The correlation energies are expressed in a quasiparticle picture. They are divided into long-range contributions that are coordinated with the basis of spatially uncorrelated Bloch orbitals and into short-range correlations derived for local rearrangement processes that are described in terms of a one-electron basis which breaks the translational symmetry of the lD system. Both contributions (long-range and short-range correlations) are fragmented into elements of physical significance (hole and electron self-energies for the former interactions; relaxation, pair-relaxation and pairremoval terms for the local virtual excitations). The magnitude of these elements is analyzed as a function of the characters of the one-electron states in the HF bands, the occupation patterns at the 3d centers, the available particle and hole channels in the elementary fluctuations and the energies and shapes of the various bands. The broad spectrum of possible amplifications and compensations leading to the quasiparticle shifts in metallomacrocycles is discussed. The different mechanisms to change the dispersions and to modify the width of the ?(k) curves are studied. It is shown that electron correlation and relaxation in transition-metal polymers can lead even to a broadening of the energy bands. This behavior is in contrast to the influence of many-body effects in simpler homogeneous materials where electron correlation is in any case accompanied by a narrowing of the dispersions (i.e., detraction of the group velocities of particles and holes). Possible modifications in the shapes of the one-particle curves and the quasiparticle bands are also considered in the text [transition from a “normal ?(k) dispersion” to an energy band with a negative slope as a result of electron correlation]. Simplified formulas are derived that allow for a rough assessment of the various correction terms even in structurally complicated transition-metal stacks with extended organic ligands. The approximate relations are used to correct the HF band structures of complex onedimensional metallomacrocycles as well as simpler crystalline materials by means of the quasiparticle approximation.     

New aromatic benzazole polymers. I. Benzobisthiazole and benzobisoxazole polymers with main-chain triarylamino units

Thermally stable, nonrigid-rod poly(benzobisthiazoles), (R)TPA-PBZT , where R = H, Me, NMe₂, and OH, and poly(benzobisoxazoles), (R)TPA-PBO , where R = Me, NMe₂ containing electron-rich triarylamine groups with various para-substituents (Rs) on the pendent phenyl ring, were synthesized from either 2,5-diamino-1,4-benzenedithiol dihydrochloride or 2,4-diamino-1,5-benzenediol dihydrochloride and the respective triarylamine-based dinitrile or diacid monomer in polyphosphoric acid. Whereas (R)TPA-PBZT polymers were obtained in moderate molecular weights, analogous (R)TPA-PBO polymers were only prepared in low molecular weights. No lyotropic behaviors, characteristic of the unmodified rigid-rod benzazole polymers, as evidenced by the absence of either stir opalescence or birefringence under crosspolarizers, were observed for these homopolymers at about 10 wt % polymer concentration. Among these polymers, only (Me)TPA-PBZT and (NMe₂)TPA-PBZT formed cast films with good mechanical integrity. In their pristine state, their film conductivity values were in the range of 10⁻¹⁰–10⁻⁹ S/cm at room temperature. Upon exposure to iodine vapor, their conductivities were increased to the maximal values of 5.0 × 10⁻⁵ S/cm ( (Me)TPA-PBZT ) and 4.1 × 10⁻⁴ S/cm ( (NMe₂)TPA-PBZT ). © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 1909–1924, 1997