Polymerization and characterization of polyfunctional amphiphilic diacetylenes

Amphiphilic diacetylenes of the type HC?C? (CH₂)_n? C?C? C?C? (CH₂)₈? COOH (n=6 and 12) were synthesized. The solid-state polymerization of the bulk crystals, mono-layers on the gas-water interface, and multilayers were investigated. The diacetylene moieties underwent polymerization upon irradiation by UV or γ-rays, showing different polymerizability depending on the material form. The polymerization of the terminal acetylene groups was not observed. Enhanced polymerizability and stability of the monolayers on subphases containing LiOH are explained by a proposed model of the monolayers. © 1995 John Wiley & Sons, Inc.     

DFT study on cooperativity in the interactions of hydrazoic acid clusters

Density functional theory at the B3LYP level with the 6‐311G** basis set is performed to calculate the systems consisting of up to four hydrazoic acid molecules. The dimers are found to exhibit cyclic and chain structures with N … H contacts at ca. 2.1–2.7 Å. However, there are only cyclic structures with N … H contacts at ca. 2.0–2.3 Å and 2.0–2.1 Å in the trimer and tetramer, respectively. Hydrogen bond distances in the trimer and tetramer are shorter than those in the cyclic dimer as a result of the stronger interaction between molecules. The contribution of cooperative effect to the interaction energy is significant. After the correction of the basis set superposition error and zero‐point energy, the binding energies are ?10.69, ?29.34, and ?54.26 kJ·mol^?1 for the most stable dimer, trimer, and tetramer, respectively. The calculated IR shifts for N? H stretching mode increase with the size of the cluster growths, reaching more than 200 cm^?1 in the tetramer. For the most stable clusters, the transition from the monomer to dimer, dimer to trimer, and trimer to tetramer involve changes of ?14.40, ?25.68, and ?31.88 kJ·mol^?1 for the enthalpies at 298.15 K and 1atm, respectively. We also perform Mulliken populations analysis and find the Mulliken populations on intermolecular N … H increasing in the sequence of the dimer, trimer, and tetramer. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 94: 279–286, 2003     

Oligonucleosides with a Nucleobase‐Including Backbone. Part 11

A linear and a convergent synthesis of uridine‐derived backbone‐base‐dedifferentiated (backbone including) oligonucleotide analogues were compared. The Sonogashira cross‐coupling of the alkyne 1 and the iodide 2 gave the dimer 4 that was C‐desilylated and again coupled with 2 to give the trimer 6 (Scheme 1). Repeating this linear sequence led to the pentamer 10 . Coupling yields were satisfactory up to formation of the trimer 6 , but decreased for the coupling to higher oligomers. Similarly, coupling of the alkynes 5, 7 , and 9 with the iodouridine 3 gave, in decreasing yields, the trimer 12 , tetramer 13 , and pentamer 14 , respectively. The dimeric iodouracil 20 was synthesized by coupling the alkyne 17 with the iodide 16 to the dimer 18 , followed by iodination at C(6/I) to 19 and O‐silylation (Scheme 2). The iodinated dimer 23 was prepared by iodinating and O‐silylating the known dimer 21 . Coupling of 20 and 23 with the dimer 5 , trimer 7 , and tetramer 9 gave the tetramers 8 and 13 , the pentamers 10 and 14 , and the hexamer 15 , respectively (Scheme 3). The oligomers up to the pentamer 14 were deprotected to provide the trimer 24 , tetramer 25 , and pentamer 26 (Scheme 4). There was no evidence for the heteropairing of the pentamer 26 and rA₇ , nor for the pairing of rU₅ and rA₇, while a UV melting experiment showed the beginning of a sigmoid curve for the interaction of rU₇ with rA₇. Therefore, the pentamer 26 does not pair more strongly with rA₇ than rU₅.     

Theoretical study on the interlay of hydrogen bonds in the trimers involving HCN and water

In this study, the hydration of hydrogen cyanide (HCN) has been investigated by means of quantum chemical ab initio calculations at the MP2/6‐311++G(3df,2p) level. Various HCN· · ·( H₂O)₂ and (HCN)₂· · ·H₂O complexes were optimized. Geometrics and energetics in these complexes have been analyzed. The hydration of the H atom leads to an elongation of the N?C and C? H bonds, whereas the hydration of the N atom results in a contraction of the N?C bond and a little elongation of the C? H bond. The interaction energy between each molecule pair in the trimers (except in HCN? H₂O? H₂O trimer) is increased relative to that in the respective dimer. The cooperativity of hydrogen bond in HCN? H₂O? H₂O trimer plays a negative contribution to the total interaction energy of the complex, whereas that in the other trimers is a positive contribution. Geometry and energy in H₂O? H₂OO? HCN? H₂O tetramer have also been analyzed. The binding energies in the trimers and tetramer have been studied by means of many‐body interaction analysis. The mechanism of HCN hydration was suggested. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009     

Characterization of the ladder polymerization of a crystalline cyclotetradiyne monomer

The polymerization of the cyclic tetradiyne monomer, [? (CH₂) ₂? C?C? C?C? (CH₂)₂? ]₄, containing interstitial chloroform has been investigated using Raman and Fourier-transform infrared spectroscopy and x-ray diffraction techniques. A loss of crystallographic register between chains occurs during the polymerization reaction, although crystalline order in the chain-axis projection is retained. These studies indicate that 50 Mrad of ⁶⁰Co γ-ray irradiation produces 1,4-addition polymerization at most of the diacetylene functionalities. Unreacted diacetylene groups are present primarily, although not completely, in soluble oligomeric material. Infrared spectroscopy indicates that this low molecular weight material has a butatriene (cumulene) backbone structure rather than the acetylenic structure of the insoluble polymer.     

Preparation of a uniform poly(methyl methacrylate) macromonomer and its polymerization

Syndiotactic poly(methyl methacrylate) (st-PMMA) macromonomer having methacryloyl end group was prepared from st-PMMA living anion and separated into uniform macromonomers by means of supercritical fluid chromatography. A uniform macromonomer with the degree of polymerization of 32 was polymerized radically in benzene at 60°C. The uniform dimer, trimer and tetramer of the uniform macromonomer were isolated from the polymerization product by means of gel-permeation chromatography (GPC). The intrinsic viscosity ([η]) in tetrahydrofuran of these uniform comblike polymers was determined by GPC/differential viscometric analysis. The plot of logarithmic [η] against logarithmic molecular weight indicated that the trimer and tetramer assume a little shrinking molecular shape as compared with the unimer and dimer.     

Crystal polymorphs of 6‐[(phenylcarbamoyl)oxy]hexa‐2,4‐diyn‐1‐yl isonicotinate

The title compound, C₁₉H₁₄N₂O₄, was found to have two crystal polymorphs, in which the molecular structures of the diacetylenic compound are broadly similar. The main structural difference between the polymorphs concerns the intermolecular hydrogen‐bonding motifs adopted, namely a one‐dimensional zigzag polymer linked by N—H…N(py) (py is pyridine) interactions in polymorph I and a centrosymmetric dimeric motif formed by N—H…O=C interactions in polymorph II. The diacetylene cores of the molecules stack along the a and b axes in polymorphs I and II, respectively. It was found that only the molecular arrangement in polymorph II satisfies Baughman's criterion to afford polydiacetylenes (PDAs) by thermal annealing or irradiation with light. This predicted polymerization activity was confirmed by experiment.     

Vinyl polymerization by metal complexes. III. Vinyl polymerization initiated by oligoamide and cupric ion system

Polymerization of methyl methacrylate and other vinyl monomers was studied in the presence of oligoamide (?-aminocaproic acid, its dimer, trimer, tetramer, and pentamer) and cupric ion in aqueous media. The polymerization was found to be of free-radical character and selective for the type of vinyl monomer. Carbon tetrachloride can accelerate the polymerization. The initiation mechanism of the polymerization is discussed. Spectroscopic measurements were indicative of formation of 1:1 complex between oligoamides and cupric ion in aqueous NaClO₄ solution. Some chemical and physical properties of the resulting polymers were measured.     

Polymerization of styrene oxide by nitronium tetrafluoroborate

The polymerization of styrene oxide by nitronium tetrafluoroborate in nitromethane and methylene chloride at 5, 20, and 50°C is investigated. GPC analyses of the products combined with isocyanate method show that both cyclic and linear oligomers are formed. In CH₃NO₂ the cyclic dimer and trimer are 2-benzyl-4-phenyl-1,3-dioxolane and 1,3,5-tribenzyl-trioxane, respectively. In CH₂Cl₂ 2,5-diphenyldioxane is isolated. In nitromethane, mainly isomerized structures with acetal linkage are produced, while in methylene chloride isomerization does not proceed. By NMR and IR spectra the presence of C?O and OH end groups in the linear oligomers is shown. There are indications that oligomers are formed both directly from the monomer and by degradation of the polymer.     

Molecular weight distribution of poly-N-vinylcarbazole obtained in catalytic solid-state polymerization

The molecular weight distribution of poly-N-vinylcarbazole (PVCar) obtained in solid-state polymerization with various catalysts or γ-rays was measured by gel-permeation chromatography, in order to determine the mechanism of the solid-state polymerization. In addition, the molecular weight distribution of PVCar obtained in the solution polymerization by the cationic catalyst was also measured. The molecular weight distribution of PVCar obtained in the catalytic solid-state polymerization was broad and had three peaks, independent of the nature of catalysts, radical and cationic. A large amount of low molecular weight oligomer (probably dimer or trimer) was formed in the catalytic solid-state polymerization of VCar. The molecular weight distribution of PVCar obtained in the cationic solution polymerization showed only one sharp peak. On the other hand, the molecular weight of PVCar obtained in the radiation-induced solid-state polymerization was larger than that obtained in the catalytic solid-state polymerization, and dimer or trimer was not formed. The molecular weight distribution of PVCar obtained was composed of one sharp peak in the high molecular weight region, and a broad peak in the low molecular weight region, and was extremely different from that of PVCar obtained in the catalytic solid-state polymerization.     

Early stages of the hydrolysis of chromium(III) in aqueous solution-XII. Kinetics of cleavage of the trimer and tetramer in acidic solution

The kinetics of cleavage of the hydrolytic trimer and tetramer of chromium(III) have been studied in acidic solution and at elevated temperatures using spectrophotometric methods. For both reactions, the variation in absorbance with time was consistent with the presence of two consecutive rate-determining processes. The two reactions were concluded to proceed according to: Product analyses and consideration of the stability constants for these oligomers indicated that their overall cleavage reactions were irreversible under the conditions studied. However, it was unclear whether the initial step in tetramer cleavage was irreversible or not. The dimer was identified as an intermediate in the cleavage of the trimer. Each of the bridge-cleavage processes (k₁ and k₂) occurred via acid-dependent pathways, involving protonation processes in addition to bridge-cleavage processes, while only some of them displayed acid independent pathways. The acid dependence of the rate constants and associated parameters at 298 K are: (i) for trimer cleavage k₁ = k_b [H⁺], where the dimer to monomer was found to be the rate-determining step at higher temperatures (≈350 K), while cleavage of the trimer to dimer and monomer becomes rate determining at lower temperature (≈ 300 K). This change in the rate-determining step is attributable to the much higher value for k₁ compared with k₂. Possible mechanisms for trimer and tetramer cleavage are discussed and their rates compared to previously studied cleavage reactions of Cr^III oligomers.     

Synthesis of cyclic chlorophyll oligomers

As a new model of photosynthetic light-harvesting antennas, cyclic dimer, trimer, and tetramer of chlorophyllous moieties were prepared by intermolecular transesterification of a hydroxy-methoxycarbonyl-chlorin using 1,3-dichlorotetrabutyl distannoxane as a catalyst. ¹H NMR and UV-vis spectra showed that the cyclic oligomers tended to form stacked conformers through intramolecular π-π interactions of the chlorin macrocycles. It was demonstrated that the cyclic trimer could form a complex with fullerenes in CDCl₃.     

Molecular structure and infrared spectra of (HXeCN)n (n=2, 3 or 4)

The structure, energetics, and vibrational spectra of the (HXeCN)2 dimer were investigated at the CCSD(T), MP2 and B3LYP levels. Such properties of the (HXeCN)3 trimer and (HXeCN)4 tetramer were investigated at the B3LYP level. The dimer, trimer, and tetramer were predicted to have a C2h, C2v, and D2d structure, respectively. In all of these oligomers, the N?Xe intermonomeric interaction is the most important one for holding the monomers together. Included with the ZPVE and BSSE, the stabilization energy of the dimer is 12.36 kcal/mol at the CCSD(T) level, while those of the dimer, trimer, and tetramer are 10.42, 18.23, and 31.34 kcal/mol, respectively, at the B3LYP level. At the B3LYP level, with respect to those of the isolated monomer, the C-Xe and Xe-H asymmetric stretching frequencies are shifted by -11.2 and +128.0 cm(-1) for the dimer, -51.6, +220.7 and -11.5, +96.6 cm(-1) for the trimer, and -14.1 and +201.8 cm(-1) for the tetramer.     

Cationic oligomerization of anethole: Selective synthesis of dimers and trimers

A linear unsaturated dimer of anethole [II, (E)-1,3-bis(p-methoxyphenyl)-2-methylpentene-1], was prepared in 98% yield with an acetyl perchlorate (AcClO₄) catalyst in a nonpolar solvent (C₆H₆) at a high temperature (70°C). At 0°C a linear unsaturated trimer was formed in high yield with dimer II. The geometric structure of the linear unsaturated dimers was determined by analysis of the nuclear Overhauser effect (NOE) on their ¹H-NMR spectra. NOE analysis showed that at 0°C with AcClO₄, trans-anethole gives the (E)-form (II), whereas cis-anethole yields the (Z)-form. On the other hand, with a metal-halide catalyst (BF₃OEt₂) a cyclic dimer and a cyclic trimer were produced in high yields in a polar solvent [(CH₂Cl₂)] at 70°C; higher oligomers (≥ tetramer) were scarcely formed. The effect of catalysts on the structure of oligomers was explained in terms of the interaction between a growing carbocation and a counterion.     

Investigation of the structure of polymer diacetylene Langmuir-Blodgett films

Abstract

The structure of Langmuir-Blodgett (LB) diacetylene films CH₃?(CH₂)₁₁?C≡C?C≡C?(CH₂)₈?COOCd_1/2 (DA1) and CH₃?(CH₂)₂₀?CO₂?CH₂?C≡C?C≡CH₂OH (DA2) was studied by X-ray small angle scattering and electron diffraction methods prior to and upon their polymerization. It has been established that Langmuir films have layer packing. The periods of the constituent layers were determined as 58 Å (for DA1) and 69 Å (for DA2). This indicates the existence of a vertical bilayered packing of molecules. It has also been established that polymerization of LB diacetylene films due to the action of UV irradiation does not change the layer thickness appreciably and the structural rearrangement reduces to a slight redistribution of the electron density along the molecules which is explained by a break of the triple bonds during the UV irradiation.     

Direct analysis of microstructures of alkyl phenol resin using atmospheric pressure chemical ionization-mass spectrometry

Alkyl phenol resin was directly analyzed using atmospheric pressure chemical ionization-mass spectrometry (APCI-MS). Analysis was performed in both positive and negative ion modes, and product ions were only observed in the negative ion mode. By interpreting the m/z values of [M – H]^? ions, the degree of polymerization, the types of linkages and the types of terminals could be determined. The monomer, dimer, trimer, tetramer and pentamer species were observed. The methylene and dimethylene ether linkages were distinguished. For the terminal types, the methylol, o-methylene quinone, hydrogen, and aldehyde were distinguished. Influence of the types of solvents and eluents on the ionization efficiencies were investigated using acetone, chloroform and tetrahydrofuran. Recommendable solvent and eluent system for the analysis of resin using APCI-MS was acetone.     

The synthesis and characterization of poly(methylene terephthalate)

Poly(methylene terephthalate) (1GT) has been synthesized via the reaction of cesium or potassium terephthalates with dibromomethane or bromochloromethane in N-methylpyrrolidone at temperatures of 80–125°C. The polymerization was relatively slower with the latter substrate, though the potassium salt was found to be equally as efficient as its cesium counterpart with dibromomethane. The polymer is insoluble in all common polyester solvents, and its high molecular weight nature (DP _n ≥ 25) was inferred from elemental analyses and its fiber forming capacity. Thermal analyses indicated that 1GT possesses poor thermal stability and decomposes rapidly during melting, the initial process being thought to be the splitting out of formaldehyde. 1GT polymers were shown to contain a homologous series of cyclic oligomers (from dimer to decamer); the two most predominant were tentatively identified as the cyclic trimer and tetramer. No change in the cyclization efficiency was observed when the potassium counterion was substituted for cesium with Br CH₂ Br whereas a drastic reduction in the cyclic content was obtained using Br CH₂ Cl (with Cs⁺). The two most important features of the polymerization are the insensitivity of the reaction to the stoichiometric equivalence of the reactants and the production of reasonably high molecular weights at low conversions. It is suspected that the polymerization might be occurring through an interfacial mechanism.     

Formation of dimer, trimer, and tetramer of C60 and C70 by γ-ray, charged-particle irradiation, and their HPLC separation

C₆₀ and C₇₀ fullerenes were irradiated by high-energy γ-rays and charged particles. Coalesced products of C₆₀ and C₇₀ have been isolated and detected in the liquid phase by a radiochromatographic technique. It was found that not only ¹¹C radioactive fullerene dimer, trimer, and possibly tetramer were produced by a recoil implantation process following nuclear reaction, but also such non-radioactive coalesced products were produced by the recombination process after ionization by γ-rays or charged particles.     

Synthesis,Structure, Optical,and Electrochemical Properties of Triple‐ and Quadruple‐Decker Co‐facial Tetrathiafulvalene Arrays

Understanding the details of the electronic structure in face‐to‐face arranged tetrathiafulvalenes (TTFs) is very important for the design of supramolecular functional materials and superior conductive organic materials. This article is a comprehensive study of the interactions among columnar stacked TTFs using trimeric (trimer) and tetrameric (tetramer) TTFs linked by alkylenedithio groups (‐S(CH₂)_nS‐, n=1–4) as models of triple‐ and quadruple‐decker TTF arrays. Single‐crystal X‐ray analyses of neutral trimeric TTFs revealed that the three TTF moieties are oriented in a zigzag arrangement. Cyclic voltammetry measurements (CV) reveal that the trimer and tetramer exhibited diverse reversible redox processes with multi‐electron transfers, depending on the length of the ‐S(CH₂)_nS‐ units and substituents. The electronic spectra of the radical cations, prepared by electrochemical oxidation, showed charge resonance (CR) bands in the NIR/IR region (1630–1850 nm), attributed to a mixed valence (MV) state of the triple‐ and quadruple‐decker TTF arrays. In the trimeric systems, the dicationic state (+2; 0.66 cation per TTF unit) was found to be a stable state, whereas the monocationic state (+1) was not observed in the electronic spectra. In the tetrameric system, substituent‐dependent redox processes were observed. Moreover, π‐trimers and π‐tetramers, which show a significant Davydov blueshift in the spectra, are formed in the tricationic (trimer) and tetracationic (tetramer) state. In addition, these attractive interactions are strongly dependent on the length of the linkage unit.     

Transformations of chloroethylenes in the presence of aprotonic acids

The cationic polymerization of vinyl chloride, vinylidene chloride, and cis- and trans- 1,2-dichloroethylenes with the use of Lewis acid-type catalysts has been studied. Vinylidene chloride is smoothly polymerized in the presence of ZnCl₂ at 40°C to form the dimer, 1,1,3,3-tetrachlorobutene-1, and poly(vinylidene chloride) having somewhat increased crystallinity (45%). Vinyl chloride is polymerized very slowly in the presence of AlCl₃ and TiCl₄ to give dimeric, trimeric, tetrameric, and low molecular weight polymer products. The polymerization is followed by carbonium ion isomerization that leads to reaction products of branched structure. The cis- and trans-1,2-dichloroethylenes react in the presence of AlCl₃ only at 50–60°C, and their polymerization is terminated at the stage of dimer and cyclic trimer formation. A mechanism of carbonium ion-initiated polymerization of chloroethylenes is proposed, and the causes which lead to early termination of polymerization are discussed.