Synthesis and Characterization of π-Conjugated Polymers with a 2,5-Substituted Phosphole Skeleton

Summary Novel π-conjugated polymers 10a-c having the phosphole ring were prepared by PdCl₂(PPh₃)₂/CuI catalyzed coupling of 1-phenyl-2,5-bis(p-bromophenyl)phosphole 8 with fluorine-substituted diethynylbenzene 9a-c. The obtained polymers 10a-c were regio-regulated with the 2,5-substituted phosphole ring in the polymer main chain, and characterized by ¹H, ³¹P NMR, and FTIR. Polymers 10a-c were found to be an extended π-conjugated system according to the results of UV-Vis absorption spectra. In the fluorescence emission spectra of 10a-c, moderate emission peaks were observed in the visible blue to green region.     

Spiroheterocyclic system. Part IV: Novel azo dye sulpha drugs of spiroheterocyclic naphthenes

Novel azo-dyes have been synthesized by diazotization of 4-amino benzene-4′-(substituted heterocyclo) sulphonamide derivatives and coupling with 1-oxa-4-thia-spiro[4,4]nonan-2-one (I) and/or with l-oxa-4-thia-spiro[4,5]decan-2-one (I′) in acid medium to give the corresponding 3-azo-(4′-substituted benzenesulphonamido)-l-oxa-4-thia-spiro[4,4]nonan-2-one (II-IX) and/or l-oxa-4-thia-spiro[4,5]decan-2-one (II′-IX′] as spiro-ligands. Treatment of these ligands with metal salts of iron (Fe³⁺), copper (Cu²⁺) and mercury (Hg²⁺) as chlorides in ethanolic solution furnished the corresponding metal chelates (II_a-c-IX_a-c) and/or (II′_a-c-IX′_a-c). The compounds were tested in vitro for antimicrobial activity to study the structure-activity relationship.     

New polymer syntheses,part 45: Corrosion inhibition behavior of novel polyurea derivatives based on diarylidenecycloalkanone moieties in the polymers backbone

A novel class of interesting polyurea derivatives 6 _a-c and 7 _a-c was synthesized using solution polycondensation technique by the interaction of 1 mole of bis (2-aminothiazol-4-ylbenzylidene)cycloalkanones monomers 3 _a,b with one moles of diisocyanate compounds in pyridine. The model compounds 4 and 5 were synthesized by the interaction of one mole of monomers 3 _a or 3 _b with two moles of phenylisocyanate in pyridine and their structures were confirmed by correct elemental and spectral analyses. The resulting polymers were characterized by elemental and spectral analyses, beside solubility and viscometry measurements. X-ray analysis showed these polymers having high degree of crystallinity in the region 2θ = 5–60^°. In addition, the morphological properties of selected examples were tested by SEM, and the electrical properties of these polymers were measured. Moreover the corrosion inhibition behavior of diarylidenecycloalkanone monomers and selected examples of polyurea derivatives were carried out on steel in 0.5 M H₂SO₄ at 40°C giving cathodic, anodic and mixed inhibition.     

Syntheses, Crystal Structures and Photophysical Properties of a Series of LnIII (Ln?=?Sm, Tb, Pr) Coordination Polymers

Four new lanthanide(Ш) coordination polymers, [Ln(p-aminobenzoate)₂(DMF)(HCOO) (H₂O)]_n (Ln = Sm 1, Tb 2, Pr 3) and {[Pr(2,5-dcp)(CH₃COO)(H₂O)]·1.5H₂O}_n (4) (DMF = N,N-dimethylformamide, 2,5-dcp = pyridine-2,5-dicarboxylate), have been synthesized by hydrothermal method. The structures are determined by the single-crystal X-ray diffraction. The four polymers all crystallize in the monoclinic space group P2₁/n. Polymers 1 and 2 are isostructural; both Sm^III ion of polymer 1 and Tb^III ion of polymer 2 are eight-coordinate. Although polymer 3 possesses the same asymmetric unit as polymers 1 and 2, the three are not isomorphous. The Pr^III ions in polymers 3 and 4 are nine-coordinate. In polymers 1, 2 and 3 the neighboring units are bridged by formyloxy and extend into infinite chains, which are connected by hydrogen bonds to form a hydrogen bond network. However, polymer 4 is bridged by pyridine-2,5-dicarboxylate and acetates to form an infinite 3D network. At room temperature, the IR, UV–Vis–NIR and emission spectra of the four polymers were measured and analyzed. The four polymers emit in the visible or NIR region. The luminescent properties are discussed.     

Synthesis of Poly(propargyl esters) with Rhodium Catalysts and Their Characterization

Summary Propargyl esters (HC≡CCH₂OC(=O)R; 1: R = n-C₅H₁₁, 2: R = CH₃, 3: R = CHBrCH₃, 4: R = C₆H₅, 5: R = C(C₆H₅)₃) were polymerized by using (nbd)Rh⁺(η⁶-Ph-B^-Ph₃) (nbd = 2,5-norbornadiene) to produce poly(1)–poly(5) with molecular weights in the range of M_n = 4,900–40,000. Poly(1), poly(3) and poly(4) were readily soluble in common organic solvents such as toluene, THF and CHCl₃, and poly(2) showed similar solubility behavior except that it was insoluble in THF. Poly(5) did not dissolve in any organic solvent. Poly(1) was yellow oil, while poly(2)–poly(5) were yellow solids. Poly(1)–poly(4) exhibited UV-vis absorptions in a range of 300–425 nm, which are attributed to the conjugation of the main chain. All the polymers were thermally stable up to 150–200 °C.     

Living cationic polymerization of styrene with 1-phenylethyl chloride/TiCl4/Bu2O

Summary Living polymerization of styrene was obtained in the system 1-phenylethyl chloride/TiC1₄/Bu₂O in mixture of 1,2-dichloroethane and n-hexane (55:45 v/v) at -15^°C. The number-average molecular weights (M_n) of the polymers obtained increased in direct proportion to the monomer conversion and agreed well with the calculated values. The first-order kinetic plots were linear. The molecular weight distributions were narrow (M_n/M_n=1.46-1.56). Received: 3 1 January 2002/Revised version: 7 October 2002/Accepted: 7 October 2002 Correspondence to Sergei V. Kostjuk     

Synthesis and properties of new highly soluble poly(amide-ester-imide)s containing poly(ethylene glycol) as a soft segment

In this study, a new class of highly soluble poly(amide-ester-imide)s (PAEI)s contains poly(ethyleneglycol) (PEG) as hydrophilic and soft segment were prepared. Poly(ethylene glycol)-bis-(N-trimellitylimido-4-phenyl carboxylic acid) (3) as a novel diacid monomer was synthesized via two step. The reaction of poly(ethylene glycol) (PEG 6000) with trimellitic anhydride chloride yield poly(ethylene glycol)-bis-trimellitic anhydride (1). The reaction of dianhydride 1 with p-aminobenzoic acid (2) produces novel diacid monomer 3. The direct polycondensation technique of the diacid 1 with several aromatic diamines was carried out in pyridine/N-methyl-2-pyrrolidone/triphenylphosphite/CaCl₂ as condensing agent. The resulting novel PAEIs with inherent viscosities ranging between 0.21 and 0.42 dl g⁻¹, were obtained in good yield. This group of polymers exhibit excellent solubility in a variety of organic solvents and water. All of these polymers were characterized with FT-IR spectroscopy. Thermal properties, ¹H-NMR and XRD study of these PAEIs were also reported. The results demonstrate that this polymers show crystalline structure as well as high thermal stability. In addition the effect of PEG length on solubility and thermal properties of the polymers were also studied.     

Syntheses, Characterization and Crystal Structures of 1D and 2D Organotin Polymers Containing 3-Methyladipic Acid Ligand

Four new organotin (IV) complexes of two types [(R₂Sn)₂(C₇H₁₀O₄)(μ₃-O)] _n (R = Me: 1; nBu: 2; and {(R₃Sn)₂[C₅H₁₀(COO)₂]} _n (R = Me: 3; nBu: 4) have been synthesized by the reaction of 3-methyladipic acid with the corresponding R₃SnCl (R = Me, nBu) under two different experimental conditions. All the complexes were characterized by elemental analysis, FT-IR, and NMR (¹H, ¹³C, ¹¹⁹Sn) spectroscopy. Except for 2, all of the complexes were also characterized by X-ray crystallography. The structural analyzes show that complex 1 is a 1D infinite chain polymer and forms a 2D organotin framework through intermolecular C–H···O interactions and weak Sn···O interactions. Complexes 3 and 4 are 2D network polymers in which 3-methyladipic acid acts as a tetra dentate ligand coordinated to the trialkyltin (IV) ion.     

Synthesis and Reactions of Organometallic Polymers Containing Titanacyclobutene Units in the Main Chain

A new class of polymers containing titanacyclobutene units in the main chain were prepared by the reaction of organic dihalides (2) with a binuclear titanium propargyl complex (3) generated in situ from bis(pentamethylcyclopentadienyl)titanium chloride (Cp*₂TiCl, 1), SmI₂, and 1,4-bis(3-bromopropynyl)benzene (2a). The dark red colored polymers (4) thus obtained are soluble in organic solvents such as tetrahydrofuran and chloroform, and they are stable at ambient temperature under argon atmosphere. The reaction of the titanium-containing polymers (4) with hydrogen chloride was found to give organic polymers (7) containing unsaturated main chain.     

Ring-opening polymerization of various oxirane derivatives using organotin phosphate condensate; Selective synthesis of the polyether containing oxirane ring in the side chain

Ring-opening polymerization (ROP) of various oxirane derivatives of the type, 2,2-R¹,R²-CCH₂O [R¹ = H (1), CH₃ (2); R² = CH₃ (a), CH₂Cl (b), CH₂OCH₃ (c)], using organotin phosphate (Bu₂SnO-Bu₃PO₄) condensate has been explored. The ROP of monosubstituted oxiranes (1a-c) afforded ring-opened polymers in high yields (1a, 1c = 99% and 1b = 69%); the resultant polymers from monomers 1a and 1b possessed high molecular weights (M_n = 9.49 × 10⁴, 10.60 × 10⁴, respectively). In contrast, both polymer yields and molecular weights for resultant polymers in the polymerization of disubstituted oxiranes (2a-c) were considerably lower than those in the polymerization of monosubstituted monomers (1a-c). ROP of glycidyl 2-methylglycidyl ether (3) possessing two oxirane groups with different reactivity was thus conducted by organotin catalyst; the high molecular weight polyether (M_n = 9.17 × 10⁴) containing oxirane ring in the side chain has successfully been obtained in moderate yield.     

Chemical transformations of functional polycarbosilanes

The functional polycarbosilane [Si(X ₂)C₂H₄] _n , whereX ₂=Cl₂ (1), was chemically transformed into the corresponding polymers, whereX ₂=F₂ (3), (2-N, N-dimethylbenzylamino)(H) (5), (9-N,N-dimethyl-1-naphthylamino)(H) (6), (1-C₁₀H₇)(H) (7), Me₂ (8a), (Me₃SiNH)₂ (10), and (vinyl)(H) (11). The functional polycarbosilane, whereX ₂=H₂ (2), was converted into the polymers, whereX ₂=Me(H) (8b) and (OMe)₂ (9). Reaction of3 with KF in the presence of 18-crown-6 gave rise to the poycarbosilane4 containing both pentacoordinate and tetracoordinate silicons in the proportion of 1:15 as shown by quantitative¹⁹F and²⁹Si NMR. Conversion of a greater proportion of silicon atoms to the pentacoordinate state was not possible because of insolubility of the resulting ionomer in the reaction medium.     

Synthesis and properties of novel polyurethanes containing 2,4-dioxybenzylidenecyanoacetate group as a NLO-chromophore for electro-optic applications

Summary Methyl 2,4-bis-(2'-hydroxyethoxy)benzylidenecyanoacetate (3) was prepared by hydrolysis of methyl 2,4-bis-(2'-vinyloxyethoxy)benzylidenecyanoacetate (2). Diol 3 was condensed with 2,4-toluenediisocyanate, 3,3'-dimethoxy-4,4'-biphenylene-diisocyanate, and 1,6-hexamethylenediisocyanate to yield polyurethanes 4–6 containing the NLO-chromophore 2,4-dioxybenzylidenecyanoacetate. The resulting polyurethanes 4–6 were soluble in common organic solvents such as acetone and DMF. Polymers 4–6 showed a thermal stability up to 280°C in TGA thermograms with T _g values obtained from DSC thermograms in the range of 66–114°C. The SHG coefficients (d₃₃) of poled polymer films were around 7.8 × 10⁻⁹ esu. Received: 25 February 2002/ Revised version: 25 March 2002/ Accepted: 29 March 2002     

Synthesis and Properties of Novel Poly(p-phenylenevinylene)s Containing a Tricarbonyl(arene)chromium Unit in the Main Chain

Summary Novel π-conjugated polymers based on poly(p-phenylenevinylene)s (PPVs) containing a tricarbonyl(arene)chromium unit in the main chain were synthesized by Horner-Wadsworth-Emmons olefination. The structures of the polymers were supported by ^lH NMR and IR spectra. The polymers obtained were soluble in common solvents such as THF, CH₂Cl₂, CHCl₃ and toluene. The molecular weights of the polymers were determined by GPC. Their thermal, optical, and electrochemical properties were investigated in detail. Received: 18 November 2002/Revised version: 10 February 2003/ Accepted: 11 February 2003 Correspondence to Yoshiki Chujo     

Synthesis and Thermal Properties of Enyne-Containing Polymers by the Polymerization of Diynes Using a Low-Valent Titanium Catalyst

Summary Polymers having conjugated enyne moieties in the main chain (3) were prepared by the polymerization of diynes (2) using a low-valent titanocene catalyst (1) generated from Cp*₂TiCl₂ and i-PrMgBr. The reactivity of the enyne-containing polymers (3) was demonstrated by the thermal cross-linking reaction at 200 °C.     

Synthesis and Characterization of ZnS and ZnO Nanoparticles via Thermal Decomposition of Two New Synthesized One-Dimensional Coordination Polymers at Two Different Temperatures

Two new Zn(II) coordination polymers from ligand 2,5-bis(3-pyridyl)-3,4-diaza-2,4-hexadiene (bpdh) with different anions, [Zn(μ-bpdh)₂(NCS)₂]_n (1) and [Zn(μ-bpdh)₂(N₃)₂]_n (2) were synthesized and characterized by IR spectroscopy, elemental analyses and X-ray crystallography. The structures of the 1 and 2 may be considered coordination polymers of zinc(II) consisting of metallocyclic chains formed by bridging bpdh ligands, making a one-dimensional array of Zn^II and bpdh in a 1:2 stoichiometry. Different morphologies of ZnS and ZnO nano-particles were obtained by thermolyses of compounds 1–2 in oleic acid at different temperatures under air atmosphere, respectively. The ZnS and ZnO nanoparticles were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM).     

Metal-Containing Polymers Synthesized via Acyclic Diene Metathesis (ADMET) Polymerization Using Electrochemically Reduced Tungsten-Based Catalyst: Polycarbogermanes

Various germanium-containing dienes, bis(4-pentenyl)diethylgermanium (1), bis(4-pentenyl)dimethylgermanium (2) and bis(3-butenyl)diethylgermanium (3), were synthesized and polymerized using an electrochemically reduced tungsten-based catalyst system via acyclic diene metathesis (ADMET) polymerization. All polymer structures were characterized by ¹H- and ¹³C-NMR spectroscopy. These results indicate the retention of the double bonds in the polymer structure with high trans content (57–70%) as expected from a step condensation reaction. These polymers have low molecular weight (M _W) that range from 7400 to 19,100. The thermal stability of polymers was evaluated by thermogravimetric analysis. The glass transition temperatures of the polymer of monomer 1, 2 and 3 were −24, −9 and −47°C, respectively. Synthesis, characterization and the general limitations of ADMET polymers obtained by this catalyst are discussed. An erratum to this article can be found at     

Hyperbranched Poly(ferrocenylene)s Containing Groups 14 and 15 Elements: Syntheses,Optical and Thermal Properties,and Pyrolytic Transformations into Nanostructured Magnetoceramics

A series of hyperbranched poly(ferrocenylene)s containing elements (E) of groups 14 [E=Si (hb-1), Ge (hb-2)] and 15 [E=P (hb-3), Sb (hb-4)] are prepared in good isolation yields (up to 82wt%) by the salt-eliminative polycoupling of dilithioferrocene with tri-(RECl₃) or tetrachlorides of the elements (ECl₄). While the polymers with no or small R groups are insoluble or partially soluble, those with long alkyl chains (R=C_nH_2n+1 with n 8) are completely soluble and film forming. The polymers exhibit solution properties characteristic of hyperbranched macromolecules: e.g. hb-1(18) shows a low intrinsic viscosity ([]=0.02dL/g) despite its high absolute molecular weight (M_w=5 × 10⁵). Spectroscopic analyses reveal that the polymers possess rigid skeleton structures with extended conjugations, with their absorption spectra tailing into the infrared region (>700nm). The polymers show good thermal stability with T_d up to ~400°C and can be graphitized into iron-containing ceramics when pyrolyzed at high temperatures, with char yields up to ~60wt%. While calcinations of the Si-containing polymers (hb-1) at 1000°C under nitrogen give ceramics containing mostly -Fe nanoparticles, those of Ge-(hb-2) and Sb-containing polymers (hb-4) are completely transformed into their iron-alloys. The ceramics from the P-containing polymers (hb-3) show diffraction patterns of iron phosphides. Iron silicide nanocrystals of large sizes are obtained when the pyrolysis of hb-1 is conducted at a high temperature of 1200°C under argon. This ceramic is highly magnetizable (M_s up to ~51emu/g) and shows near-zero remanence and coercivity; in other words, it is an outstanding soft ferromagnet with a high magnetic susceptibility and practically nil hysteresis loss.     

Syntheses and Characterization of 2D and 3D Organotin Polymers with Phenylsuccinic Acid and Trimethyltin Chloride Under Different Conditions

Two types of di- and trimethyltin(IV) polymers [(Me₂Sn)₄O₂(C₁₀H₈O₄)₄] _n 1 and [(Me₃Sn)₂(C₁₀H₈O₄)] _n ·DMF 2 have been synthesized by the reaction of trimethyltin chloride with (±)-phenylsuccinic acid under two different experimental conditions. Both of the complexes are characterized by elemental analysis, IR, NMR (¹H, ¹³C, ¹¹⁹Sn) spectroscopy and X-ray crystallographic diffraction analysis. The structural analyses show that complex 1 is a two-dimensional corrugated sheet polymer consisting of dimeric tetraorganodistannoxane units and bridging ligands. Complex 2 is a 3D corrugated polymer in which the deprotoned acid occurs as a tetradentate ligand and is bonded by the four oxygen atoms. It is worth noting that the X-ray diffraction study reveals that complex 2 crystallizes in the orthorhombic space group P212121, which is chiral space group.     

Structural and Magnetic Properties of One-Dimensional Squarate Bridged Coordination Polymers Containing 2-Aminomethylpyridine Ligand

Three novel one-dimensional (1D) coordination polymers with general formula {[M(μ-sq)₂(amp)₂]·H₂O}_n [M=Cu(II) (1), Zn(II) (2)] and [Cd(μ-sq)₂(amp)₂]_n (3) [sq: Squarate; amp:2-aminomethylpyridine] have been prepared and spectroscopically studied. Each metal (II) ion in 1–3 is octahedrally coordinated by two sq and two amp ligands. The amp ligands are N,N′ coordinated, while the sq ligands bridge the metal centers forming 1D linear chain structure. The individual chains are linked by O–H···O hydrogen bonds involving the hydrogens of water molecules (1–2), amino hydrogens and squarate O atoms (1–3). The hydrogen bonded layers are further assembled into three-dimensional supramolecular networks by weak aromatic π–π interactions. EPR results indicate that the ground state of the paramagnetic electron in 1 and Cu²⁺ doped complexes 2–3 is d_{x² - y²} d_{{x^{2} - y^{2} }} . Magnetic measurements reveal that complex 1 shows paramagnetic behavior.     

Synthesis and Gas Permeability of Novel Poly(diphenylacetylenes) Having Polyethylene Glycol Moieties

4-Trimethylsilyldiphenylacetylenes with methyl group or bromine atom (Me₃SiC₆H₄C≡CC₆H₄R, R = m-CH₃, p-CH₃, m-Br, p-Br, 1a–d, respectively) were polymerized with TaCl₅/ n-Bu₄Sn to afford poly(diphenylacetylene) derivatives (2a–d). The polymers (2a–d) had high molecular weight over 5×10⁵, and gave free-standing membranes by solution casting method. Chlorination of the obtained poly[1-(3-methylphenyl)-2-(4-trimethylsilyl)phenylacetylene] was carried out by using sulfuryl chloride, and then substitution of polyethylene glycol was performed to give poly(diphenylacetylene) possessing polyethylene glycol moieties. Its carbon dioxide permeability (P_{CO 2}) and permselectivity (P_{CO 2}/P_{N 2}) were 2,970 barrers and 9.0, respectively.