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1.
3,3′‐Dichloro‐N,N′‐biphthalimide (3,3′‐DCBPI), 3,4′‐dichloro‐N,N′‐biphthalimide (3,4′‐DCBPI), and 4,4′‐dichloro‐N,N′‐biphthalimide (4,4′‐DCBPI) were synthesized from 3‐ or 4‐chlorophthalic anhydrides and hydrazine in glacial acetic acid. The yield of 3,3′‐DCBPI (90%) was much higher than that of 4,4′‐DCBPI (33%) because of the better stability of the intermediate, 3‐chloro‐N‐aminophthalimide, and 3,3′‐DCBPI. A series of hydrazine‐based polyimides were prepared from isomeric DCBPIs and 4,4′‐thiobisbenzenethiol (TBBT) in N,N‐dimethylacetamide in the presence of tributylamine. Inherent viscosity of these polymers was in the range of 0.51–0.69 dL/g in 1‐methyl‐2‐pyrrolidinone (NMP) at 30 °C. These polyimides were soluble in 1,1,2,2‐terachloroethane, NMP, and phenols. The 5% weight‐loss temperatures (T5%s) of the polymers were near 450 °C in N2. Their glass‐transition temperatures (Tgs) determined by dynamic mechanical thermal analysis and differential scanning calorimetry increased according to the order of polyimides based on 4,4′‐DCBPI, 3,4′‐DCBPI, and 3,3′‐DCBPI. The hydrolytic stability of these polymers was measured under acid, basic, and neutral conditions and the results indicated that the order was 3,3′‐DCBPI/TBBT > 3,4′‐DCBPI/TBBT > 4,4′‐DCBPI/TBBT. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4933–4940, 2007  相似文献   

2.
Two new coordination polymers of lanthanum(III) benzoate having pyridine N-oxide and 4,4′-bipyridyl-N,N′-dioxide as ancillary ligands are synthesized and characterized. Different binding modes of the N-oxide are demonstrated; pyridine N-oxide binds as a bridging ligand, whereas 4,4′-bipyridyl-N,N′-dioxide is monodentate.  相似文献   

3.
In the title compound, catena‐poly[[[N,N′‐bis(pyridin‐3‐ylmethyl)‐[1,1′‐biphenyl]‐4,4′‐dicarboxamide]chloridozinc(II)]‐μ‐[1,1′‐biphenyl]‐4,4′‐dicarboxylato‐[[N,N′‐bis(pyridin‐3‐ylmethyl)‐[1,1′‐biphenyl]‐4,4′‐dicarboxamide]chloridozinc(II)]‐μ‐[N,N′‐bis(pyridin‐3‐ylmethyl)‐[1,1′‐biphenyl]‐4,4′‐dicarboxamide]], [Zn2(C14H8O4)Cl2(C26H22N4O2)3]n, the ZnII centre is four‐coordinate and approximately tetrahedral, bonding to one carboxylate O atom from a bidentate bridging dianionic [1,1′‐biphenyl]‐4,4′‐dicarboxylate ligand, to two pyridine N atoms from two N,N′‐bis(pyridin‐3‐ylmethyl)‐[1,1′‐biphenyl]‐4,4′‐dicarboxamide ligands and to one chloride ligand. The pyridyl ligands exhibit bidentate bridging and monodentate terminal coordination modes. The bidentate bridging pyridyl ligand and the bridging [1,1′‐biphenyl]‐4,4′‐dicarboxylate ligand both lie on special positions, with inversion centres at the mid‐points of their central C—C bonds. These bridging groups link the ZnII centres into a one‐dimensional tape structure that propagates along the crystallographic b direction. The tapes are interlinked into a two‐dimensional layer in the ab plane through N—H...O hydrogen bonds between the monodentate ligands. In addition, the thermal stability and solid‐state photoluminescence properties of the title compound are reported.  相似文献   

4.
Singlet and triplet spectra of phosphorescent organic light-emitting diode dopants such as bis(2-methyldibenzo[f,h]quinoxaline)(acetylacetonate)iridium(III) in inhomogeneous amorphous hosts are simulated by time-dependent density functional theory (TDDFT) using molecular dynamics and effective fragment potentials (EFPs). The EFPs of the host molecules N,N′-di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine and 4,4′-bis(N-carbazolyl)-1,1′-biphenyl are constructed from small fragments. The procedure for breaking large molecules into fragments and constructing an EFP is presented. It is demonstrated that polarizable inhomogeneous environment affects the position, intensity, and width of the spectral bands and, therefore, should be taken into account in accurate simulations of spectral bands.  相似文献   

5.
Some members of four series of polyesters were synthesized by the direct polycondensation of two types of dicarboxylic acids (4,4′-dicarboxy-α,ω-diphenoxyalkanes and 4,4′-dicarboxy-α,ω-dibenzoyloxyalkanes) with two types of bisphenols (4,4′-dihydroxy-α,ω-diphenoxyalkanes and 4,4′-dihydroxy-α,ω-dibenzoyloxyalkanes) using tosyl chloride in pyridine in the presence of N, N-dimethylformamide. The 1H-NMR spectra of the polymers synthesized showed that these polymers have an ordenated structure. The mesogenic properties of these polymers were studied by optical microscopy and differential scanning calorimetry. Many of the polymers show nematic mesomorphism.  相似文献   

6.
Two new bis(benzylidenephthalide)monomers were synthesized by melt condensation of phenylacetic acid with 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) and with 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA). A mixture of three isomers for each monomer was obtained and polymerized with diamines to produce new polyimidines. Polymerizations were conducted with m-xylylenediamine (MXDA) or 4,4′-oxydianiline (ODA) in quantitative yields for the undehydrated intermediate. Inherent viscosities ranged from 0.17 to 0.35 dL/g in N,N-dimethylformamide (DMF) or N-methyl-2-pyrrolidone (NMP). These intermediate poly(hydroxylactams) were thermally dehydrated to polyimidines which exhibited a 10% weight loss, as high as 546°C in nitrogen. Inherent viscosities of the dehydrated (cured) polyimidines ranged from 0.14 to 0.20 dL/g in NMP. Brittle films could be cast from NMP solutions.  相似文献   

7.
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  相似文献   

8.
A series of organosoluble aromatic polyimides (PIs) was synthesized from 5,5′‐bis[4‐(4‐aminophenoxy)phenyl]‐4,7‐methanohexahydroindan (3) and commercial available aromatic dianhydrides such as 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), 4,4′‐oxydiphthalic anhydride (ODPA), 4,4′‐sulfonyl diphthalic anhydride (SDPA), or 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropanic dianhydride (6FDA). PIs (IIIc–f), which were synthesized by direct polymerization in m‐cresol, had inherent viscosities of 0.83–1.05 dL/g. These polymers could easily be dissolved in N,N′‐dimethylacetamide (DMAc), N‐methyl‐2‐pyrrolidone (NMP), N,N‐dimethylformamide (DMF), pyridine, m‐cresol, and dichloromethane. Whereas copolymerization was proceeded with equivalent molar ratios of pyromellitic dianhydride (PMDA)/6FDA, 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (BTDA)/6FDA, or BTDA/SDPA, or ½ for PMDA/SDPA, copolyimides (co‐PIs), derived from 3 and mixed dianhydrides, were soluble in NMP. All the soluble PIs could form transparent, flexible, and tough films, and they showed amorphous characteristics. These films had tensile strengths of 88–111 MPa, elongations at break of 5–10% and initial moduli of 2.01–2.67 GPa. The glass transition temperatures of these polymers were in the range of 252–311°C. Except for IIIe, the 10% weight loss temperatures (Td) of PIs were above 500°C, and the amount of carbonized residues of the PIs at 800°C in nitrogen atmosphere were above 50%. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1681–1691, 1999  相似文献   

9.
With regard to crystal engineering, building block or modular assembly methodologies have shown great success in the design and construction of metal–organic coordination polymers. The critical factor for the construction of coordination polymers is the rational choice of the organic building blocks and the metal centre. The reaction of Zn(OAc)2·2H2O (OAc is acetate) with 3‐nitrobenzoic acid (HNBA) and 4,4′‐bipyridine (4,4′‐bipy) under hydrothermal conditions produced a two‐dimensional zinc(II) supramolecular architecture, catena‐poly[[bis(3‐nitrobenzoato‐κ2O,O′)zinc(II)]‐μ‐4,4′‐bipyridine‐κ2N:N′], [Zn(C7H4NO4)2(C10H8N2)]n or [Zn(NBA)2(4,4′‐bipy)]n, which was characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and single‐crystal X‐ray diffraction analysis. The ZnII ions are connected by the 4,4′‐bipy ligands to form a one‐dimensional zigzag chain and the chains are decorated with anionic NBA ligands which interact further through aromatic π–π stacking interactions, expanding the structure into a threefold interpenetrated two‐dimensional supramolecular architecture. The solid‐state fluorescence analysis indicates a slight blue shift compared with pure 4,4′‐bipyridine and HNBA.  相似文献   

10.
This article describes the synthesis of N,N′-bis(3,3′-maleimidophenyl) sulfone (S) and its Michael addition products with (4,4′-diaminodiphenyl) methane (S-M), 4,4′-diaminodiphenyl ether (S-E), (3,3′-diaminodiphenyl) sulfone (S-DDSm), (4,4′-diaminodiphenyl) sulfone (S-DDSp), (3,3′,3″-tris aminophenyl) phosphine oxide (S-TAP), and 9,9-bis(p-aminophenyl) fluorene (S-B). Curing behavior of these bisimides was investigated by differential scanning calorimetry. Activation energy of curing reaction was determined by using isothermal and multiple heating rate method. Thermal stability of bisimides was evaluated by thermogravimetric analysis. Better char yields were obtained in S-TAP resins.  相似文献   

11.
Both of the title compounds, catena‐poly­[[[tetra­aqua­magnesium(I)]‐μ‐4,4′‐bi­pyridine‐κ2N:N′] diiodide bis(4,4′‐bi­pyridine) solvate], {[Mg(C10H8N2)(H2O)4]I2·2C10H8N2}n, (I), and catena‐poly­[[[μ‐4,4′‐bi­pyridine‐bis­[di­iodo­bis­(propan‐1‐ol)­strontium(I)]]‐di‐μ‐4,4′‐bi­pyridine‐κ4N:N′] bis(4,4′‐bi­pyri­dine) solvate], {[Sr2I4(C10H8N2)3(C3H8O)4]·2C10H8N2}n, (II), are one‐dimensional polymers which are single‐ and double‐stranded, respectively, the metal atoms being linked by the 4,4′‐bi­pyridine moieties. The Mg complex, (I), is [cis‐{(H2O)4Mg(N‐4,4′‐bi­pyridine‐N′)(2/2)}](∞|∞)I2·4,4′‐bi­pyridine and Mg has a six‐coordinate quasi‐octahedral coordination environment. The Sr complex, (II), is isomorphous with its previously defined Ba counterpart [Kepert, Waters & White (1996). Aust. J. Chem. 49 , 117–135], being [(propan‐1‐ol)2I2Sr(N‐4,4′‐bi­pyridine‐N′)(3/2)](∞|∞)·4,4′‐bi­pyridine, with the I atoms trans‐axial in a seven‐coordinate pentagonal–bipyramidal Sr environment.  相似文献   

12.
A novel aromatic diamine monomer bearing tertbutyl and 4‐tertbutylphenyl groups, 3,3′‐ditertbutyl‐4,4′‐diaminodiphenyl‐4′′‐tertbutylphenylmethane (TADBP), was prepared and characterized. A series of non‐coplanar polyimides (PIs) were synthesized via a conventional one‐step polycondensation from TADBP and various aromatic dianhydrides including pyromellitic dianhydride (PMDA), 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), 4,4′‐oxydiphthalic anhydride (OPDA), 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride (BTDA) and 4,4′‐(hexafluoroisopropylidene)dipthalic anhydride (6FDA). All PIs exhibit excellent solubility in common organic solvents such as N,N‐dimethylformamide (DMF), N,N‐dimethylacetamide (DMAc), N‐methyl‐2‐pyrrolidone (NMP), dimethyl sulfoxide (DMSO), chloroform (CHCl3), tetrahydrofuran (THF), and so on. Furthermore, the obtained transparent, strong and flexible polyimide films present good thermal stability and outstanding optical properties. Their glass transition temperatures (Tgs) are in the range of 298 to 347°C, and 10% weight loss temperatures are in excess of 490°C with more than 53% char yield at 800°C in nitrogen. All the polyimides can be cast into transparent and flexible films with tensile strength of 80.5–101 MPa, elongation at break of 8.4%–10.5%, and Young's modulus of 2.3–2.8 GPa. Meanwhile, the PIs show the cutoff wavelengths of 302–356 nm, as well as low moisture absorption (0.30% –0.55%) and low dielectric constant (2.78–3.12 at 1 MHz).  相似文献   

13.
Cured N,N,N′,N′-tetraglycidyl-4,4′-diaminodiphenylmethane (TGDDM) based epoxy resins were investigated by high-resolution solid-state 13C-NMR spectroscopy. Associated hardeners were the most commonly used low reactivity 4,4--diaminodiphenylsulphone (DDS), as well as, for comparisons reasons, the higher reactivity 4,4′-diaminodiphenylmethane (DDM) with, in each case, a1 to 1 or 1 to 0.6 epoxy/NH ratio. In order to interpret the spectra, the poorly resolved aliphatic region was decomposed into elementary lines, the structural assignments of which were made using solution 13C-NMR data resulting from a previous model compound study. The main structural feature of all investigated systems is the predominance of small cyclic units resulting from intramolecular reactions of N,N-diglycidylaniline groups. The resins are therefore far less crosslinked that it could be anticipated from the functionality of the reactants. Using the low reactivity DDS still increases this effect, due to a higher proportion of residual non reacted secondary amines. Reducing the initial ratio of hardener could on the contrary lead to a higher proportion of reacted amine function, and thus to a higher crosslinking degree. A qualitative picture of such networks is given at the end.  相似文献   

14.
Dichloro­(4,4′‐dipentyl‐2,2′‐bipyridine‐κ2N,N′)platinum(II), [PtCl2(C20H28N2)], adopts a discrete π–π stacking structure, where the alkyl chains are located in a random manner. In contrast, dichloro­(4,4′‐diheptyl‐2,2′‐bipyridine‐κ2N,N′)platinum(II), [PtCl2(C24H36N2)], forms a layer structure comprised of alkyl chain layers and paired coordination sites, as observed for analogous complexes with longer alkyl chains.  相似文献   

15.
The conformation of [bis‐(N,N′‐difluoroboryl)]‐3,3′‐diethyl‐4,4′,8,8′,9,9′,10,10′‐octamethyl‐2,2′‐bidipyrrin (1) in solution was studied by analyzing the 13C? 19F and 19F? 19F through‐space spin–spin couplings. The 1H and 13C NMR spectra were assigned on the basis of nuclear Overhauser effect spectroscopy (NOESY), heteronuclear single‐quantum correlation (HSQC), and heteronuclear multiple‐bond correlation (HMBC) experiments. The 19F spectrum of 1 was compared with that of 2‐ethyl‐1,3,5,6,7‐pentamethyl‐4,4‐difluoro‐4‐bor‐3a,4a‐diaza‐s‐indacen (2). The 19F? 19F through‐space spin? spin coupling in 1 was thus assigned and the coupling constant was obtained by simulating the coupling patterns. The obtained conformation of 1 was compared with those of the known complexes [bis‐(N,N′‐difluoroboryl)]‐3,3′,8,8′,9,9′‐hexaethyl‐4,4′,10,10′‐tetramethyl‐6,6′‐(4‐methylphenyl)‐2,2′‐bidipyrrin (3)and [bis‐(N,N′‐difluoroboryl)]‐9,9′‐diethyl‐4,4′,8,8′,10,10′‐hexamethyl‐3,3′‐bis(methoxycarbonylethyl)‐2,2′‐bidipyrrin (4). The conformational dynamics of 1, 3, and 4 was surveyed by observing the temperature dependence of the through‐space coupling constants between 253 and 333 K. The 13C? 19F and 19F? 19F through‐space spin–spin couplings thus confirm similar conformations of different BisBODIPYs in solution in contrast to earlier findings in the solid state. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

16.
The synthesis of three novel 5-methylfuryl-containing Schiff bases: N,N′-bis(5-methylfurfurylidene)-4,4′-diaminodiphenylmethane, N,N′-bis(5-methylfurfurylidene)-1,4-phenylenediamine, and N,N′-bis(5methylfurfurylidene)benzidine and the corresponding bis(aminophosphonates) derived from them, 4,4′-bis{N-methyl(diethoxyphosphonyl)-1-[(5-methyl)-2-furyl]} diaminodiphenylmethane, 1,4-bis { N-methyl(diethoxyphosphonyl)-1-[(5-methyl)-2-furyl]} diaminobenzene, and bis{N-methyl(diethoxyphosphonyl)-1-[(5-methyl)-2-furyl]}- benzidine, is reported. The compounds have been characterized by elemental analysis, TLC, IR, and NMR ( 1 H, 13 C, and 31 P) spectra. For comparison, new 13 C and 31 P NMR data of three furyl-containing analogues of the above bis(aminophosphonates) are also regarded. The NMR studies of the two series of bis(aminophosphonates) reveal the presence of one diastereomer (meso or racemic form).  相似文献   

17.
A series of N-methyl-substituted aromatic polyamides derived from the secondary aromatic diamines 4,4′-bis(methylamino)diphenylmethane, 3,3′-bis(methylamino)diphenylmethane, 4,4′-bis(methylamino)benzophenone or 3,3′-bis(methylamino)benzophenone and isophthaloyl dichloride, and terephthaloyl dichloride or 3,3′-diphenylmethane dicarboxylic acid dichloride was prepared by high-temperature solution polymerization in s-tetrachloroethane. Compared with analogous unsubstituted and partly N-methylated aromatic polyamides, the full N-methylated polyamides exhibited significantly lower glass transition temperatures (Tg), reduced crystallinity, improved thermal stability, and good solubility in chlorinated solvents.  相似文献   

18.
A dinuclear manganese(III) tetradentate Schiff-base complex, [Mn2(salophen)2(4,4′-bipy)3](BPh4)2 (1) (salophen = N,N′-o-phenylene-bis(salicylideneaminato)), has been synthesized and structurally characterized. Compound 1 crystallized in the triclinic, P 1 space group, a = 13.431(4), b = 13.791(4), c = 13.886(4) Å, α = 73.599(5)°, β = 80.410(6)°, γ = 71.241(5)°, V = 2328.3(12) Å3. Complex 1 contains two Mn(salophen) moieties bridged by 4,4′-bipy to form a dinuclear unit, with two terminal 4,4′-bipy ligands. Variable temperature magnetic susceptibility (2–300 K) shows very weak ferromagnetic interactions between the Mn(III) ions.  相似文献   

19.
The title inorganic–organic hybrid complex, [CdBr2(C10H8N2)]n, features two‐dimensional [CdBr2(4,4′‐bipy)]n (4,4′‐bipy is 4,4′‐bipyridine) neutral networks, based on the octahedral Cd atom coordinated by four μ2‐Br and two μ2‐4,4′‐bipy at trans positions, yielding a CdBr4N2 octahedron. It crystallizes in the orthorhombic system (Cmmm). All the crystallographically independent atoms are on special positions, namely Cd on mmm, Br on mm, N on mm2, and C on sites of symmetry m or mm2. Optical absorption spectroscopy reveals the presence of an optical gap of 3.76 eV, indicating that the complex is a wide‐gap semiconductor. Photoluminescence investigation reveals that the complex displays strong colour‐tunable emissions, which might originate from a ligand‐to‐ligand charge‐transfer (LLCT) transition. Thermogravimetric differential thermal analysis shows that the complex is thermally stable up to 493 K.  相似文献   

20.
The two‐dimensional mixed‐ligand network catena‐[(μ‐4,4′‐bipyridine)‐bis(μ‐L‐tryptophanato‐κ3N,O,O′)‐diaqua‐dicopper(II) dinitrate] is constructed through the bridging action of both the tridentate amino carboxylato and the bidentate 4,4′‐bipyridine ligand. The enantiomeric L‐tryptophanato ligand acts as an N,O chelate towards one copper atom and bridges through the second carboxylate oxygen atom to the adjacent copper ion. Stacking of the corrugated nets creates channels which are occupied by the hydrogen‐bonded and very weakly Cu‐coordinating nitrate ions.  相似文献   

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