Synthesis of 1,1,9,9-tetrafluoro[2.2]paracyclophane and its polymerization by vapor deposition method

1,1,9,9-Tetrafluoro[2.2]paracyclophane ( 1 ) was prepared successfully as white crystals in 72% yield via two-step reactions from 1,9-diketo[2.2]-paracyclophane. The polymerization of 1 by the vapor deposition method was carried out at pyrolysis temperature range of 400 to 800°C and deposition temperature range of ?20 to 20°C, and a tough, transparent poly(α,α-difluoro-p-xylylene) film was obtained in 72% yield at the pyrolysis temperature of 750°C and the deposition temperature of ?20°C. It was found that the pyrolysis of 1 gave a reactive α,α-difluoro-p-xylylene, which polymerized on the head-to-tail addition to give poly(α,α-difluoro-p-xylylene). Some properties such as solubility, thermal stability, glass transition temperature, and density for poly(α,α-difluoro-p-xylylene) were studied. © 1995 John Wiley & Sons, Inc.     

Chemical vapour deposition polymerization of substituted [2.2]paracyclophanes

Chemical vapour deposition polymerisation of substituted [2.2]paracyclophanes is applied to the functionalised coating of stainless steel surfaces. Poly[o-trifluoroacetyl-p-xylylene-co-p-xylylene] ( 2a ), poly[o-hydroxymethyl-p-xylylene-co-p-xylylene] ( 2b ), poly[o-amino-p-xylylene-co-p-xylylene] ( 2c ) and poly(p-xylylene-2,3-dicarboxylic anhydride) ( 2d ) were deposited as thin layers.     

Heats of formation of [2.2]paracyclophane-1-ene and [2.2]paracyclophane-1,9-diene - an experimental study

The enthalpies of formation [Delta(g)] of tricyclo[8.2.2.2(4,7)]hexadeca-1(13),2,4(16),5,7(15),10(14),11-heptaene (2, 1,2-dehydro[2.2]paracyclophane or [2.2]paracyclophane-1-ene) and tricyclo[8.2.2.2(4,7)]hexadeca-1(13),2,4(16),5,7(15),8,10(14),11-octaene (3, 1,2,9,10-dehydro[2.2]paracyclophane or [2.2]paracyclophane-1,9-diene) have been determined by measuring their heats of combustion in a microcalorimeter and their heats of sublimation by the transpiration method. Values of the strain energies (SE) [SE(2) = 34.7 kcal mol(-)(1), SE(3) = 42.0 kcal mol(-)(1)] have been derived from the gas-phase heats of formation and are compared with those from MM3 and PM3 calculations and with the corresponding value SE(1) = 30.1 kcal mol(-)(1) for the parent tricyclo[8.2.2.2(4,7)]hexadeca-1(13),4(16),5,7(15),10(14),11-hexaene (1, [2.2]paracyclophane). The higher strain energies of 2 and 3 (by 4.6 and 11.9 kcal mol(-)(1)) are in accord with the well-known increased reactivities of their aromatic rings as a consequence of their increased bending. As revealed by an X-ray crystal structure analysis, the bending in the monoene 2 corresponds to that of 1 and 3 at one of two bridging corners.     

Ethynyl[2.2]paracyclophanes and 4-isocyano[2.2]paracyclophane as ligands in organometallic chemistry

An alternative synthesis of (±)-4-ethynyl[2.2]paracyclophane (PCPCCH) (5) and 4,16-diethynyl[2.2]paracyclophane (6) via the Corey-Fuchs reaction has been developed. The olefinic intermediate 4-dibromovinyl[2.2]paracyclophane (3) has been isolated and structurally characterized. The racemic terminal alkyne 5 was employed as starting material for assembling of a luminescent extended π-conjugated system containing a thiophene unit and for a catalytic bis-silylation reaction yielding the olefinic dithioether Z-PhSCH₂Me₂SiC(H)C(PCP)SiMe₂CH₂SPh (9). The dimetallatetrahedran [Co₂(CO)₆(μ-η²-PCP-CCH)] (10) has been prepared and its crystal structure determined by an X-ray diffraction analysis. Alkyne 5 has also been used for the preparation of the Pt(0) complex [Pt(PPh₃)₂(PCPCCH)] (11) and the heterodinuclear dimetallacyclopentenone [(OC)₂Fe{μC(O)C(PCP)C(H)}(μ-dppm)Pt(PPh₃)] (12). The synthesis and reactivity of 4-isocyano[2.2]paracyclophane (15) towards heterobimetallic iron-platinum and palladium-platinum complexes is also presented. Opening of the dative iron → platinum bond of [(OC)₄Fe(μ-dppm)PtCl₂] (16) occurred upon addition of 15 to a CH₂Cl₂ solution of 16 leading to [(OC)₄Fe{μ-dppm}PtCl₂(CNPCP)] (17). Treatment of [ClPd(μ-dppm)₂PtCl] (18) with isocyanide 15 in a 1:1 ratio affords the A-frame compound [ClPd(μ-dppm)₂(μ-CNPCP)PtCl] (19), resulting from formal insertion of 15 into the Pd-Pt bond. Addition of 2 equiv. of 15-18 leads to the ionic A-frame compound [ClPd(μ-dppm)₂(μ-CNPCP)Pt(CNPCP)]Cl (20).     

Synthesis and ring-opening metathesis of tetraalkoxy-substituted [2.2]paracyclophane-1,9-dienes

Tetraalkoxy-substituted [2.2]paracyclophane-1,9-dienes can be prepared in three steps from dithia[3.3]paracyclophanes. A mixture of pseudo-geminal and pseudo-ortho diastereomers is produced and the pure compounds can be separated by fractional crystallization. The solid state structures of these diastereomers reveal strongly distorted aromatic rings consistent with high levels of ring strain. Reaction of these diastereomers with the second generation Grubbs catalyst shows that only the pseudo-geminal isomer can be ring opened to give cis,trans-distrylbenzenes. The origin of this selectivity is discussed and the photoisomerization of the as-formed cis,trans-product to the all trans isomer is demonstrated.     

Conformational rigidity and flexibility of the paracyclophane skeleton in substituted [2.2]paracyclophanes

The character of distortions of the paracyclophane skeleton in various substituted [2.2]paracyclophanes was analyzed based on X ray diffraction data. The rigidity of the skeleton is provided by ethylene bridges and flexibility of the benzene rings, which adopt a boat conformation. The flexibility of the skeleton is manifested in the displacement of the benzene rings with respect to each other and conformational changes of ethylene bridges. The changes in these characteristics are very sensitive to intra- and intermolecular steric factors and are indicative of the absence of strong specific stacking interactions between the be nzene rings. Precision X-ray diffraction study and quantum-chemical calculations for unsubstituted [2.2]paracyclophane and 4,7-benzoquinono[2.2]paracyclophane demonstrated that there are no attractive interactions between the benzene rings, and the electron density is localized predominantly on the outer surface of the rings. This fact can be considered as the cage molecular effect of the [2.2]paracyclophane skeleton.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1707–1732, September, 2004.     

Full multinuclear resonance analysis of 4-amino-1,1,2,2,9,9,10,10-octafluoro[2.2]paracyclophane

The complete assignment of 19F, 1H and 13C NMR spectra for a monosubstituted octafluoro[2.2]paracyclophane derivative is described for the first time. The unambiguous assignments were achieved through the combination of 19F--1H HOESY, 1H COSY and 19F COSY techniques and then further confirmed employing a complementary approach using a Karplus-dependent 3JCF interaction. Interesting aspects of the coupling patterns for various JHH, JHF, JCF and JFF interactions are also discussed.     

Synthesis of novel mono- and diaryl-substituted [2.2]paracyclophanes

The cross-coupling reactions of 4-bromo[2.2]paracyclophane withp-tolylmagnesium bromide in the presence of various palladium and nickel complexes have been studied. It was found that [1,1 -bis(diphenylphosphinoferrocene)]palladium dichloride (PdCl₂ · dppf) shows the highest catalitic activity in this reaction. A series of new mono- and diaryl [2.2]paracyclophane derivatives with various substituents in the arene ring have been synthesized using this catalyst. It was shown that it is possible to cross-couple organozinc [2.2]paracyclophane derivatives with aromatic bromides. The composition and structure of the compounds obtained have been established on the basis of elemental analysis and spectral data. Some correlations between the structure and spectral parameters of mono- and diarylsubstituted [2.2]paracyclophanes have been found.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1081–1085, June, 1994.The present work was financially supported by the Russian Foundation for Basic Research (Project No. 93-03-5246).The authors wish to express their gratitude to Prof. N. A. Bumagin for his scientific interest and helpful discussions.     

Vapor phase polymerization of 3,4‐ethylenedioxythiophene on flexible substrate and its application on heat generation

An oxidative chemical vapor phase polymerization process is applied to coat flexible polyethylene terephthalate (PET) fabrics with a uniform poly(3,4‐ethylenedioxythiophene) (PEDOT) film. This vapor phase polymerization method is a solventfree technique, which could yield a low resistance in the PEDOT‐coated PET fabric. The resistance as low as 52 Ω square^?1 is achieved. The polymerization conditions, such as the concentration of oxidant, reaction time, and temperature, have been systematically investigated. The coated fabric samples exhibit an increase in temperature when subjected to a fixed DC voltage. This result indicates a potential application of these PEDOT‐coated fabrics as electric heating materials. Copyright © 2009 John Wiley & Sons, Ltd.     

Investigation of the correlations between 19F and 1H NMR signals for various mono‐ and di‐substituted octafluoro[2.2]paracyclophanes

A selection of mono‐ and pseudo ortho di‐substituted octafluoro[2.2]paracyclophane derivatives were analyzed using ¹⁹F‐¹H HOESY, ¹H COSY and ¹⁹F COSY techniques. This resulted in the unambiguous assignment of the ¹⁹F and ¹H NMR resonances, and also revealed interesting solvent effects and noteworthy coupling patterns for various J_HH, J_HF, and J_FF interactions, including observable through bond ⁷J_FF and ⁸J_FF couplings. For the four mono‐substituted derivatives, the assignments were achieved through the combination of ¹⁹F‐¹H HOESY, ¹H COSY and ¹⁹F COSY techniques. The C₂ symmetry of the six pseudo ortho di‐substituted derivatives that were examined produced simplified spectra, and careful inspection of the characteristic ¹H coupling patterns led to the assignment of ¹H signals. Therefore only ¹⁹F‐¹H HOESY experiments were required to complete the assignments for those molecules. Refinements and alternative strategies for previous protocols are presented for the molecules that were less responsive to nuclear Overhauser effect (nOe) experiments. Copyright © 2009 John Wiley & Sons, Ltd.     

Vapor phase oxidative synthesis of conjugated polymers and applications

Since their discovery, electrically conductive polymers have gained immense interest both in the fields of basic and applied research. Despite their vast potential in the fabrication of efficient, flexible, and low‐cost electronic and optoelectronic devices, they are often difficult to process by wet‐chemical methods due to their very low to poor solubility in organic solvents. The use of vapor‐based synthetic routes, in which conductive polymers can be synthesized and deposited as a thin film directly on a substrate from the vapor phase, provides many unique advantages. This article discusses oxidative vapor deposition processes, primarily vapor phase polymerization and oxidative chemical vapor deposition, of conjugated polymers and their applications. The mild operating conditions (near room temperature processing) allow conformal and functional coatings of conjugated polymers on delicate substrates. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

单晶硅上化学气相沉积铜薄膜的机理研究

A versatile metal-organic chemical vapor deposition (MOCVD) system was designed and constructed. Copper films were deposited on silicon (100) substrates by chemical vapor deposition (CVD) using Cu(hfac)2 as a precursor. The growth of Cu nucleus on silicon substrates by H2 reduction of Cu(hfac)2 was studied by atomic force microscopy and scanning electron microscopy. The growth mode of Cu nucleus is initially Volmer-Weber mode (island), and then transforms to Stranski-Rastanov mode (layer-by-layer plus island).The mechanism of Cu nucleation on silicon (100) substrates was further investigated by X-ray photoelectron spectroscopy. From Cu2p, O1s, F1s, Si2p patterns, the observed C=O, OH and CF3/CF2 should belong to Cu(hfac) formed by the thermal dissociation of Cu(hfac)2. H2 reacts with hfac on the surface, producing OH. With its accumulation, OH reacts with hfac, forming HO-hfac, and desorbs, meanwhile, the copper oxide is reduced, and thus the redox reaction between Cu(hafc)2 and H2 occurs.     

Vapor deposition of ultrathin hydrophilic polymer coatings enabling candle soot composite for highly sensitive humidity sensors

Candle soot (CS) is a desirable carbon nanomaterial for sensors owing to its highly porous nanostructure and large specific surface area. CS is advantageous in its low-cost and facile preparation compared to graphene and carbon nanotubes, but its pristine nanostructure is susceptible to collapse, hampering its application in electronic devices. This article reports conformal coating of nanoscale crosslinked hydrophilic polymer on CS film using initiated chemical vapor deposition, which well preserved the CS nanostructure and obtained nanoporous CS@polymer composites. Tuning coating thickness enabled composites with different morphologies and specific surface areas. Surprisingly, the humidity sensor made from composite with the lowest filling degree, thus largest specific surface area, showed relatively low sensitivity, which is likely due to its discontinuous structure, thus insufficient conductive channels. Composite sensor with optimum filling degree shows excellent sensing response of more than 10³ with the linearity of R² = 0.9400 within a broad relative humidity range from 11% to 96%. The composite sensor also exhibits outstanding sensing performance compared to literature with low hysteresis (3.00%), a satisfactory response time (28.69 s), and a fast recovery time (0.19 s). The composite sensor is fairly stable and durable even after 24 h soaking in water. Furthermore, embedding a humidity sensor into a face mask realizes real-time monitoring of human breath and cough, suggesting promising applications in respiratory monitoring.     

On-wafer thermomechanical characterization of a thin film polyimide formed by vapor deposition polymerization for through-silicon via applications: Comparison to plasma-enhanced chemical vapor deposition SiO2

Thin-film polyimides were prepared by solvent-less vapor deposition polymerization (VDP) from pyromellitic dianhydride and 4,4′-oxydianiline at 200 °C for liner dielectric formation of vertical interconnects called through-silicon vias (TSVs) used in three-dimensionally stacked integrated circuit (3DICs). FTIR, synchrotron XPS, and TDS were employed for determining the imidization ratio, and in addition, the mechanical properties, coefficient of thermal expansion and Young's modulus, of the VDP polyimide were characterized on Si wafers. The VDP polyimide exhibited extremely high conformality, beyond 75%, toward high-aspect-ratio deep Si holes, compared with conventional SiO₂ prepared by plasma-enhanced chemical vapor deposition. The adhesion between the VDP polyimide and Si wafer was enhanced by an Al-chelate promotor. Remarkably, the VDP polyimide TSV liner dielectrics showed much less thermomechanical stresses applied to the Si surrounding the TSVs than the plasma-chemical vapor deposition SiO₂. The small keep-out zone is expected for scaling down highly reliable 3DICs for the upcoming real artificial intelligence society.     

Discrimination of pseudo‐meta and pseudo‐para diamino‐octafluoro[2.2]paracyclophanes by 1H, 19F,and 13C NMR

Pseudo‐meta and pseudo‐para diamino‐octafluoro[2.2]paracyclophanes are challenging to separate either by chromatography or recrystallization, but through the use of a mixture of the two isomers, the ¹H, ¹⁹F, and ¹³C NMR spectra of these compounds have been fully and unambiguously assigned using ¹H COSY, ¹H‐¹⁹F HOESY, ¹H‐¹³C HSQC, ¹H‐¹³C HMBC, and ¹⁹F‐¹³C HSQC techniques. This permits the easy identification of either of the individual isomers. In addition, the ¹³C spectrum of the pseudo‐ortho analogue is reported and assigned for the first time. The gem shift effect in this series of bridge‐fluorinated paracyclophanes serves to deshield ¹H resonances and shield ¹³C. Copyright © 2012 John Wiley & Sons, Ltd.     

简便的双环化反应合成3,7-二甲基-4a,16-二羟基-1H-苯并[5,6]茚并[2,1-1]氧杂蒽-1,9-二酮化合物及其结构表征

标题化合物C26H26O5以2,3-萘二甲醛和5-甲基-1,3-环己二酮为原料,在醋酸溶剂中,室温下经搅拌多组分一锅法合成得到.其结构通过单晶X-射线衍射法确定,晶体属单斜晶系,空间群P21,相对分子质量Mr=418.47,晶胞参数a=0.990 04(8) nm,b=1.090 98(9)nm,c=1.042 46(11) nm,V=1.087 53(17) nm3,Z=2,晶胞密度Dc=1.278 g/cm3,吸收系数μ=0.088mm-1,单胞中电子的数目F(000) =444.晶体结构用直接法解出,经全矩阵最小二乘法对原子参数进行修正,最终的偏离因子为R1 =0.053 3,wR2=0.129 3.在晶体结构中新形成的吡喃环为半椅式构象,而茚中五元环则为信封式构象.     

Cyclopolymerization of 3-phenyl[5]ferrocenophane-1,5-dimethylene: Synthesis and electronic properties of a polyferrocenophane

Radical cyclopolymerization of 3-phenyl[5]ferrocenophane-1,5-dimethylene ( 2 ) and copolymerization with styrene gave polymers ( 3 and 4 ) with [3]ferrocenophane moieties pendant to the backbone. Cyclic voltammetry (CV) on polymer 3 in CH₂Cl₂ showed two oxidation waves at −0.13 and +0.05 V (versus ferrocene/ferrocenium) and CV on copolymer 4 showed one oxidation potential at −0.03 V. CV on 3 in dimethylacetamide showed only one oxidation potential at −0.10 V. Near-IR spectroscopy of partially oxidized 3 showed a broad intervalence band at ca. 2000 nm, indicative of low-energy barriers to electron hopping. Conductivity measurements on 3 and poly(vinylferrocene) (PVFc) oxidatively doped with iodine vapors under an argon atmosphere showed a maximum conductivity ca. 5 × 10⁻⁵ S/cm before the samples cracked, while 4 exhibited a maximum conductivity of 1.6 × 10⁻⁶ S/cm. On iodine doping under ambient conditions, polymers 3 , 4 , and PVFc showed maximum conductivities of 7.6 × 10⁻⁴, 9.5 × 10⁻⁵, and 5.5 × 10⁻⁵ S/cm, respectively. Conductivity measurement were also performed on samples of 3 ⁺BF₄⁻ with oxidation levels ranging from 8 to 56%. Conductivities of these samples ranged from ca. 10⁻¹⁰ to 10⁻⁹ S/cm under vacuum and ca. 10⁻⁶ S/cm under ambient conditions, indicating that atmospheric moisture has a strong effect on the conductivity. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 3365–3376, 1997     

超分子化合物[UO2Cl4][phenH]2的合成、晶体结构、荧光性质及[UO2Cl4][phenH]2/PVA薄膜的发光性能

水热条件下合成了一种含铀的超分子化合物[UO2Cl4][phenH]2(phen=1,10-邻菲罗啉),进行了X射线单晶衍射、红外光谱、紫外光谱和荧光光谱分析。 晶体结构分析表明,该化合物由2个[phenH]+阳离子和1个阴离子[UO2Cl4]2-组成。 红外光谱和X射线单晶衍射表明,标题化合物的三维框架是由N-H…Cl、C-H…Cl和C-H…O弱氢键相互作用所构建。 中心U原子是六配位,有4个Cl原子和2个O原子。 此外,没参与配位的phen利用氢键和π…π堆积与[UO2Cl4]2-相互作用。 含U原子的阴离子是一种扭曲八面体结构。 利用溶胶-凝胶法合成了化合物的PVA薄膜。 标题化合物和薄膜均有较强的荧光性。CCDC:713149     

一种新的有机-无机混配配位聚合物[Zn(N3)2(bpp)]n的自组装及晶体结构(bpp=1，3-二吡啶丙烷)

A novel coordination polymer [Zn(N₃)₂(bpp)]_n[bpp=1，3-bis(4-pyridyl)-propane] was synthesized at room temperature and structurally characterized by means of X-ray single crystal diffraction. The results show that the polymer exhibits a linear chain structure; the Zn-Zn distance is 12.235?. Each Zn(Ⅱ) ion is coordinated by two nitrogen atoms from bpp ligands and two nitrogen atoms from azido (N₃^-) groups， the coordination geometry of Zn(Ⅱ) ion is a slightly distorted tetrahedron， the angles around Zn(Ⅱ) ions are from 103.27° to 121.37°. In the solid-state structure of the polymer， the linear chains are stacked with parallel mode along a direction. Moreover， between adjacent chains， there are π-π interactions between pyridine rings， which are arranged in face-to-face fashion with interplanar distances of av. 3.821?. CCDC： 189591.