Conjugated polymers display unique electronic and optical properties, which favor their use in applications as optoelectronic materials and molecular devices. Despite the recent remarkable progress in the chemistry of conjugated polymers, the synthesis of conjugated polymers containing cyclophane units in the main chain is limited to only a few examples. This Minireview presents recent developments in the synthesis, properties, and applications of through-space conjugated polymers based on cyclophanes. 相似文献
Benzimidazoles are commonly used as an electron acceptor unit in the synthesis of donor acceptor donor type conjugated polymers. This review offers an overview of the utility of benzimidazole derivatives in the synthesis of various donor acceptor donor type of conjugated polymers, covering the research trends in experimental studies. The selected molecules in this overview have been limited with the donor-acceptor-donor type of conjugated polymers including benzimidazole as an acceptor unit and the corresponding studies up to 2016 have been shown. The polymers examined in this paper are discussed in two sections. The first section includes the studies about the effect of benzimidazole unit on the optical feature of resulting donor-acceptor type polymers. The second section illustrates the benzimidazole-based donor-acceptor-donor type conjugated polymers which are utilized in photovoltaic applications. 相似文献
Metal-polymer nanocomposites, which comprise nanoparticles of metals and/or their oxides and carbides uniformly distributed
in stabilizing polymer matrices, are prepared through solid-phase polymerization of metal-containing monomers followed by
controlled thermolysis of synthesized metal-containing polymers. Using X-ray diffraction, electron microscopy, ferromagnetic
resonance, and IR spectroscopy, it is shown that nanoparticles present in these systems have a characteristic core-shell structure
that comprises a metal-containing core and a surface layer, i.e., a polymer shell. Parameters of the components are estimated. 相似文献
The main types of unit variability in metal-containing polymers, including those typical of traditional polymers and those
peculiar only to polymers with metal-containing groups, are surveyed and classified. The methods for controlling unit variability
and the possibility of taking it into account and using it for practical purposes are analyzed. The main problems in this
field and the prospects for their solution are considered.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2403–2420, December, 1998. 相似文献
Transition metal catalysed C−H bond activation chemistry has emerged as an exciting and promising approach in organic synthesis. This allows us to synthesize a wider range of functional molecules and conjugated polymers in a more convenient and more atom economical way. The formation of C−C bonds in the construction of pi-conjugated systems, particularly for conjugated polymers, has benefited much from the advances in C−H bond activation chemistry. Compared to conventional transition-metal catalysed cross-coupling polymerization such as Suzuki and Stille cross-coupling, pre-functionalization of aromatic monomers, such as halogenation, borylation and stannylation, is no longer required for direct arylation polymerization (DArP), which involve C−H/C−X cross-coupling, and oxidative direct arylation polymerization (Ox-DArP), which involves C−H/C−H cross-coupling protocols driven by the activation of monomers’ C(sp2)−H bonds. Furthermore, poly(annulation) via C−H bond activation chemistry leads to the formation of unique pi-conjugated moieties as part of the polymeric backbone. This review thus summarises advances to date in the synthesis of conjugated polymers utilizing transition metal catalysed C−H bond activation chemistry. A variety of conjugated polymers via DArP including poly(thiophene), thieno[3,4-c]pyrrole-4,6-dione)-containing, fluorenyl-containing, benzothiadiazole-containing and diketopyrrolopyrrole-containing copolymers, were summarized. Conjugated polymers obtained through Ox-DArP were outlined and compared. Furthermore, poly(annulation) using transition metal catalysed C−H bond activation chemistry was also reviewed. In the last part of this review, difficulties and perspective to make use of transition metal catalysed C−H activation polymerization to prepare conjugated polymers were discussed and commented. 相似文献
In the past few decades, conjugated polymers have aroused extensive interest in organic electronic applications. The electrical performance of conjugated polymers has a close relationship with their backbone conformation. The conformation of the polymer backbone strongly affects the πelectron delocalization along polymer chains, the energy band gap, interchain interactions, and further affects charge transport properties. To realize a rigid coplanar backbone that usually possesses efficient intrachain charge transport properties and enhanced π–π stackings, such conformation control becomes a useful strategy to achieve high-performance (semi)conducting polymers. This minireview summarizes the most important polymer structures through conformation control at the molecular level, and then divides these rigid coplanar conjugated polymers into three categories: 1) noncovalent interactions locked conjugated polymers; 2) double-bond linked conjugated polymers; 3) ladder conjugated polymers. The effect of the conformation control on physical nature, optoelectronic properties, and their device performance is also discussed, as well as the challenges of chemical synthesis and structural characterization. 相似文献
Divalent metal salts (I) of monohydroxyethyl phthalate have catalytic activity for polymerization of isocyanate groups. The synthesis of novel metal-containing isocyanurate-type crosslinked polyurethanes were investigated by the crosslinking reaction of I in DMF with diisocyanates or urethane prepolymers, that is, diisocyanate adducts of polyethylene glycol. 2,4-Toluene diisocyanate and diphenylmethane diisocyanate were used as diisocyanates, and DMF was the solvent. The crosslinking reactions were followed by determining the gelation time. Gelation time decreased with increasing temperature. The Ca salt was more effective than the Mg salt in the crosslinking reaction. The yields of resulting metal-containing three-dimensional polymers decreased with increasing metal content in the feed. The Ca salt was more easily introduced into the network polymers than the Mg salt was. Decomposition temperatures decreased on introducing metals into the network polymers. Some physical properties of the metal-containing network polymers are also discussed. 相似文献
A combination of transition metals and π-conjugated molecules or polymers as redox-active ligands affords the hybrid conjugated complexes. A variety of structural design is possible based on the coordination number and geometry to construct an efficient multi-redox system. 相似文献
The paper gives a review of publications on polymers with conjugated matrices (PPy, PTh, PAni, hydrocarbon or mixed chains...) which incorporate metallocene complexes (Fe, Ru, Co; Ni, Ti, Zr, Ta) with two cyclopentadienyl ligands (Cp) and their derivatives, in particular with methylated cyclopentadienyl rings (Cp*), as well as hemi-metallocene complexes (Fe, Ru, Co, Mn), as pendant groups or inside the principal chain (part B). The information on related short-chain systems, monomers and oligomers, is also included. In part A, a brief overview of various conjugated polymer materials is presented, with their classification in accordance with the conductivity mechanism (ionic, electronic or mixed conductors) or with the structural type (linear-chain organic or mixed polymers, derivatization, metallopolymers, multi-dimensional structures, alternating and block copolymers with organic or mixed units, hybrid materials with a mixture of conjugated and inert polymers, polymers inside a solid matrix, conjugated polymers with incorporated nanoelements of transition metals, carbon, semiconductors etc. 相似文献
Signal amplification for ultra-sensitive detection has been achieved by energy migration in conjugated semiconducting polymeric assemblies. Critical to optimizing this effect is the synthesis of non-aggregate polymers, the multidimensional directional transport of excited states (excitons), and extending the intrinsic excited state lifetime of conjugated polymers. We developed new water-soluble non-ionic conjugated polymers for use in biosensory applications, which can be used to provide highly sensitive/specific ultra-trace detection that is immune to specificity problems that plauge ionic conjugated polymers. 相似文献
A series of chiral side-chain liquid crystalline (LC) polysiloxanes bearing fluorinated mesogens were synthesized with a cholesteric LC monomer and a fluorinated nematic LC monomer. They were characterized by use of various experimental techniques, and effect of fluorinated mesogens on characteristic of LC polysiloxanes was studied as well. In photoluminescence spectra, a narrow and a broad peak occur at around 270-317 nm, originated, respectively, from fluorinated phenyl groups and the conjugated xenene structure. The specific rotation analysis of all polymers showed negative values, but absolute values were lower than those of the chiral monomers. All polymers showed smectic LC phase with very wide temperature ranges on heating and cooling cycles. Especially, only polymers bearing more fluorinated component exhibited smectic-cholesteric phase transition when they were heated. As the polymers contained more fluorinated mesogens, segregation of the fluorinated segment to the surface should occur at mesomorphic temperature. The highly ordered lamellar mesogen-siloxane matrix systems should be disturbed severely by separation of fluorinated mesogens, suggesting mesogenic orders transition from lamellar smectic to cholesteric phase. 相似文献
This article provides a comprehensive review of the synthesis, properties and applications of organometallic polymers of the transition metals. The different classes of organometallic polymers are described according to their structural make‐up, as well as by their methods of synthesis. A number of examples of each class are given to emphasize the richness and diversity in these areas of research. In addition to linear polymers, hyperbranched, crosslinked, star and dendritic polymers are also described. The properties that transition metal‐containing organometallic polymers possess, as well as the applications that these materials have found in various domains are highlighted.
This paper is an up-to-date mini-review based on literature data and own results regarding synthesis and properties of conducting (pseudo)rotaxane supramolecular structures. Conjugated polymers, such as polyarylene, polyheteroarylene, polyaniline, polyarylenevinylene or polyaryleneimine, were used as axle, while the macrocyclic components were cyclodextrins, cucurbiturils, cyclophanes or crown ethers. Properties of the supramolecular structure such as solubility, thermal or chemical stability, conductivity, etc. can be drastically modified by the inclusion of hydrophobic conjugated polymers inside the macrocycle, without any chemical modification. For instance, the photophysical properties (i.e. quantum yield of fluorescence and electroluminescence) of the supramolecular structures were enhanced when compared with uninsulated conjugated polymers. The doping process is also affected, because the access of a dopant to the conjugated chain is limited only to the uncovered domains of the conjugated chain. 相似文献
Current approaches to synthesize π‐conjugated polymers (CPs) are dominated by thermally driven, transition‐metal‐mediated reactions. Herein we show that electron‐deficient Grignard monomers readily polymerize under visible‐light irradiation at room temperature in the absence of a catalyst. The product distribution can be tuned by the wavelength of irradiation based on the absorption of the polymer. Conversion studies are consistent with an uncontrolled chain‐growth process; correspondingly, chain extension produces all‐conjugated n‐type block copolymers. Preliminary results demonstrate that the polymerization can be expanded to donor–acceptor alternating copolymers. We anticipate that this method can serve as a platform to access new architectures of n‐type CPs without the need for transition‐metal catalysis. 相似文献
A series of metal-containing polyurethane-ureas containing ionic links in the main chain was synthesized by the polyaddition reaction of hexamethylene diisocyanate with mixtures of metal salts of mono(hydroxyethyl) phthalate and bisureas containing two hydroxyl groups which were obtained from monoethanolamine and diisocyanates. The polyurethane-ureas obtained were generally yellowish powders or solids. Close agreement between observed and calculated values of metal content of the metal-containing polyurethane-ureas was obtained. The viscosities (in dimethylformamide) of polyurethane-ureas decreased markedly with increase of metal content. Moreover, the decomposition temperatures were lowered a little by introducing metals into the polyurethane-ureas. Dimethylformamide, m-cresol, and dimethyl sulfoxide were comparatively good solvents for the metal-containing polyurethane-ureas; however, the polymers were insoluble in all other solvents. 相似文献