PHENYLENE ACETYLENE

L.S. Swanson, J. Shinar, Y.W. Ding, and T.J. Barton, Photoluminescence, electroluminescence, and optically detected magnetic resonance study of 2,5-dialkoxy derivatives of poly(p-phenylene acetylene) (PPA) and PPA-based light-emitting diodes, Synth. Met., 55 1-6, 1993. 

Week et al. [65] further reported the Co salen complex supported on norbomene polymers (23, 24) with stable phenylene-acetylene linker (Figure 8). The polymer-supported salen catalysts were investigated for HKR of the racemic terminal epoxides that showed outstanding catalytic activities and comparable selectivities to the original catalysts reported by Jacobsen. However, the polymeric catalyst was recycled only once after its precipitation with diethylether as the catalyst became less soluble and less reactive in subsequent catalytic... 

Within the context of the current systems, only the weak fluorescing features of C6o that are maximized at 710 nm should be mentioned explicitly. A representative emission spectrum is illustrated in Fig. 8.2a. Regarding, the phenylene-acetylene building blocks, the major features include strong visible light fluorescence with quantum yields close to unity. Similarly to the absorption maxima, the fluorescence... 

In the chromophore-quencher system (1) a ferrocenyl unit is connected to a Ru(tpy)2 + unit via a p-phenylene-acetylene spacer [141]. The weak emission of the Ru(tpy)2 chromophore is completely quenched in the dyad [142]. For this system, an EnT mechanism could be inferred by analogy with the behavior of related bimolecular systems [140], but PET followed by fast back electron transfer cannot be ruled out. This mechanistic ambiguity is common to most studies on related chro-mophore-ferrocene dyads [143-146]. 

Polymers based on 1,3,5-trisubstituted phenylacetylenic wedges and 1,4-disubstituted phenylene acetylenic linear segments with terminal solubilizing groups have also been reported.24... 

Week [203] developed a monomer salen complex linked to a norbomene via a stable phenylene-acetylene linker and its subsequent polymerization by means of the controlled ROMP method using 3 generation Grubb s catalyst (Scheme 137). This polymerization methodology led to fully functionalized immobilized metal-salen catalyst. By this way, the supported catalyst showed catalytic activities and stereoselectivities similar to the nonsupported Jacobsen catalyst. Moreover, activities and selectivities seemed to depend on the density of the catalytic moieties homopolymer 324 were less selective than their copolymer analogs 325. For example, AE of 1,2-dihydronaphtalene led in both cases to total conversion and 76% ee for the homopolymer 324 vs 81% ee for copolymer 325a. Recycle was possible and after 3 recyles a drastic decrease in ee was observed. AE of dihydronaphtalene led to 81% ee for the first cycle vs 6% ee for the third one. 

B. R. Hsieh, Synthesis of poly(phenylene acetylene) from poly(phenylene vinylene), Polym. Bull. 25 177 (1991). 

These yielded non-resonant x ixa(3w < >,a),w) at 1.907 /tm of up to 1.2 X 10 esu. Meyer et al. [520] carried out two-photon absorption measurements on poly(2,5-dibutoxy-p-phenylene acetylene) and related polymers. Representative data of these authors are shown in Fig. 12-30. 

In more recent work, the Swager group [845] described a chemosensor for TNT based on fluoroescence of a porous form of a phenylene/acetylene containing CP, shown in Eg. (17.31. 

Hoger S (2005) Shape-persistent phenylene-acetylene macrocycles large rings-low yield Angew Chem Int Ed 44(25) 3806-3808... 

Common conductive polymers are poly acetylene, polyphenylene, poly-(phenylene sulfide), polypyrrole, and polyvinylcarba2ole (123) (see Electrically conductive polymers). A static-dissipative polymer based on a polyether copolymer has been aimounced (124). In general, electroconductive polymers have proven to be expensive and difficult to process. In most cases they are blended with another polymer to improve the processibiUty. Conductive polymers have met with limited commercial success. 

The polymers which have stimulated the greatest interest are the polymers of acetylene, thiophene, pyrrole and aniline, poly-p-phenylene, polyphenylvinylene and poly-l,6-heptadiyne. Of these materials polypyrrole has been available from BASF under the trade name Lutamer P160 since 1988. 

Figure 8.12. A conjugated chain in poly(acetylene). (a) changes to (b) when a charge passes along the backbone of the molecule, (c) and (d) show chains of poly(acetylene) and poly(para phenylene) respectively, each containing solitons (after Windle 1996).

The versatility of poly(phenylcne) chemistry can also be seen in that it constitutes a platform for the design of other conjugated polymers with aromatic building blocks. Thus, one can proceed from 1,4- to 1,3-, and 1,2-phenylene compounds, and the benzene block can also be replaced by other aromatic cores such as naphthalene or anthracene, helerocyclcs such as thiophene or pyridine as well as by their substituted or bridged derivatives. Conceptually, poly(pheny ene)s can also be regarded as the parent structure of a series of related polymers which arc obtained not by linking the phenylene units directly, but by incorporation of other conjugated, e.g. olefinic or acetylenic, moieties. 

Most conducting polymers, such as doped poly(acetylene), poly(p-pheny-lene), and poly(/ -phenylene sulfide), are not stable in air. Their electrical conductivity degrades rapidly, apparently due to reaction with oxygen and/or water. Poly(pyrrole) by contrast appears to be stable in the doped conductive state. 

Figure 13 shows the irreversible conversion of a nonconjugated poly (p-phenylene pentadienylene) to a lithiun-doped conjugated derivative which has a semiconducting level of conductivity (0.1 to 1.0 S/cm) (29). Obviously, the neutral conjugated derivative of poly (p-phenylene pentadienylene) can then be reversibly generated from the n-type doped material by electrochemical undoping or by p-type compensation. A very similar synthetic method for the conversion of poly(acetylene-co-1,3-butadiene) to polyacetylene has been reported (30), Figure 14. This synthesis of polyacetylene from a nonconjugated precursor polymer containing isolated CH2 units in an otherwise conjugated chain is to be contrasted with the early approach of Marvel et al (6) in which an all-sp3 carbon chain was employed.

Acetylene dicarboxylate and maleic anhydride failed to react with simple methylene cyclopropenes, but reacted readily with calicene derivatives, as shown by Prinz-bach293. Thus ADD combined with benzocalicene 497 to give the dimethyl tri-phenylene dicarboxylate 499, whose formation can be rationalized via (2 + 2) cycloaddition across the semicyclic double bond as well as (4 + 2) cycloaddition involving the three-membered ring (498/501). The asymmetric substitution of 499 excludes cycloaddition of ADD to the C /C2 triafulvene bond (500), which would demand a symmetrical substituent distribution in the final triphenylene derivative. 

As demonstrated in previous sections, the carbazole unit was introduced as a pendant group or as a chain member in major classes of EL polymers such as PPVs (95-105,141,177, 190) and PFs (62, 63, 242-245). A variety of 2,7-carbazole-derived polymers with different conjugated units, such as 2-alkoxy- and 2,5-dialkoxy-l,4-phenylene (549) and l,l -binaphtha-lene-6,6 -diyl (550 [658]), 2,5-pyridine (551), 2,7-fluorene (245 [345,346]), 2,5 -bithiophene (554 [345]), 5,8-quinoxaline (552), quinquethiophene-SjS -dioxide (450 [550]), 2,5-thiophene (553), 2,5-furan (555), and acetylene (556 [659]) were reported by Leclerc and coworkers... 

Poly(acetylenes) [16], poly(diacetylenes) [17], poly(phenylenes) [18] and poly(phenylenevinylenes) [19] have been proposed as main chains. The new molecular design that has to be developed now concerns the question of where to place the open-shell centres on the pendents in the side chains of the polymers (Iwamura, 1987, 1988 Iwamura and Murata, 1989 Murata et a/., 1987 Ovchinnikov, 1978 Tyutyulkov et al., 1985 Yamaguchi et al., 1987). 

Bunz demonstrated a facile procedure for the preparation of high quality PAEs by a palladium-catalyzed cross-coupling reaction of acetylene gas with diiodoarenes. The polymerization proceeds at 50 °C, and poly(phenylene-ethynylene)s 114 were produced. Catalyst loadings of 0.1-0.2 mol% of palladium were best to achieve the complete i ... 

PAVs, where electrically conductive films with good transparency are easily obtained from their precursor polymers, are one group of -conjugated polymers and regarded as an alternating copolymer of acetylene and arylene. They have variations in chemical structure such as poly(p-phenylene vinylene), (PPV), poly(2,5-thienylene vinylene), (PTV), and poly(2,5-dimethoxy-p-phenylene vinylene), (MOPPVY9-1D. They have... 

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