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Lecture 22 Notes 140415 1 ;> ^ c^ ^ ^£S V K^* f ^ ^ 5 ^\ E \ • ' OV>£MAVW ,57 feC.W\ _ *itf-' ' J!.< '* 5 r \ I' \-J ft w^sVjnC ACS Macro Letters Scheme 1. Synthesis of 4,7-Substituted ACSMacr(Uetter£> pubs.acs.org/macroletters [2.2.2]Paracyclophane-Trienes 4a-c [2.2.2]Paracyclophane-Trienes—Attractive Monomers for ROMP Dominic Maker, Christopher Maier, Kerstin Brodner, and Uwe H. F. Bunz* Organisch-Chemisches Institut, Ruprecht-Karls-Universitat Heidelberg, INF 270, D-69120 Heidelberg, Germany 0 Supporting Information ABSTRACT: Three derivatives of 4,7-substituted [2.2.2]- paracyclophane-trienes were synthesized and used in ring-opening metathesis polymerization (ROMP), resulting in well-soluble poly(para-phenylenevinylene)s (PPV). The paracyclophane-tri- enes were prepared using an iterative buildup of a phenylene— ethynylene backbone, followed by a cis selective Grignard reduction and an intramolecular McMurry reaction. The monomers were applied in ROMP to result in well-soluble PPV derivatives with an unusual substituent pattern. The PPVs were spin-coated into amorphous, highly fluorescent films. To the best of our knowledge, we are the first to synthesize 4,7- Figure 2. Photographs of (A) absorption and (B) emission under substituted [ 2.2.2 Jparacyclophane-trienes and use them as ROMP monomers. ultraviolet illumination (365 nm) of polymer and monomer solutions in CHClj. (C) Photographs of spin-coated films out of C6HSC1 under ultraviolet illumination (365 nm). ue to their spectacular optical and optc"'l'"-Trn"L6 ring-opened into PPV, whereas the (Z,Z,Z,Z)-isomer does not D^properties, conjugated polyrqe/s such as polyfluorene.1 have enough strain energy to be active (Figure 1)." hydrochloric acid, overnight in the dark. Phase separation, polythiophene, poly(phenyleneethynylene) (PPE),' or poly- filtration through a plug of silica, and evaporation of the solvent (para-phenylenevinylene) (PPV\ have been studied intensely.5 nder light exclusion give 3a-c with a nearly complete all-cis Their potential as semiconductors in applications such as onfiguration according to ]H NMR. The dialdehydes 3a—c organic field-effect transistors (OFET),6 organic photovoltaics Scheme 2. Polymerization of Monomers 4a-c to PPV vere directly applied in the pseudo high dilution McMurry (OPV),7 or organic light-emitting diodes (OLEDs)8 is Derivatives Sa—c yclization using a syringe pump, protected with aluminum foil, significant. 'he [2.2.2]paracyclophane-trienes 4a—c are obtained in good PPV mightjie^hp r^pct^y-imifted semiconducting polymer. ields (55-64%) after scaling up. This is higher than the yields UnsuSstitutedPPV has successfully been exploited ror ULhLJs* (Z.Z.Z.Z) (E.Z.E.Z) ublished for similar systems.24' 8'29 4a—c were isolated as pale and OPVs.10 Due to the parents' poor solubility, it is processed ellow-colored oils which show weak fluorescence in their pure Figure 1. Structures of the [2.2.2.2]paracyclophane-tctraenes. out of a precursor polymer by extrusion of leaving groups, as nd dissolved states.10 studied by Wessling et al., which gives the parent PPV.11 If Aromatic proton signals in 'H NMR spectra are high-field solubilizing groups are attached to the PPV backbone, Herein we report the synthesis of dodecyl-, dodccyloxy-, and lifted, overlapping with vinylic signals, reflecting the electronic 2-ethylhexyloxy substituted [2.2.2]paracyclophane-trienes 4a—c nteraction within the system. Surprisingly cyclophanes 4a-c processable PPVs with controlled morphology are accessible.12 ire oils, in contrast to their unsubstituted parent molecule11 or Dozens of different side chains were attached to the PPV as monomers of well-soluble PPVs with an unusual substituent pattern. We developed a new synthetic route for these icir ortho substituted derivatives.29 backbone, highlighting relationships between polymer struc- [2.2.2]paracyclophane-trienes and applied them in ROMP to In Scheme 2, ROMP of 4a-c into PPVs 5a-c is shown; ture, phototuminescence yield, and efficiency of electro- give the PPVs 5a-c. 'able 1 summarizes the properties of the resulting PPVs. luminescence. ll>14 Scheme 1 shows the key synthetic steps. In the original ilymerization of 4a at room temperature yields PPV 5a with a Substituted and soluble PPVs are synthesized by Gitch-type, synthesis of the parent 4, Tanner et al. used a Wittig reaction olydispersity of 2.8. Increasing the temperature lowers the Pd-catalyzed, and other methods.1^"1* Acyclic diene metathesis building up the cis double bonds. Trying the same with para- olydispersity of 5a to 1.9, assuming that higher temperatures (ADMET) or ring-opening metathesis polymerization substituted benzene derivatives led to a mixture of cis and trans nproves the initiation of ROMP of 4a. The alkoxy substituted (ROMP) of suitable precursors is an attractive alternative for isomers, hardly separable. Consequently, we developed an erivatives 4b and 4c do not show any reaction at room defect free PPVs.19 After Bazan et al. studied the ROMP of alternative route. Sonogashira-Hagihara coupling gives la—c, ;mperature or in refluxing THF. A change to the higher paracyclophenes into PPV precursor polymers,20 Turner et al. which are easily and cis selectively transformed into 2a—c - Ill aii inliAlllulauUl McMurry reaction, yielding the 4,7- oiling solvent toluene (110 °C reaction temperature) elegantly developed a direct ROMP-approach of substituted through a Grignard reduction.26 substituted [ 2.2.2 ]paracyclophane-trienes 4a—c. reduces PPVs 5b and Sc with polydispersities of 1.4 and 1.7. [2.2]paracyclophane-dienes giving PPV-homo-21 and -block- For cyclization we used the McMurry reaction but To avoid the problem of isomerization of 3a—C, we The higher reaction temperature is necessary due to the copolymers.22' * However, the paracyclophane-diene mono- encountered several problems. Deprotection of acetals 2a—c employed the configurationally stable acetals 2a-c in the oxygen in the side chains of 4b,c, which works as anchor group mers are difficult to synthesize, yet ROMP is a suitable and with hydrochloric acid in THF yields crude diatdehydes 3a—c, intramolecular McMurry reaction.27 Acceptable yields are for the catalyst, inducing an energy barrier for ROMP. 'H powerful method for the direct synthesis of soluble PPV which can be purified by column chromatography. Unfortu- obtained (100 mg ~40%) on small scales but yields drop NMR spectroscopy of polymers 5a—c (see Supporting derivatives with low polydispersities. nately, when dissolved, 3a—c isomerize rapidly. The yield of the upon scale-up, and the competing intermolecular polymer- Information) shows a trans/cis ratio about 59—70%, Inspired by Mullen et al and Oda et al." we contended desired all-cis isomers drop. Nevertheless, 3a—c can be coupled ization becomes prevalent. Reductive ring closure, yielding a respectively, indicating that the double bonds formed during that larger cyclophenes might have enough strain energy to yive _ single instead of a double bond, is another side reaction when ROMP are mostly trans-con figured and those that are not using 2a—c, complicating purification. ROMP-able monomers We found that unsubstituted [2.2.2]- Received: March S, 2014 opened by ROMP tend to isomerize easily (calculated trans/cis The solution to the problem of isomerization and low yields paracyclophane-triene follows ROMP into insoluble PPV. The Accepted: Apnl 8, 2014 ratio: 33%). Thermogravimetric analysis of the polymers during scale-up is the simple omission of the purification of the (E,Z,E,Z)-isomer" of [2.2.2.2]paracyciophane-tetraene is also indicates no weight loss up to 300 °C. As metathesis is quite dialdehydes 3a-c. Dioxolanes 2a-c are deprotected by diluted sensitive to steric effects, we assume that the double bond r ACS Publications ag/10.1031/miS0013Si I ACS M •oirtt 2014, ), 414-41* < ' fa 6XS- OS. -' ( ^^ ^ + 's Jktf 22 Introduction to Chain Molecules - xxxxxxxxx A A A A / XX XX XX XX A A A A / Figure 1.3 .Sections nl polyvinyl X" chains ol iljftcring tacticily: (a» isoiaclic. (h) syndiotactic. and (cl aluctic. Chapter 5 is devoted to a discussion of their preparation and characteri/ation. For now. only the terminology involved in their description concerns us. Three different situations can be distin- guished along a chain containing pseudoasymmetric carbons: I. l\ntuct'u-. All sLibsiiiuents lie on the same side of the extended chain. Alternatively, the stereoconfiguration at the asymmetric centers is the same. say. -DDDDDDDDD-. 1. Syndiotactic. Substituents on the fully extended chain lie on alternating sides of the backbone. This alternation ot 'configuration can be represented as DLDLDLDLDLDL-. 3. Alactic. Substituents are distributed at random along the chain, tor example. DDLDLLLDLDLL-. Figure U shows sections of polymer chains of these three types: the substituent X equals phenyl for polystyrene and methyl lor polypropylene. The general term for this stereoregularity is tiifiiiiiy. a term derived from the Greek word meaning "to put in order." Polymers of different tactieily have quite different properties, especially in the solid state. As we will see in Chapter H. one of the requirements for polymer cry stallmity is a high degree of microstructural regularity to enable the chains to pack in an orderly manner. Thus atactic polypropylene is a soft, tacky substance, whereas both isoiaclic and syndiotactic polypropylene are highly crystalline. 1.6.3 Geometrical Isomerism The final type of isomerism we take up in this section is nicely illustrated by the various possible structures that result from the polymerization of 1.3-diencs. Three important monomers of ihis type are 1.3-butadiene, 1.3-isoprene. and 1,3-chloroprene. Structure (I.X) through Structure (I.XII). respectively: (I.X) ^ 204 Copolymers, Microstructure, and Stereoregularity Solution Since the total numbers of dsads and triads always occur as ratios in Equation 5.9.3 and Equation 5.9.4, both the numerators and denominators of these ratios can be divided by the total number of (Kails or Iliads to convert these total numbers into fractions, i.e., Thus the fractions in Table 5.7 can he substituted for the i/s in Equation 5.9.3 and Equation 5.9.4.
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