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. 2022 Dec 27;55(24):10854-10864.
doi: 10.1021/acs.macromol.2c02111. Epub 2022 Dec 7.

Synthesis and Ring-Opening Metathesis Polymerization of o-Dialkoxy Paracyclophanedienes

Yurachat Janpatompong  1 , Andrew M Spring  1 , Venukrishnan Komanduri  1 , Raja U Khan  1 , Michael L Turner  1
Affiliations

Synthesis and Ring-Opening Metathesis Polymerization of o-Dialkoxy Paracyclophanedienes

Yurachat Janpatompong et al. Macromolecules. .

Abstract

The highly strained ortho-diethylhexyloxy [2.2]paracyclophane-1,9-diene (M1) can be synthesized by ring contraction of a dithia[3.3]paracyclophane using a benzyne-induced Stevens rearrangement. This paracyclophanediene undergoes ring-opening metathesis polymerization to give well-defined 2,3-dialkoxyphenylenevinylene polymers with an alternating cis/trans alkene stereochemistry and controllable molecular weight. Fully conjugated block copolymers with electron-rich and electron-deficient phenylene vinylene polymer segments can be prepared by sequential monomer additions. These polymers can be readily isomerized to the all-trans stereochemistry polymer. The optical and electrochemical properties of these polymers were investigated by theory and experiment.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Synthesis of 2,3-Dialkoxy-1,4-PPV
Scheme 2
Scheme 2. (a) ROMP of o-Alkoxy Monomer M1 Using the Second- and Third-Generation Grubbs Catalysts; (b) Sequential ROMP Approach of M1 and M2 to D–A Diblock Arylenevinylene Copolymers
Scheme 3
Scheme 3. Synthesis of Dialkoxy Paracyclophanediene Monomer M1
Figure 1
Figure 1
DFT-optimized geometry of M1.
Figure 2
Figure 2
ROMP of monomers M1 with the G2 catalyst. (a) Molecular weight distribution of polymers 8a–c (SEC in THF) and (b) Dependence of Mn of the polymers 8a–c on the [M]/[G2] ratio.
Figure 3
Figure 3
MALDI-TOF mass spectrum of polymer 8a with an expected degree of polymerization of 10 repeat units.
Figure 4
Figure 4
Photoisomerization of the 8a (a) 1H NMR spectrum of cis/trans-vinylene polymer 8a in CD2Cl2 (b) trans-8a in CD2Cl2 (c) SEC traces of 8a and trans-8a in THF.
Figure 5
Figure 5
Synthesis of the D–A diblock copolymer via the sequential ROMP of cyclophanediene monomers M1 and M2 (SEC in THF).
Figure 6
Figure 6
Photoisomerization of D–A diblock copolymer 9 from cis/trans to trans alkene stereochemistry: (a) 1H NMR spectra of 9, (b) trans-9 in DCM-d2, and (c) SEC traces of 9 and trans-9 in CHCl3.
Figure 7
Figure 7
Absorption and emission profiles of copolymers (a) 8a–c (Ex = 380 nm), (b) trans8a (Ex = 430 nm), and (c) block copolymer 9 (Ex = 330 nm) and trans-9 (Ex = 430 nm) in CHCl3.
Figure 8
Figure 8
Electrochemical HOMO and LUMO energy levels of the polymers.
Figure 9
Figure 9
Frontier orbitals for TD-DFT calculation using B3LYP/6-311G(d,p) of a dimer of cis/trans8 and all-trans8.
Figure 10
Figure 10
Frontier orbitals for TD-DFT calculation using B3LYP/6-311G(d,p) of a dimer of cis/trans9 and all-trans D–A diblock copolymer 9.
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