

FOLLOWUS
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
jz10@pku.edu.cn (J.Z.)
xhwan@pku.edu.cn (X.H.W.)
Received:21 October 2019,
Revised:2019-11-26,
Accepted:28 November 2019,
Online First:18 February 2020,
Published:2020-07
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Wang, S.; Cai, S. L.; Zhang, J.; Wan, X. H. Tunable , Cis-cisoid, helical conformation of poly(3,5-disubstibuted phenylacetylene)s stabilized by , n,→, π,* interaction. Chinese J. Polym. Sci. 2020, 38, 685–695 DOI: 10.1007/s10118-020-2376-z.
Sheng Wang, Si-Liang Cai, Jie Zhang, et al. Tunable
Wang, S.; Cai, S. L.; Zhang, J.; Wan, X. H. Tunable , Cis-cisoid, helical conformation of poly(3,5-disubstibuted phenylacetylene)s stabilized by , n,→, π,* interaction. Chinese J. Polym. Sci. 2020, 38, 685–695 DOI: 10.1007/s10118-020-2376-z. DOI:
Sheng Wang, Si-Liang Cai, Jie Zhang, et al. Tunable
A series of novel
cis
poly(phenylacetylene)s (PPAs) substituted at
meta
-position(s) by two alkoxycarbonyl pendants
i.e.
sP-Me-C8/rP-Me-C8
P-Me-C12
sP-Et-C4
sP-2C4
and
sP-Oct-C4
were synthesized under the catalysis of [Rh(nbd)Cl]
2
(nbd = norbornadiene). The dependence of elongation
screw sense
and stimuli response of helical polyene backbone on the structure of pendant
solvent
and temperature was systematically investigated in both solution and solid states. Because of
n
→
π
* interaction between vicinal carbonyl groups
sP-Me-C8/rP-Me-C8
could adopt contracted
cis-cisoid
helix in THF
toluene
CH
2
Cl
2
and CHCl
3
. Such an intramolecular interaction was sensitive to the hydrogen bond donating ability of solvent and temperature
but insensitive to the dielectric constant and polarity of solvent. In poly(3-methoxycarbonyl-5-alkoxycarbonylphenylacetylene)
the longer the chiral alkyl chain was
the easier the stable
cis-cisoid
helix could be achieved. However
when the methoxycarbonyl was changed to ethoxycarbonyl
sec
-butyloxycarbonyl
and octyloxycarbonyl pendant groups
only
cis-transoid
helix was obtained at room temperature due to the increased steric hindrance. Moreover
lowering temperature was found to facilitate the stabilization of
n
→
π
* interactions
and reversible temperature-dependent stereomutations were achieved in
sP-Me-C8
and
sP-Et-C4
depending on the solvent where they were dissolved. These results suggested that the long alkyl chain
small pendant size
and lower temperature favored the stabilization of intramolecular
n
→
π
* interactions and the formation of contracted
cis-cisoid
helices for poly(3
5-diester substituted phenylacetylene)s.
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