Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 140, Issue 2, Pages 667-674Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b09965
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Funding
- Xunta de Galicia (Centro Singular de Investigacion de Galicia) [GRC2014/040]
- Fundacion Gil Davila fellowship
- Servicio de Microscopia Electronica (RIAIDT, USC)
- Ministerio de Ciencia e Innovacion [CTQ2014-61470-EXP, CTQ2015-70519-P]
- European Union (European Regional Development Fund-ERDF)
- Servicio de Nanotecnologia y Analisis de Superficies (CACTI, UVIGO)
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Both the role of the absolute configuration and the tendency of a chiral monomer to promote a certain helical scaffold in a poly(phenylacetylene) (PPA) have been evaluated to study the communication between two chiral monomers within a copolymer chain. Nineteen different PPA copolymer series-47 helical copolymers altogether-were prepared to explore the existence of a chiral-to-chiral communication mechanism. From the data obtained, we found that communication between two different chiral monomers emerges when both exhibit two special features: (a) a different conformational composition-one must exist in a single low-energy conformation (chiral Sergeant) and the other must present two conformers (chiral Soldier)-and (b) the induction of a similar scaffold in the PPA, either cis-cisoidal or cis-transoidal. In the selected systems, the chiral Soldier includes the 4-ethynylangide (para position) of either (R)- or (S)-2-methoxy-2-phenylacetic acid pendants characterized by their conformational flexibility (equilibrium between synperiplanar and antiperiplanar conformations). The chiral Sergeant contains the same chiral groups but linked to the backbone in meta position [3-ethynylanilide of (R)- or (S)-2-methoxy-2-phenylacetic acid] and is selected on the basis of its restricted antiperiplanar conformation. Incorporation of a very small amount (1%) of the Sergeant into a chain composed of just the Soldier transforms the originally axially racemic chain into a helix with strong sense preference (either M or P) that is determined by the absolute configuration of the Soldier.
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