Arias, SandraRodríguez Riego, RafaelRiguera Vega, RicardoQuiñoá Cabana, EmilioFreire Iribarne, Félix Manuel2018-01-262019-12-142017-12-14Arias, S., Rodríguez, R., Quiñoá, E., Riguera, R., & Freire, F. (2018). Chiral Coalition in Helical Sense Enhancement of Copolymers: The Role of the Absolute Configuration of Comonomers. Journal Of The American Chemical Society, 140(2), 667-674. http://dx.doi.org/10.1021/jacs.7b099650002-7863http://hdl.handle.net/10347/16391NOTICE: This is the peer reviewed version of the following article: Arias, S.; Rodríguez, R., Quiñoá, E.; Riguera, R.; Freire, F.. Chiral Coalition in Helical Sense Enhancement of Copolymers: the Role of the Absolute Configuration of Comonomers Promoting the Helical Scaffold. J. Am. Chem. Soc. 2018, 140, 667-674. This article may be used for noncommercial purposes in accordance with ACS Terms and Conditions for self-archivingBoth the role of the absolute configuration and the tendency of a chiral monomer to promote a certain helical scaffold in a polyphenylacetylene (PPA) —that depends on the conformational composition at the pendant group— have been evaluated to study the communication between two chiral monomers within a copolymer chain. 19 different PPA copolymer series —47 copolymers altogether— were prepared to explore the existence of a chiral to chiral communication mechanism in helical copolymers. From the data obtained, we found that communication between two different chiral monomers within a copolymer chain emerge when the two monomers exhibit two special features: (a) a different conformational composition —one chiral monomer must exist in a single low energy conformation ("chiral Sergeant") and the other must present an equilibrium between two different conformers ("chiral Soldier")—, and (b) both chiral monomers must promote a similar scaffold in the PPA, either cis-cisoidal or cis-transoidal. In the selected systems, the chiral Soldier includes the 4-ethynylanilide (para position) of either (R)- or (S)-2-methoxy-2-phenylacetic acid [(R)- or (S)-1], pendants characterized by their conformational flexibility once polymerized (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, (R)- or (S)-2] and is selected on the basis of its restricted antiperiplanar conformation. Incorporation of a very small amount (1%) of the Sergeant [either (R)- or (S)-2] to a chain composed just by 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. For instance, both poly-[(R)-10.9-co-(R)-20.1] and poly-[(R)-10.9-co-(S)-20.1] adopt M helical structures due to the absolute configuration of the soldier, although the extent of the chiral amplification induced by the Sergeant is different as a consequence of a different communication mechanism between the (R)-Sergeant/(R)-Soldier and the (S)-Sergeant/(R)-Soldiereng© American Chemical SocietyChiral CommunicationHelical PolymersPoly(phenylacetylene)sChiral ConflictSergeants and Soldiers effectjournal article10.1021/jacs.7b099651520-5126open access