A macromolecular conformational change driven by a minute chiral solvation energy

Green, Mark M.; Khatri, C A.; Peterson, Norman C.

doi:10.1021/ja00064a086

Cited by 194 publications

(133 citation statements)

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“…Nowadays, inter-or intra-molecular interactions (like van der Waals, CH/π, hydrogen bonding, coulombic, charge-transfer and metal-ligand coordinating interactions) have been used to facilitate the chirality induction of optically active polymers from optically inactive polymers. As early as in 1993, Green et al observed for the first time a macromolecular conformational change driven by a minute chiral solvation energy [26,57]. The chirality transfer from non-racemic solvents, such as (S)-1-chloro-2-methylbutane and (R)-2-chloroalkanes, to CD-silent poly(nhexyl isocyanate) (PHIC) macromolecules was successfully realized (Figure 2).…”

Section: Chirality Of Polymers Induced By Chiral Solvationmentioning

confidence: 99%

“…Nowadays, methods for introducing asymmetry have been expanded widely, for example, using asymmetric liquid crystal field, supramolecular interactions with small chiral molecules, chiral circular polarized light and chiral solvation [21,[24][25][26][27][28]. Among these, chiral solvation method by simply using chiral solvent molecules as chiral source provides a relatively greener way to prepare optically active polymers.…”

Section: Introductionmentioning

confidence: 99%

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Chiral Solvation Induced Supramolecular Chiral Assembly of Achiral Polymers

Zhang¹,

Zhao²,

Yin³

2017

Molecular Self-Assembly in Nanoscience and Nanotechnology

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To date, liquid crystal chirality, mechanophysical chirality, circularly polarized photon chirality, gelation and chiral solvation are all feasible candidates to generate optically active polymers and supramolecular chirality when employing achiral molecules as starting substances. Among this, chiral-solvation-induced chirality is one of the dominant methods for construction of chirality from achiral sources, such as achiral poly(n-hexyl isocyanate) (PHIC), π-conjugated polymers, oligo(p-phenylenevinylene), polyacetylenes, σ-conjugated polysilanes and side-chain polymers. Supramolecular chirality is well established through their intra-or inter-molecular noncovalent interactions, such as van der Waals, CH/π, dipole-dipole interactions, hydrogen bonding and metal-ligand coordinating interactions. Compared with the traditional methods, this strategy avoids the use of expensive chiral reagents and also expands the scope towards challenging substrates. This chapter highlights a series of studies that include: (i) the development-historical background of chiral solvent induction strategy; (ii) the chiral-solvation-induced chirality in small molecules and oligomers; and (iii) recent developments in polymers, especially in π-conjugated polymers and σ-conjugated polymers.

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Section: Chirality Of Polymers Induced By Chiral Solvationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Chiral Solvation Induced Supramolecular Chiral Assembly of Achiral Polymers

Zhang¹,

Zhao²,

Yin³

2017

Molecular Self-Assembly in Nanoscience and Nanotechnology

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“…Green et al observed for the first time the generation of optically active poly(n-hexyl isocyanate) (PHIC) with a preferred handed helix in non-racemic solvents, such as (S)-1-chloro-2-methylbutane and a series of (R)-2-chloroalkanes, proven by CD signals (Figures 10 and 11) [111,112]. Yashima et al reported generating optically-active cis-transoid polyphenylacetylene conveying carboxyl groups due to hydrogen bonding interactions with various chiral amines and chiral amino alcohols in polar DMSO (Figure 12) [113][114][115].…”

Section: Optically Active Polymers In the Ground Statementioning

confidence: 99%

Supramolecular Chirality: Solvent Chirality Transfer in Molecular Chemistry and Polymer Chemistry

Fujiki

2014

Symmetry

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Controlled mirror symmetry breaking arising from chemical and physical origin is currently one of the hottest issues in the field of supramolecular chirality. The dynamic twisting abilities of solvent molecules are often ignored and unknown, although the targeted molecules and polymers in a fluid solution are surrounded by solvent molecules. We should pay more attention to the facts that mostly all of the chemical and physical properties of these molecules and polymers in the ground and photoexcited states are significantly influenced by the surrounding solvent molecules with much conformational freedom through non-covalent supramolecular interactions between these substances and solvent molecules. This review highlights a series of studies that include: (i) historical background, covering chiral NaClO 3 crystallization in the presence of D-sugars in the late 19th century; (ii) early solvent chirality effects for optically inactive chromophores/fluorophores in the 1960s-1980s; and (iii) the recent development of mirror symmetry breaking from the corresponding achiral or optically inactive molecules and polymers with the help of molecular chirality as the solvent use quantity.

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“…To obtain these compounds in one predominant configuration over time, a possible strategy is to add stereogenic elements to their backbone; intramolecular diastereoselective interactions happen and favour one of equilibrating diastereomers [136,137]. If the chiral compounds are charged, an alternative strategy to control their configuration is to consider their asymmetric ion pairing with chiral counter-ions [138]; intermolecularrather than intramolecular -diastereoselective interactions then control the stereoselectivity (Pfeiffer effect) [139,140]. Unfortunately, in most of the previous examples, the extent of the asymmetry-induction was determined by chiroptical measurements (ORD, CD) that gave qualitative and not quantitative information.…”

Section: Stereoselective Chemistry Induced By Chiral Anionsmentioning

confidence: 99%