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Related Concept Videos

Molecules with Multiple Chiral Centers02:25

Molecules with Multiple Chiral Centers

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Molecules that possess multiple chiral centers can afford a large number of stereoisomers. For instance, while some molecules like 2-butanol have one chiral center, defined as a tetrahedral carbon atom with four different substituents attached, several molecules like butane-2,3-diol have multiple chiral centers. A simple formula to predict the number of stereoisomers possible for a molecule with n chiral centers is 2n. However, there can be a lower number where some of the stereoisomers are...
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The concept of prochirality leads to the nomenclature of the individual faces of a molecule and plays a crucial role in the enantioselective reaction. It is a concept where two or more achiral molecules react to produce chiral products. A typical process is the reaction of an achiral ketone to generate a chiral alcohol. Here, the achiral reactant reacts with an achiral reducing agent, sodium borohydride, to generate an equimolar mixture of the chiral enantiomers of the product. For example, an...
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Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
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Chirality is most prevalent in carbon-based tetrahedral compounds, but this important facet of molecular symmetry extends to sp3-hybridized nitrogen, phosphorus and sulfur centers, including trivalent molecules with lone pairs. Here, the lone pair behaves as a functional group in addition to the other three substituents to form an analogous tetrahedral center that can be chiral.
A consequence of chirality is the need for enantiomeric resolution. While this is theoretically possible for all...
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Chirality is a term that describes the lack of mirror symmetry in an object. In other words, chiral objects cannot be superposed on their mirror images. For example, our feet are chiral, as the mirror image of the left foot, the right foot, cannot be superposed on the left foot.
Chiral objects exhibit a sense of handedness when they interact with another chiral object. For example, our left foot can only fit in the left shoe and not in the right shoe. Achiral objects — objects that have...
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Properties of Enantiomers and Optical Activity02:24

Properties of Enantiomers and Optical Activity

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It is essential to understand the difference between chiral and achiral interactions and the implications thereof in optical activity and their applications. Just as our feet, which are chiral, interact uniquely with chiral objects, such as a pair of shoes, but identically with achiral socks, enantiomers of a molecule exhibit different properties only when they interact with other chiral media. An example of a significant implication from this facet is the phenomenon known as optical activity,...
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Supramolecular Chiral Aggregates Exhibiting Nonlinear CD-ee Dependence.

Xiaosheng Yan1, Qian Wang1, Xuanxuan Chen1

  • 1Department of Chemistry, College of Chemistry and Chemical Engineering, The MOE Key Laboratory of Spectrochemical Analysis and Instrumentation, iChEM, Xiamen University, Xiamen, 361005, China.

Advanced Materials (Deerfield Beach, Fla.)
|September 3, 2020
PubMed
Summary

Nonlinear CD-ee dependence in chiral aggregates is explored. While positive effects (MRE) are understood, negative nonlinearities are less reported, hindering mechanistic understanding and application development.

Keywords:
majority-rules effectnegative nonlinear dependencepositive nonlinear dependencesupramolecular aggregatessupramolecular chirality

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Area of Science:

  • Supramolecular Chemistry
  • Chiral Amplification
  • Spectroscopy

Background:

  • Dynamic supramolecular helical aggregates typically show linear CD-ee dependence.
  • Positive nonlinear CD-ee dependence (Majority-Rules Effect, MRE) indicates chiral amplification and is relatively well-understood.
  • Negative nonlinear CD-ee dependence is infrequently observed and poorly understood.

Purpose of the Study:

  • To summarize the current understanding of both positive and negative nonlinear CD-ee dependence in supramolecular helical aggregates.
  • To provide insights and guidance for designing building blocks that exhibit negative nonlinear CD-ee dependence.
  • To advance the understanding of the mechanisms governing these phenomena.

Main Methods:

  • Review of existing literature on nonlinear CD-ee dependence in supramolecular systems.
  • Analysis of factors influencing nonlinear CD-ee dependence, including building block structure and aggregation behavior.
  • Discussion of theoretical modeling approaches, such as mismatch penalty and helix reversal energy.

Main Results:

  • Comprehensive overview of positive nonlinear CD-ee dependence (MRE) with diverse examples.
  • Highlighting the scarcity and lack of understanding surrounding negative nonlinear CD-ee dependence.
  • Identification of research gaps and potential strategies for future investigations.

Conclusions:

  • Understanding positive nonlinear CD-ee dependence can inform the design of systems exhibiting negative nonlinearities.
  • Further research is needed to elucidate the mechanisms behind negative nonlinear CD-ee dependence.
  • Functional supramolecular aggregates with controlled nonlinear optical activity hold potential for various applications.