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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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Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
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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.
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Prochirality

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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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Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
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Replacing each alpha-hydrogen in chloroethane by bromine (or a different functional group) yields a pair of enantiomers. Such protons are called prochiral or enantiotopic and are related by a mirror plane. Enantiotopic protons are chemically equivalent in an achiral environment. Because most proton NMR spectra are recorded using achiral solvents, enantiotopic hydrogens yield a single signal.
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Potential Multiaxial Molecular Ferroelectricity through Chiral Cation Replacement.

Sam Y Thompson1, Rebecca H Abeyasekere1, Samuel J Page1

  • 1Department of Chemistry, Durham University, Lower Mount Joy, South Road, Durham DH1 3LE, U.K.

Crystal Growth & Design
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Summary

Researchers developed new multiaxial molecular ferroelectrics by adding chiral cations. These materials exhibit 24 polarization directions, overcoming a key design challenge in molecular ferroelectric design.

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Area of Science:

  • Materials Science
  • Solid-State Chemistry
  • Crystallography

Background:

  • Molecular ferroelectrics offer advantages like chemical versatility and low toxicity.
  • A significant challenge is achieving multiaxial properties comparable to inorganic perovskites.
  • Existing molecular ferroelectrics often lack the complex polarization behavior of their inorganic counterparts.

Purpose of the Study:

  • To design and synthesize novel molecular ferroelectrics with multiaxial properties.
  • To explore the introduction of chiral cations to induce complex phase transitions.
  • To investigate the structural and dynamic properties of these new materials.

Main Methods:

  • Synthesis of novel molecular compounds incorporating chiral cations.
  • X-ray diffraction to determine crystal structures and phase transitions.
  • Solid-state Nuclear Magnetic Resonance (NMR) spectroscopy to study molecular dynamics.

Main Results:

  • Successfully synthesized new molecular ferroelectrics by incorporating chiral cations.
  • Observed an Aizu m3̅mFm phase transition in three compounds, leading to 24 equivalent polarization directions.
  • 1H solid-state NMR confirmed rapid rotation of organic cations, simplifying crystallographic analysis.

Conclusions:

  • The introduction of chiral cations is a viable strategy for achieving multiaxial ferroelectricity in molecular materials.
  • These new compounds exhibit a high degree of polarization complexity, approaching that of inorganic ferroelectrics.
  • The observed cation dynamics influence the crystallographic determination and highlight the unique nature of these molecular ferroelectrics.