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Stereoisomerism02:52

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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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In this lesson, we delve into the role of ring conformation and its stability, which determines the spatial arrangement and, consequently, the molecular symmetry and stereoisomerism of cyclic compounds. 1,2-Dimethylcyclohexane is used as a case study to evaluate the possible number of stereoisomers. Here, given the multiple (n = 2) chiral centers, there are 2n = 4 possible configurations that lack a plane of symmetry, as the ring skeleton exists in a non-planar chair conformation. In addition,...
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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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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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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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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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Chiral manganese halide isomers: decoding the spatial stacking effect on second-harmonic generation circular

Jing Li1, Jianwu Wei1, Qiulian Luo1

  • 1School of Chemistry and Chemical Engineering, State Key Laboratory of Featured Metal Materials and Life-cycle Safety for Composite Structures, Guangxi Key Laboratory of Electrochemical Energy Materials, Guangxi University Nanning 530004 Guangxi P. R. China bbluo@gxu.edu.cn qipang@gxu.edu.cn.

Chemical Science
|March 18, 2026
PubMed
Summary
This summary is machine-generated.

Chiral hybrid metal halides show potential for optoelectronics. Spatial stacking significantly impacts their second-harmonic generation circular dichroism (SHG-CD), with specific isomers demonstrating enhanced NLO responses.

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Area of Science:

  • Materials Science
  • Optoelectronics
  • Chirality Studies

Background:

  • Chiral hybrid metal halides (CHMHs) are promising for chiral optoelectronics and nonlinear optics (NLO).
  • The influence of crystal structure, specifically spatial stacking, on second-harmonic generation circular dichroism (SHG-CD) in CHMHs remains poorly understood.
  • Understanding these structure-property relationships is crucial for designing advanced NLO materials.

Purpose of the Study:

  • To investigate the effect of spatial stacking on SHG-CD in chiral manganese(ii) halide isomers.
  • To synthesize and characterize two pairs of chiral manganese(ii) halide isomers with different crystal structures ((R)-α-Mn, (S)-α-Mn, (R)-β-Mn, (S)-β-Mn).
  • To evaluate their photoluminescence, NLO properties, and SHG-CD responses.

Main Methods:

  • Synthesis of chiral manganese(ii) halide isomers ((R)-α-Mn, (S)-α-Mn, (R)-β-Mn, (S)-β-Mn) crystallizing in distinct chiral space groups (C222₁ and P2₁).
  • Characterization of photoluminescence quantum yields and circularly polarized luminescence.
  • Measurement of nonlinear optical (NLO) responses, including second-harmonic generation (SHG) intensities and polarization ratios.
  • Quantification of SHG-CD using the SHG-CD factor (g_SHG-CD).

Main Results:

  • The synthesized isomers exhibited near-unity photoluminescence quantum yields and efficient circularly polarized luminescence (g_lum ≈ 1.0 × 10⁻³).
  • Significant NLO responses were observed, with SHG intensities 2.03 and 1.30 times that of KH₂PO₄ for (R)-α-Mn and (R)-β-Mn, respectively.
  • (R)-α-Mn showed a substantially larger SHG-CD response (g_SHG-CD = -0.56) compared to (R)-β-Mn (g_SHG-CD = -0.30).

Conclusions:

  • Spatial stacking significantly influences the SHG-CD response in CHMHs.
  • The denser asymmetric hydrogen-bonding network and distorted [MnBr₄]²⁻ tetrahedra in (R)- and (S)-α-Mn enhance the dipole moment and improve SHG-CD.
  • This study highlights the critical role of crystal packing in tailoring chiral NLO properties for advanced applications.