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Hydrogen Bonds01:04

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A hydrogen bond is formed when a weakly positive hydrogen atom already bonded to one electronegative atom (for example, the oxygen in the water molecule) is attracted to another electronegative atom from another polar molecule, such as water (H2O), hydrogen fluoride (HF), or ammonia (NH3). The huge electronegativity difference between the H atom (2.1) and the atom to which it is bonded (4.0 for an F atom, 3.5 for an O atom, or 3.0 for an N atom), combined with the very small size of an H atom...
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Alkyl halides are halogen-substituted alkanes wherein one or more hydrogen atoms of an alkane is replaced by a halogen atom such as fluorine, chlorine, bromine, or iodine. The carbon atom in an alkyl halide is bonded to the halogen atom, which is sp3-hybridized and exhibits a tetrahedral shape.
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The vibrational frequency of a bond is directly proportional to its bond strength. As a result, stronger bonds vibrate at higher frequencies, while weaker bonds vibrate at lower frequencies. The stretching vibration of the strong O–H bond in alcohols and phenols (very dilute solution or gas phase) appears as a sharp peak at 3600–3650 cm−1.
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The mathematical expression known as the wave function, ψ, contains information about each orbital and the wavelike properties of electrons in an isolated atom. When atoms are bound together in a molecule, the wave functions combine to produce new mathematical descriptions that have different shapes. This process of combining the wave functions for atomic orbitals is called hybridization and is mathematically accomplished by the linear combination of atomic orbitals. The new orbitals that...
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From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding
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From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding

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Halogen Bond Unlocks Ultra-High Birefringence.

Jin Chen1,2, Miao-Bin Xu1, Huai-Yu Wu1

  • 1College of Chemistry and Materials Science, Fujian Normal University, Fuzhou, 350007, China.

Angewandte Chemie (International Ed. in English)
|July 10, 2024
PubMed
Summary

Researchers developed a new supramolecular framework (INA) with exceptionally high birefringence (0.778), surpassing commercial crystals. This advancement utilizes halogen bonds to enhance optical material performance.

Keywords:
Aliovalent substitutionBirefringenceHalogen bondsStructure-property relationshipsSupramolecular frameworks

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Area of Science:

  • Materials Science
  • Crystallography
  • Optics

Background:

  • Birefringence (Δn) is vital for optical materials, but achieving high values (Δn >0.3) is challenging.
  • Supramolecular frameworks with π-conjugated components offer potential for enhanced birefringence due to their tunable structures and inherent anisotropy.

Purpose of the Study:

  • To design and synthesize novel supramolecular frameworks with significantly improved birefringence.
  • To investigate the role of halogen bonding in enhancing in-plane anisotropy and birefringent performance.

Main Methods:

  • Synthesis of (C6H6NO2)+Cl− (NAC) and subsequent construction of a halogen-bonded supramolecular framework I+(C6H4NO2)− (INA) via halogen aliovalent substitution.
  • Analysis of crystal structures to understand the arrangement of birefringent-active units and the nature of halogen bonds ([O⋅⋅⋅I+⋅⋅⋅N]).
  • Measurement of birefringence values at 550 nm for both NAC and INA.

Main Results:

  • INA exhibited a high birefringence value of 0.778 at 550 nm, which is double that of NAC (0.363 at 550 nm).
  • The [O⋅⋅⋅I+⋅⋅⋅N] halogen bond in INA demonstrated strong interactions and directionality, leading to pronounced in-plane anisotropy.
  • INA's birefringence significantly exceeds that of commercial crystals like CaCO3 (0.172 at 546 nm) and represents the highest reported for ultraviolet birefringent crystals.

Conclusions:

  • A novel design strategy using halogen bonds as connection sites for birefringent units was successfully implemented.
  • The developed INA framework shows exceptional birefringent performance, offering a new pathway for high-performance ultraviolet birefringent crystals.
  • This research opens avenues for designing advanced optical materials with tailored anisotropic properties.