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Ionic Crystal Structures02:42

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Ionic crystals consist of two or more different kinds of ions that usually have different sizes. The packing of these ions into a crystal structure is more complex than the packing of metal atoms that are the same size.
Most monatomic ions behave as charged spheres, and their attraction for ions of opposite charge is the same in every direction. Consequently, stable structures for ionic compounds result (1) when ions of one charge are surrounded by as many ions as possible of the opposite...
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Crystallization is a phase transformation process in which crystals are precipitated from a supersaturated solution or formed from other sources. During crystallization, atoms or molecules arrange themselves into a well-defined, rigid crystal lattice to minimize energy.
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Ethers represent a class of chemical compounds that become more dangerous with prolonged storage because they tend to form explosive peroxides when standing in the air. Autoxidation is the spontaneous oxidation of a compound in air. In the presence of oxygen, ethers slowly oxidize to form hydroperoxides and dialkyl peroxides.
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In the presence of organic peroxides, the addition of hydrogen bromide to an alkene yields the isomer that is not predicted by Markovnikov’s rule. For example, the addition of hydrogen bromide to 2-methylpropene in the presence of peroxides gives 1-bromo-2-methylpropane. This addition reaction proceeds via a free radical mechanism, which reverses the regioselectivity. The free radical reaction mechanism involves three stages: initiation, propagation, and termination.
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Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
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Tetrahedral Complexes
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Thermochemiluminescent peroxide crystals.

Stefan Schramm1, Durga Prasad Karothu1, Nathan M Lui1

  • 1New York University Abu Dhabi, P.O. Box 129188, Abu Dhabi, UAE.

Nature Communications
|March 3, 2019
PubMed
Summary
This summary is machine-generated.

Researchers detected heat-induced light emission, or thermochemiluminescence, from macroscopic organic peroxide crystals. This breakthrough demonstrates direct heat-to-light conversion in solid materials, previously unobserved.

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Area of Science:

  • Solid-state chemistry
  • Photophysics
  • Organic chemistry

Background:

  • Chemiluminescence is the emission of light from chemical reactions, typically observed in solutions.
  • Direct observation of chemiluminescence in macroscopic crystalline solids has been elusive.
  • Understanding energy transduction in solid materials is crucial for novel optical applications.

Purpose of the Study:

  • To demonstrate and characterize thermally induced chemiluminescence in macroscopic organic peroxide crystals.
  • To investigate the mechanism of solid-state thermochemiluminescence.
  • To establish the generality of this phenomenon across different peroxide classes.

Main Methods:

  • Heating centimeter-size crystals of organic peroxides (lophine hydroperoxide, 1,2-dioxetane, endoperoxide, aroyl peroxide) to elevated temperatures (~115°C).
  • Detecting and spectrally analyzing the emitted light.
  • Comparing solid-state emission spectra with those in solution.

Main Results:

  • Thermally induced chemiluminescence was detected from lophine hydroperoxide crystals, emitting blue-green light (λmax = 530 nm).
  • The solid-state emission was attributed to deprotonated lophine, similar to solution-phase reactions.
  • Thermochemiluminescence was observed in other crystalline peroxides, with emission colors ranging from blue to red.

Conclusions:

  • Direct transduction of heat into light via thermochemiluminescence is achievable in bulk crystalline organic peroxides.
  • This phenomenon is not limited to solutions and is common among various crystalline peroxide types.
  • The findings open new avenues for solid-state light-emitting materials and thermal energy conversion.