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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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Controlling Triplet-Harvesting Pathways and Nonlinear Optical Properties in Cu(I) Iodide-Based Polymers through

Joy Chatterjee1, Riteeka Tanwar1, Anupama S2

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We report a structural transition in copper iodide polymers, leading to efficient thermally activated delayed fluorescence and strong orange emission. These hybrid materials also show promise as nonlinear optical components.

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Area of Science:

  • Materials Science
  • Inorganic Chemistry
  • Optoelectronics

Background:

  • Organic-inorganic hybrid metal halides are crucial for optoelectronics and sensing.
  • Tuning ligand coordination influences the structure and properties of metal halide polymers.

Purpose of the Study:

  • To investigate structural transitions in Cu(I) iodide-based polymers.
  • To explore the optoelectronic and nonlinear optical properties of resulting materials.

Main Methods:

  • Synthesis of Cu(I) iodide polymers with different π*-acceptor ligands (3-cyanopyridine and its amino analogue).
  • Photoluminescence spectroscopy (temperature-dependent).
  • Nonlinear optical characterization (third harmonic generation).

Main Results:

  • A staircase polymer structure with 3-cyanopyridine exhibits efficient thermally activated delayed fluorescence (TADF) from (metal+halide)-to-ligand charge transfer states (singlet-triplet energy splitting ~9 meV).
  • A 1D polymeric structure of Cu4I4 cubane-type clusters forms with the amino ligand, showing strong cluster-centered (3CC) orange emission at room temperature.
  • The cubane-type cluster polymer demonstrates efficient nonlinear optical properties, including third harmonic generation (χ(3) = 1.32 × 10⁻¹⁸ m² V⁻²) and a high laser-induced damage threshold (25.87 GW/cm²).

Conclusions:

  • Ligand coordination dictates structural transitions in Cu(I) iodide polymers, enabling distinct optoelectronic functionalities.
  • The cubane-type cluster polymer exhibits self-trapped excitonic emission and significant nonlinear optical activity.
  • These hybrid materials offer tunable properties for advanced optoelectronic and photonic applications.