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Structural Phase Transformations Induced by Guest Molecules in a Nickel-Based 2D Square Lattice Coordination Network.

Xia Li1, Debobroto Sensharma1, Varvara I Nikolayenko1

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A novel coordination network, sql-(azpy)(pdia)-Ni, exhibits elastic-like properties, transitioning between porous and nonporous phases due to adaptive guest binding. This material shows potential for humidity control applications.

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Area of Science:

  • Materials Science
  • Crystallography
  • Supramolecular Chemistry

Background:

  • Two-dimensional (2D) coordination networks with square lattice (sql) topology are known for guest-responsive structural transformations.
  • Previous studies on switching sql networks reported distinct phase expansions, similar to clay-like materials.

Purpose of the Study:

  • To synthesize and characterize a new 2D sql topology coordination network, sql-(azpy)(pdia)-Ni, using diazene-containing ligands.
  • To investigate the guest binding properties and structural switching behavior of the synthesized network.

Main Methods:

  • Synthesis of the sql-(azpy)(pdia)-Ni coordination network.
  • Single-crystal X-ray diffraction (SCXRD) for structural analysis of different phases.
  • Variable temperature powder X-ray diffraction (PXRD) for phase transformation studies.
  • Dynamic water vapor sorption analysis.

Main Results:

  • The sql-(azpy)(pdia)-Ni network demonstrated guest-induced switching between closed (nonporous) β and open (porous) α phases.
  • Unlike previous sql networks, a continuum of phases was observed, indicating elastic-like properties due to adaptive guest binding.
  • Structural transformations were facilitated by the phenyldiazenyl moiety on the pdia ligand, acting as a hinge for layer slippage and expansion.
  • The network showed reversible water vapor sorption with a stepped isotherm at ~50% relative humidity (RH), suitable for humidity control.

Conclusions:

  • The novel sql-(azpy)(pdia)-Ni coordination network exhibits unique elastic-like behavior and forms a continuum of phases upon guest inclusion.
  • The pendant phenyldiazenyl group plays a crucial role in enabling the observed structural flexibility and layer slippage.
  • The material's reversible water sorption properties at ~50% RH suggest potential applications in humidity regulation.