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A New Family of Layered Metal-Organic Semiconductors: Cu/V-Organophosphonates

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WILEY-V C H VERLAG GMBH
DOI: 10.1002/smll.202304057

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layered magnetic materials; layered metal organic semiconductors; metal organic frameworks

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In this study, a layered redox-active, antiferromagnetic metal organic semiconductor crystals with the chemical formula [Cu(H2O)(2)V(& mu;-O)(PPA)(2)] (where PPA is phenylphosphonate) was designed and synthesized. The crystal structure of [Cu(H2O)(2)V(& mu;-O)(PPA)(2)] was found to have metal phosphonate layers separated by phenyl groups. The [Cu(H2O)(2)V(& mu;-O)(PPA)(2)] crystal showed an indirect band gap of 2.19 eV and exhibited photoluminescent properties with PL peaks at 1.8 and 2.2 eV.
Herein, we report the design and synthesis of a layered redox-active, antiferromagnetic metal organic semiconductor crystals with the chemical formula [Cu(H2O)(2)V(& mu;-O)(PPA)(2)] (where PPA is phenylphosphonate). The crystal structure of [Cu(H2O)(2)V(& mu;-O)(PPA)(2)] shows that the metal phosphonate layers are separated by phenyl groups of the phenyl phosphonate linker. Tauc plotting of diffuse reflectance spectra indicates that [Cu(H2O)(2)V(& mu;-O)(PPA)(2)] has an indirect band gap of 2.19 eV. Photoluminescence (PL) spectra indicate a complex landscape of energy states with PL peaks at 1.8 and 2.2 eV. [Cu(H2O)(2)V(& mu;-O)(PPA)(2)] has estimated hybrid ionic and electronic conductivity values between 0.13 and 0.6 S m(-1). Temperature-dependent magnetization measurements show that [Cu(H2O)(2)V(& mu;-O)(PPA)(2)] exhibits short range antiferromagnetic order between Cu(II) and V(IV) ions. [Cu(H2O)(2)V(& mu;-O)(PPA)(2)] is also photoluminescent with photoluminescence quantum yield of 0.02%. [Cu(H2O)(2)V(& mu;-O)(PPA)(2)] shows high electrochemical, and thermal stability.

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