The novel polymeric formates of general formula [(Fmd)- LnIII(HCOO)4]∞ (Fmd+ = NH2-CH+-NH2; Ln = Eu (1), Gd (2), Tb (3), Dy (4)] were synthesized through solvothermal methods in formamide solutions. The compounds are isotructural; they crystallize in the orthorhombic C2221 chiral space group. The coordination geometry at the metal centers is square antiprismatic (coordination number eight), with each formate ligand bridging adjacent lanthanide ions. The overall negative three-dimensional (3D) framework charge is balanced by the formamidinium cations sitting inside the channels along the a axis, forming extensive N−H···O hydrogen bonding with the surrounding cage. All the compounds have been characterized through single-crystal/powder X-ray diffraction, IR spectroscopy, and TG-MS analysis. Finally, their luminescence and magnetic properties have been assessed, leading to remarkable emission intensities, especially for the Tb(III) compound (Φ = 0.83), with corresponding lifetime decays in the micro (Dy) and millisecond (Tb, Eu) time scale. A weak but sizable antiferromagnetic interaction has been observed for the Gd(III) derivative.

Amine-Templated Polymeric Lanthanide Formates: Synthesis, Characterization, and Applications in Luminescence and Magnetism / Andrea Rossin;Giuliano Giambastiani;Maurizio Peruzzini;Roberta Sessoli. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - STAMPA. - 51:(2012), pp. 6962-6968. [10.1021/ic300854b]

Amine-Templated Polymeric Lanthanide Formates: Synthesis, Characterization, and Applications in Luminescence and Magnetism

SESSOLI, ROBERTA
2012

Abstract

The novel polymeric formates of general formula [(Fmd)- LnIII(HCOO)4]∞ (Fmd+ = NH2-CH+-NH2; Ln = Eu (1), Gd (2), Tb (3), Dy (4)] were synthesized through solvothermal methods in formamide solutions. The compounds are isotructural; they crystallize in the orthorhombic C2221 chiral space group. The coordination geometry at the metal centers is square antiprismatic (coordination number eight), with each formate ligand bridging adjacent lanthanide ions. The overall negative three-dimensional (3D) framework charge is balanced by the formamidinium cations sitting inside the channels along the a axis, forming extensive N−H···O hydrogen bonding with the surrounding cage. All the compounds have been characterized through single-crystal/powder X-ray diffraction, IR spectroscopy, and TG-MS analysis. Finally, their luminescence and magnetic properties have been assessed, leading to remarkable emission intensities, especially for the Tb(III) compound (Φ = 0.83), with corresponding lifetime decays in the micro (Dy) and millisecond (Tb, Eu) time scale. A weak but sizable antiferromagnetic interaction has been observed for the Gd(III) derivative.
51
6962
6968
Andrea Rossin;Giuliano Giambastiani;Maurizio Peruzzini;Roberta Sessoli
File in questo prodotto:
File Dimensione Formato  
ic300854b.pdf

Accesso chiuso

Tipologia: Versione finale referata (Postprint, Accepted manuscript)
Licenza: DRM non definito
Dimensione 1.75 MB
Formato Adobe PDF
1.75 MB Adobe PDF   Visualizza/Apri   Richiedi una copia

I documenti in FLORE sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2158/651827
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 66
  • ???jsp.display-item.citation.isi??? 64
social impact