Binuclear Lanthanide-Radical Complexes Featuring Two Centers with Different Magnetic and Luminescence Properties.
Binuclear complexes with general formula [Ln2(hfac)6(H2O)2(dppnTEMPO)] (LnIII= Gd, Tb, and Dy) have been obtained using the paramagnetic ligand 1-piperidinyl-4-[(diphenylphosphinyl)amino]-2,2,6,6-tetramethyl (dppnTEMPO) as a bridge. One of the lanthanide ions is ferromagnetically coupled with the TEMPO moiety. Two of the complexes (Dy and Tb) show slow relaxation of the magnetization, and the non-magneto-equivalence of the two LnIIIions was clearly observed. The ab initio CASSCF calculations were employed to confirm this behavior, as well as to rationalize the Ln-Rad interaction. The simulations of the magnetic properties were allowed by the insights given by the calculations. The inequivalence of the TbIIIions was also proved by emission spectroscopy.
Universidade Federal Fluminense , Instituto de Quı́mica, 24020-150, Niterói, Rio de Janeiro, Brazil.
Samira G
SG
Reis
Universidade Federal Fluminense , Instituto de Quı́mica, 24020-150, Niterói, Rio de Janeiro, Brazil.|Università degli Studi di Firenze , via della Lastruccia 3, 50019, Sesto Fiorentino, Firenze, Italy.
Matteo
M
Briganti
Universidade Federal Fluminense , Instituto de Fı́sica, 24210-346, Niterói, Rio de Janeiro, Brazil.|Consiglio Nazionale delle Ricerche - Istituto di Chimica dei Composti Organo-Metallici , via Madonna del Piano 10, 50019, Sesto Fiorentino, Firenze, Italy.
Stéphane
S
Soriano
Universidade Federal Rural do Rio de Janeiro , Departamento de Química, 23870-000, Seropédica, Rio de Janeiro, Brazil.
Guilherme P
GP
Guedes
Universidade Federal Fluminense , Instituto de Quı́mica, 24020-150, Niterói, Rio de Janeiro, Brazil.
Sergiu
S
Calancea
National Institute for Laser, Plasma and Radiation , Str. Atomistilor 409, 077125-Magurele, Romania.
Carmen
C
Tiseanu
Universidade Federal do Rio de Janeiro , Instituto de Física, Rio de Janeiro, 21941-972, Rio de Janeiro, Brazil.
Miguel A
MA
Novak
Área de Química Orgánica, Universidad de Almería , Crta. Sacramento s/n, 04120, Almería, Spain.
Miguel A
MA
Del Águila-Sánchez
Università degli Studi di Firenze , via della Lastruccia 3, 50019, Sesto Fiorentino, Firenze, Italy.
Federico
F
Totti
Área de Química Orgánica, Universidad de Almería , Crta. Sacramento s/n, 04120, Almería, Spain.
Fernando
F
Lopez-Ortiz
Inorganic Chemistry Laboratory, Faculty of Chemistry, University of Bucharest , 020464, Bucharest, Romania.
Marius
M
Andruh
Universidade Federal Fluminense , Instituto de Quı́mica, 24020-150, Niterói, Rio de Janeiro, Brazil.
Maria G F
MG
Vaz