RESUMEN
In the series of homo-leptic trinuclear complexes {[Ln3(L)4Cl4(MeOH)(H2O)]·Cl} (Ln = La, 1; Ln = Eu, 2; Ln = Tb, 3 or Ln = Gd, 4) self-assembled from the allyl-modified benzimidazole-type ligand HL (4-allyl-2-(1H-benzo[d]imidazol-2-yl)-6-methoxyphenol) and LnCl3·6H2O, a suitable energy level match endows efficient green luminescence (Φ(overall) = 72%) of Tb3-arrayed complex 3. The copolymerization between each of these complex monomers 1-4 and C=C-containing MMA (methyl methacrylate) or NBE (norbornene) shows that degradative chain transfer of the terminal four flexible allyl groups within restrains their radical polymerization with MMA while it does not hinder their effective ring-opening metathesis polymerization (ROMP) with NBE. Thus, two kinds of PMMA-supported doping hybrid materials 1@PMMA, 2@PMMA, 3@PMMA and 4@PMMA and PNBE-supported metallopolymer-type hybrid materials Poly(NBE-1), Poly(NBE-2), Poly(NBE-3) and Poly(NBE-4) are obtained, respectively. Especially for both 3@PMMA and Poly(NBE-3) with high color-purity characteristic green emission of Tb(3+) ions, improved physical properties including significantly enhanced luminescence (Φ(overall) = 76% or 83%) are observed, and covalent-bonding endows a higher-concentration self-quenching as compared to physical doping.
Asunto(s)
Bencimidazoles/química , Complejos de Coordinación/síntesis química , Luminiscencia , Plásticos/síntesis química , Polimetil Metacrilato/síntesis química , Terbio/química , Complejos de Coordinación/química , Ligandos , Modelos Moleculares , Estructura Molecular , Plásticos/química , Polimetil Metacrilato/químicaRESUMEN
Through the self-assembly of the (OH)2-Salophen H4L (H4L=N,N'-bis(3-hydroxylsalicylidene)benzene-1,2-diamine) with LnCl3·6H2O or Ln(NO3)3·6H2O (Ln=La, Yb or Gd) in different solvent systems MeCN-EtOH and MeCN-DMF, the mixed (L)(4-) and (H2L)(2-) coordination modes induce the formation of anion-independent while pseudo-polymorphic homoleptic linear tetranuclear complexes [Ln4(H2L)2(L)2(EtOH)2] (Ln=La, 1; Ln=Yb, 2 or Ln=Gd, 3) and [Ln4(H2L)2(L)2(DMF)2] (Ln=La, 4; Ln=Yb, 5 or Ln=Gd, 6), respectively. The result of their photophysical properties shows the characteristic NIR luminescence for both Yb(3+)-based complexes 2 and 5 with emissive lifetimes in microsecond ranges, while the difference of nearby and/or distant oscillator-based (OH and/or CH) vibrations from two coordinated EtOH or DMF molecules within the inner coordination spheres of Yb(3+) ions in the two complexes has a decisive effect on their NIR luminescent properties.
Asunto(s)
Complejos de Coordinación/química , Sustancias Luminiscentes/química , Salicilatos/química , Iterbio/química , Complejos de Coordinación/síntesis química , Diaminas/química , Luminiscencia , Sustancias Luminiscentes/síntesis química , Mediciones Luminiscentes , Modelos Moleculares , Salicilatos/síntesis química , Espectroscopía Infrarroja CortaRESUMEN
Through the self-assembly of the precursor [Zn(L)(MeCN)] (H2L=N,N'-bis(3-methoxy-salicylidene)cyclohexane-1,2-diamine) with LnCl3·6H2O (Ln=La, Nd, Yb, Er or Gd) and NaN3 in alcohol-containing solutions, two series of mixed anions-induced Zn2Ln-arrayed complexes [Zn2(L)2(MeOH)ClLn(N3)]·Cl (Ln=La, 1; Ln=Nd, 2; Ln=Yb, 3; Ln=Er, 4 or Ln=Gd, 5) and Zn2Ln3-arrayed complexes [Zn2(L)3Cl2(µ2-OH)(µ3-OH)2Ln3(N3)2] (Ln=La, 6; Ln=Nd, 7; Ln=Yb, 8; Ln=Er, 9 or Ln=Gd, 10) are obtained at room temperature or under reflux, respectively. In contrast to Zn2Ln-arrayed complexes with the two Zn2+ ions in the inner cis-N2O2 cores and one Ln3+ ion in the outer O2O2 moieties, the demetalation of partial precursors leads to the selective exchange of Zn2+ centers for the Ln3+ ions for the formation of novel heterometallic Zn2Ln3-arrayed complexes with the Ln3+ ions in both the inner cis-N2O2 core and the outer O2O2 moieties of the ligands. The result of their photophysical properties shows that the characteristic near-infrared (NIR) luminescence of Nd3+ or Yb3+ ion has been sensitized from the excited state (both 1LC and 3LC) of the ligand H2L, while relatively lower quantum yields for Zn2Ln3-arrayed complexes than those for Zn2Ln-arrayed complexes, correspondingly, should be due to the luminescent quenching with the involvement of OH- oscillators around the Ln3+ ions.