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Increased interest in the emission properties of lanthanide(III) (Eu and Tb) complexes containing ultraviolet and visible sensitizers is being driven by the desire to produce efficient and selective luminescent probes of biological structure. Of special interest are cryptates and other macrocyclic chelating ligands that efficiently encapsulate the lanthanide ions. These species also form relatively stable systems and in some cases are well protected from penetration of the first coordination sphere by solvent molecules and counterions. This work describes the X-ray structure and various spectroscopic measurements on a europium cryptate containing 3,3'-biisoquinoline-2,2'-dioxide (biqO2). This cryptate has been previously recognized for special stability and luminescence efficiency. The compound, (Eu:biqO2.2.2)(CF3SO3)3.CH3CN.H2O, forms rhombic crystals with the space group Pbca. Absorption, emission, and excitation spectra at 293, 77, and 4 K as well as luminescence decay time measurements are used to characterize the solid state and solutions. The ligand-to-metal energy-transfer mechanism and thermally activated back-energy-transfer processes are analyzed and compared to previously published results on related Eu(III) cryptate systems. Preliminary results on the use of high liquid pressure to perturb ligand singlet and triplet states and, as a consequence, probe the ligand-metal orbital interactions are also presented.

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Novel amide cross-linked alkylene/siloxane hybrid materials (di-amidosils) synthesized by the sol-gel process have been investigated. Two samples identified by the notation d-A(x) with x = 4 and 8 (where x is the number of methylene groups of the alkylene chain) have been produced as transparent, amorphous, rigid monoliths, thermally stable up to about 381 and 400 ºC, respectively. In the d-A(8) hybrid the siliceous framework is composed of [(SiO) 3 Si(CH 2)-] and [(SiO) 2 (HO)Si(CH 2)-] substructures. Structural unit distances of 4.1 and 4.2 Å and average interparticle distances of 12 and 17 Å have been determined for d-A(4) and d-A(8), respectively. In these compounds the alkyl chains are disordered and adopt gauche conformations. While a negligible proportion of the amide linkages remain non-bonded, the great majority of these groups belong to highly disordered strong hydrogen-bonded amide-amide associations. The hybrids introduced are room temperature white light emitters, presenting an emission large, broad band in the blue/purplishblue spectral region. The origin of such band have been ascribed to the convolution of donoracceptor pair (D-A) recombinations that occur in the NH groups of the urea linkages and in the siliceous nanodomains. The maximum quantum yield value of the d-A(8) di-amidosil is 5.4 %.

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