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1.
Inorg Chem ; 60(2): 1208-1219, 2021 Jan 18.
Article in English | MEDLINE | ID: mdl-33378202

ABSTRACT

Two coordination polymers with formulas [CuI(dapym)]n and [Cu2I2(dapym)]n (dapym = 2,4-diaminopyrimidine) have been synthesized in water at room temperature. According to the stoichiometry used, mono (1D) and the two-dimensional (2D) structures can be obtained. Both are made up of Cu2I2 double chains. Their high insolubility in the reaction medium also makes it possible to obtain them on a nanometric scale. Their structural flexibility and short Cu-Cu distances provoke interesting optoelectronic properties and respond to physical stimuli such as pressure and temperature, making them interesting for sensor applications. The experimental and theoretical studies allow us to propose different emission mechanisms with different behaviors despite containing the same organic ligand. These behaviors are attributed to their structural differences. The emission spectra versus pressure and temperature suggest competencies between different transitions, founding critical Cu2I2 environments, i.e., symmetric in the 1D compound and asymmetric for the 2D one. The intensity in the 2D compound's emission increases with decreasing temperature, and this behavior can be rationalized with a structural constriction that decreases the Cu-Cu and Cu-I distances. However, compound 1D exhibits a contrary behavior that may be related to a change of the organic ligand's molecular configuration. These changes imply that a more significant Π-Π interaction counteracts the contraction in distances and angles when the temperature decreased. Also, the experimental conductivity measurements and theoretical calculations show a semiconductor behavior. The absorption of the 1D compound in UV, its intense emission at room temperature, and the reduction to nanometric size have allowed us to combine it homogeneously with ethyl vinyl acetate (EVA), creating a new composite material. The external quantum efficiency of this material in a Si photovoltaic mini-module has shown that this compound is an active species with application in solar cells since it can move the photons of the incident radiation (UV region) to longer wavelengths.

2.
Phys Chem Chem Phys ; 18(21): 14720-9, 2016 06 07.
Article in English | MEDLINE | ID: mdl-27185655

ABSTRACT

Nanocrystalline Lu3Ga5O12 garnets doped with Tm(3+)/Yb(3+) ions have been synthesized by a low cost and environmentally benign sol-gel technique and characterized for their structural, Stokes and anti-Stokes luminescence properties. The diffuse reflectance spectra of doped Lu3Ga5O12 nano-garnets have been measured to derive the partial energy level structure of Tm(3+) and Yb(3+) ions and possible energy transfer channels between them. Upon laser excitation at 473 nm, weak red and intense near-infrared Stokes emissions have been observed in the nano-garnets. The decay curves of (3)H4 and (1)G4 levels of Tm(3+) ions and the (2)F5/2 level of Yb(3+) ions have been measured upon resonant laser excitation and are found to be non-exponential in nature due to multipolar interactions. In order to know the kind of multipolar interaction among optically active ions, the decay curves are analyzed through the generalized Yokota-Tanimoto model. Moreover, under 970 nm laser excitation, intense blue anti-Stokes emission is observed by the naked eye in Tm(3+)-Yb(3+) co-doped Lu3Ga5O12 nano-garnets. The results show that as-synthesized nano-garnets may be useful in the field of phosphors and photonics.

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