Incorporation of Photo- and Thermoresponsive N-Salicylidene Aniline Derivatives into Cobalt and Zinc Layered Hydroxides.

In search of new multifunctional hybrid materials and in order to investigate the influence of chemical modification on the possible synergy between properties, the carboxylate and sulfonate derivatives of photo- and thermochromic N-salicylidene aniline were successfully inserted into Co(II)- and Zn(II)-based layered simple hydroxides, resulting in four novel hybrids: Co-N-Sali-COO, Co-N-Sali-SO3, Zn-N-Sali-COO, and Zn-N-Sali-SO3. All synthesized hybrids adopt a double organic layered configuration, which prevents the cis-trans photoisomerization ability of N-Sali-R molecules in the hybrids. However, the Zn hybrids exhibit fluorescence upon exposure to UV light due to the excited-state intramolecular proton transfer (ESIPT) mechanism. The thermally stimulated keto-enol tautomerization of N-salicylidene aniline in the hybrids was related with the changes in interlamellar spacings observed by temperature-dependent PXRD. This tautomerization process was prominently evident in the Co-N-Sali-SO3 hybrid (about 11% increase in d-spacing upon decreasing the temperature to -180 °C). Finally, the Co-N-Sali-R hybrids exhibit the typical magnetic behavior associated with Co(II)-based LSHs (ferrimagnetic ordering at TN = 6.8 and 7.7 K for Co-N-Sali-COO and Co-N-Sali-SO3, respectively). This work offers insights into isomerization in LSHs and the ESIPT mechanism's potential in new luminescent materials and prospects for designing new multifunctional materials.

Upconversion in a d-f [RuYb3] Supramolecular Assembly.

We have prepared a hetero-tetrametallic assembly consisting of three ytterbium ions coordinated to a central [Ru(bpm)3]2+ (bpm = 2,2'-bipyrimidine) motif. Irradiation into the absorption band of the peripheral ytterbium ions at 980 nm engenders emission of the 3MLCT state of the central [Ru(bpm)3]2+ core at 636 nm, which represents the first example of f → d molecular upconversion (UC). Time-resolved measurements reveal a slow rise of the UC emission, which was modeled with a mathematical treatment of the observed kinetics according to a cooperative photosensitization mechanism using a virtual Yb centered doubly excited state followed by energy transfer to the Ru centered 1MLCT state.

Cooperative Luminescence and Cooperative Sensitisation Upconversion of Lanthanide Complexes in Solution.

Upconversion materials have led to various breakthrough applications in solar energy conversion, imaging, and biomedicine. One key impediment is the facilitation of such processes at the molecular scale in solution where quenching effects are much more pronounced. In this work, molecular solution-state cooperative luminescence (CL) upconversion arising from a Yb excited state is explored and the mechanistic origin behind cooperative sensitisation (CS) upconversion in Yb/Tb systems is investigated. Counterintuitively, the best UC performances were obtained for Yb/Tb ratios close to parity, resulting in the brightest molecular upconversion complexes with a quantum yield of 2.8×10-6 at a low laser power density of 2.86 W cm-2 .

Dual role of tannic acid and pyrogallol incorporated in plaster of Paris: Morphology modification and release for antimicrobial properties.

The design of bioactive plasters is of major interest for the amelioration of dental and bone cements. In this article, a one pot and environmentally friendly strategy based on the addition of a cheap polyphenol-tannic acid (TA) or the main phenolic constituent of TA, namely pyrogallol (PY)- able to interact with calcium sulfate is proposed. Tannic acid and pyrogallol not only modify the morphology of the obtained plaster+TA/PY composites but a part of it is released and provides strong-up to twenty fold- antibacterial effect against Staphylococcus aureus. It is shown that the higher antibacterial efficiency of PY is related to a greater release compared to TA even if in solution the antibacterial effect of PY is lower than that of TA when reported on the basis of the molar concentration in PY units.