Thermochromic luminescence of copper iodide clusters: the case of phosphine ligands.

Three copper(I) iodide clusters coordinated by different phosphine ligands formulated [Cu(4)I(4)(PPh(3))(4)] (1), [Cu(4)I(4)(Pcpent(3))(4)] (2), and [Cu(4)I(4)(PPh(2)Pr)(4)] (3) (PPh(3) = triphenylphosphine, Pcpent(3) = tricyclopentylphosphine, and PPh(2)Pr = diphenylpropylphosphine) have been synthesized and characterized by (1)H and (31)P NMR, elemental analysis and single crystal X-ray diffraction analysis. They crystallize in different space groups, namely, monoclinic P21/c, cubic Pa3̅, and tetragonal I4̅2m for 1, 2, and 3, respectively. The photoluminescence properties of clusters 1 and 3 show reversible luminescence thermochromism with two highly intense emission bands whose intensities are temperature dependent. In accordance to Density Functional Theory (DFT) calculations, these two emission bands have been attributed to two different transitions, a cluster centered (CC) one and a mixed XMCT/XLCT one. Cluster 2 does not exhibit luminescence variation in temperature because of the lack of the latter transition. The absorption spectra of the three clusters have been also rationalized by time dependent DFT (TDDFT) calculations. A simplified model is suggested to represent the luminescence thermochromism attributed to the two different excited states in thermal equilibrium. In contrast with the pyridine derivatives, similar excitation profiles and low activation energy for these phosphine-based clusters reflect high coupling of the two emissive states. The effect of the Cu-Cu interactions on the emission properties of these clusters is also discussed. Especially, cluster 3 with long Cu-Cu contacts exhibits a controlled thermochromic luminescence which is to our knowledge, unknown for this family of copper iodide clusters. These phosphine-based clusters appear particularly interesting for the synthesis of original emissive materials

Geometry Flexibility of Copper Iodide Clusters: Variability in Luminescence Thermochromism.

An original copper(I) iodide cluster of novel geometry obtained by using a diphosphine ligand is reported and is formulated [Cu6I6(PPh2(CH2)3PPh2)3] (1). Interestingly, this sort of “eared cubane” cluster based on the [Cu6I6] inorganic core can be viewed as a combination of the two known [Cu4I4] units, namely, the cubane and the open-chair isomeric geometries. The synthesis, structural and photophysical characterisations, as well as theoretical study of this copper iodide along with the derived cubane (3) and open-chair (2) [Cu4I4(PPh3)4] forms, were investigated. A new polymorph of the cubane [Cu4I4(PPh3)4] cluster is indeed presented (3). The structural differences of the clusters were analyzed by solid-state nuclear magnetic resonance spectroscopy. Luminescence properties of the three clusters were studied in detail as a function of the temperature showing reversible luminescence thermochromism for 1 with an intense orange emission at room temperature. This behavior presents different feature compared to the cubane cluster and completely contrasts with the open isomer, which is almost nonemissive at room temperature. Indeed, the thermochromism of 1 differs by a concomitant increase of the two emission bands by lowering the temperature, in contrast to an equilibrium phenomenon for 3. The luminescence properties of 2 are very different by exhibiting only one single band when cooled. To rationalize the different optical properties observed, density functional theory calculations were performed for the three clusters giving straightforward explanation for the different luminescence thermochromism observed, which is attributed to different contributions of the ligands to the molecular orbitals. Comparison of 3 with its [Cu4I4(PPh3)4] cubane polymorphs highlights the sensibility of the emission properties to the cuprophilic interactions

Hybrid sol–gel coatings for corrosion protection of galvanized steel in simulated concrete pore solution

The aim of this experimental research was to study the electrochemical behavior of organic– inorganic hybrid (OIH) coatings for corrosion protection of hot-dip galvanized steel (HDGS) in the first instants of immersion in simulated concrete pore solution (SCPS) (pH > 12.5). The electrochemical performance of the OIH coatings was assessed by electrochemical impedance spectroscopy, potentiodynamic polarization curves, macrocell current density, and polarization resistance. The OIH coatings were prepared via the sol–gel method and were deposited on HDGS surfaces by dip-coating using one or three dip steps. The electrochemical results obtained for HDGS samples coated with OIH matrices in SCPS showed higher corrosion resistance than bare HDGS; as the molecular weight (MW) of Jeffamine increased the barrier protection of the coating decreased. The lowest protection efficiency was found for HDGS samples synthesized with oligopolymers with an MW of 2000. Coatings produced with an oligopolymer of 230 MW conferred the highest protection. The surface morphology of the OIH coatings deposited on HDGS surfaces was studied by atomic force microscopy. The results show that the roughness of the OIH films depends on the MW of Jeffamine and on the number of dip-coating steps used. Thermogravimetry results show that the Jeffamine MW affected the thermal properties of the prepared OIH samples. The prepared OIH materials are thermally stable within the range of 20–80 C.The authors would like to gratefully acknowledge the financial support from Fundacao para a Ciencia e Tecnologia (FCT) for the PhD grant SFRH/BD/62601/2009 and EU COST action MP1202: HINT-"Rational design of hybrid organic-inorganic interfaces: the next step towards functional materials.''info:eu-repo/semantics/publishedVersio