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One of the main goals of molecular electronics is to achieve electronic functions from devices consisting of tailored organic molecules connecting two metal electrodes. The fabrication of nanometre-scale spaced electrodes still results in expensive, and often scarcely reproducible, devices. On the other hand, the 'conductance' of long organic molecules--generally dominated by the tunnelling mechanism--is very poor. Here, we show that by incorporating a large number of metal centres into rigid molecular backbones we can obtain very long (up to 40 nm) and highly 'conductive' molecular wires. The metal-centre molecular wires are assembled in situ on metal surfaces via a sequential stepwise coordination of metal ions by terpyridine-based ligands. They form highly ordered molecular films of elevated mechanical robustness. The electrical properties, characterized by a junction based on Hg electrodes, indicate that the 'conductance' of these metal-centre molecular wires does not decrease significantly even for very long molecular wires, and depends on the nature of the incorporated redox centre. The outstanding electrical and mechanical characteristics of these easy-to-assemble molecular systems open the door to a new generation of molecular wires, able to bridge large-gap electrodes, and to form robust films for organic electronics.

The synthesis of a new ligand (1) containing a single phenanthroline (phen) chromophore and a flexibly connected diethylenetriamine tetracarboxylic acid unit (DTTA) as a lanthanide (Ln) coordination site is reported [1 is 4-[(9-methyl-1,10-phenantrol-2-yl)methyl]-1,4,7-triazaheptane-1,1,7,7-tetraacetic acid]. From 1, an extended series of water-soluble Ln.1 complexes was obtained, where Ln is Eu(III), Tb(III), Gd(III), Sm(III), Dy(III), Pr(III), Ho(III), Yb(III), Nd(III), and Er(III). The stoichiometry for the association was found 1:1, with an association constant K(A) > or = 10(7) s(-1) as determined by employing luminescence spectroscopy. The luminescence and photophysical properties of the series of lanthanide complexes were investigated in both H2O and D2O solutions. High efficiencies for the sensitized emission, phi(se), in air-equilibrated water were observed for the Ln.1 complexes of Eu(III) and Tb(III) in the visible region (phi(se) = 0.24 and 0.15, respectively) and of Sm(III), Dy(III), Pr(III), Ho(III), Yb(III), Nd(III), and Er(III) in the vis and/or near-infrared region [phi(se) = 2.5 x 10(-3), 5 x 10(-4), 3 x 10(-5), 2 x 10(-5), 2 x 10(-4), 4 x 10(-5), and (in D2O) 4 x 10(-5), respectively]. For Eu.1 and Tb.1, luminescence data for water and deuterated water allowed us to estimate that no solvent molecules (q) are bound to the ion centers (q = 0). Luminescence quenching by oxygen was investigated in selected cases.

Hybrid perovskite solar cells have been capturing an enormous research interest in the energy sector due to their extraordinary performances and ease of fabrication. However, low device lifetime, mainly due to material and device degradation upon water exposure, challenges their near-future commercialization. Here, we synthesized a new fluorous organic cation used as organic spacer to form a low-dimensional perovskite (LDP) with an enhanced water-resistant character. The LDP is integrated with three-dimensional (3D) perovskite absorbers in the form of MAFAPbI (FA = NHCH = NH, MA = CHNH) and CsFAMAPbIBr In both cases, a LDP layer self-assembles as a thin capping layer on the top of the 3D bulk, making the perovskite surface hydrophobic. Our easy and robust approach, validated for different perovskite compositions, limits the interface deterioration in perovskite solar cells yielding to >20% power conversion efficient solar cells with improved stability, especially pronounced in the first hours of functioning under environmental conditions. As a consequence, single and multijunction perovskite devices, such as tandem solar cells, can benefit from the use of the waterproof stabilization here demonstrated, a concept which can be further expanded in the perovskite optoelectronic industry beyond photovoltaics.