RESUMEN
Ternary metal chalcogenide nanocrystals (NCs) offer exciting opportunities as novel materials to be explored on the nanoscale showing optoelectronic properties tunable with size and composition. CuInS2 (CIS) NCs are the most widely studied representatives of this family as they can be easily prepared with good size control and in high yield by reacting the metal precursors (copper iodide and indium acetate) in dodecanethiol (DDT). Despite the widespread use of this synthesis method, both the reaction mechanism and the surface state of the obtained NCs remain elusive. Here, we perform in situ X-ray diffraction using synchrotron radiation to monitor the pre- and postnucleation stages of the formation of CIS NCs. SAXS measurements show that the reaction intermediate formed at 100 °C presents a periodic lamellar structure with a characteristic spacing of 34.9 Å. WAXS measurements performed after nucleation of the CIS NCs at 230 °C demonstrate that their growth kinetics depend on the degree of precursor conversion achieved in the initial stage at 100 °C. NC formation requires the cleavage of S-C bonds. We reveal by means of combined 1D and 2D proton and carbon NMR analyses that the generated dodecyl radicals lead to the formation of a new thioether species R-S-R. The latter is part of a ligand double layer, which consists of dynamically bound dodecanethiolate ligands as well as of head-to-tail bound R-S-R molecules. This ligand double layer and a high ligand density (3.6 DDT molecules per nm2) are at the origin of the apparent difficulty to functionalize the surface of CIS NCs obtained with the DDT method.
RESUMEN
Conductive polymers such as poly(3,4-ethylenedioxythiophene) (PEDOT) are used in a wide range of applications as transparent electrodes, hole injecting layers or thermoelectric materials for room-temperature applications. However, progress is needed to enhance the electrical conductivities of the materials and to provide understanding about their structure-transport relationships. This work presents the synthesis of highly conductive PEDOT-based polymers using iron(iii) trifluoromethanesulfonate as oxidant for the first time. The metallic behaviour of the polymer is revealed by conductivity monitoring from 3 to 300 K. The electrical conductivity is further improved (to 2273 S cm-1) using acids, leading to a positive temperature coefficient of resistivity at an unprecedented 45.5% oxidation state. X-ray photoemission spectroscopy (XPS) and time of flight-secondary ion mass spectrometry (ToF-SIMS) analyses demonstrate a complete replacement of the trifluoromethanesulfonate anions by hydrogen sulphate counter ions. This substitution results in an increased concentration of charge carriers (measured in organic electrochemical transistors) along with an enhancement of the mean size of crystalline domains, highlighted by small and wide angle X-ray scattering (SAXS/WAXS), which explains the 80% increase of electrical conductivity.
RESUMEN
Single-chain magnets (SCMs) are materials composed of magnetically isolated one-dimensional (1D) units exhibiting slow relaxation of magnetization. The occurrence of SCM behavior requires the fulfillment of stringent conditions for exchange and anisotropy interactions. Herein, we report the synthesis, the structure, and the magnetic characterization of the first actinide-containing SCM. The 5f-3d heterometallic 1D chains [{[UO2(salen)(py)][M(py)4](NO3)}]n, (M=Cd (1) and M=Mn (2); py=pyridine) are assembled trough cation-cation interaction from the reaction of the uranyl(V) complex [UO2(salen)py][Cp*2Co] (Cp*=pentamethylcyclopentadienyl) with Cd(NO3)2 or Mn(NO3)2 in pyridine. The infinite UMn chain displays a high relaxation barrier of 134±0.8 K (93±0.5 cm(-1)), probably as a result of strong intra-chain magnetic interactions combined with the high Ising anisotropy of the uranyl(V) dioxo group. It also exhibits an open magnetic hysteresis loop at T<6 K, with an impressive coercive field of 3.4 T at 2 K.