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Smart composite films of nanometric thickness based on copper-iodine coordination polymers. Toward sensors.

ABSTRACT: One-pot reactions between CuI and methyl or methyl 2-amino-isonicotinate give rise to the formation of two coordination polymers (CPs) based on double zig-zag Cu₂I₂ chains. The presence of a NH₂ group in the isonicotinate ligand produces different supramolecular interactions affecting the Cu-Cu distances and symmetry of the Cu₂I₂ chains. These structural variations significantly modulate their physical properties. Thus, both CPs are semiconductors and also show reversible thermo/mechanoluminescence. X-ray diffraction studies carried out under different temperature and pressure conditions in combination with theoretical calculations have been used to rationalize the multi-stimuli-responsive properties. Importantly, a bottom-up procedure based on fast precipitation leads to nanofibers of both CPs. The dimensions of these nanofibres enable the preparation of thermo/mechanochromic film composites with polyvinylidene difluoride. These films are tens of nanometers in thickness while being centimeters in length, representing smaller thicknesses so far reported for thin-film composites. This nanomaterial integration of CPs could represent a source of alternative nanomaterials for opto-electronic device fabrication.

SUBMITTER: Conesa-Egea J

PROVIDER: S-EPMC6202926 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Optical materials with high refractive index (n) have been rapidly improved because of urgent demands imposed by the development of advanced photonic and electronic devices such as solar cells, light emitting diodes (LED and Organic LED), optical lenses and filters, anti-reflection films, and optical adhesives. One successful method to obtain high refractive index materials is the blending of metal oxide nanoparticles such as TiO? and ZrO? with high n values of 2.1-2.7 into conventional polymers. However, these nanoparticles have a tendency to agglomerate by themselves in a conventional polymer matrix, due to the strong attractive forces between them. Therefore, there is a limitation in the blending amount of inorganic nanoparticles. In this paper, various hydrophilic polymers such as poly(N-hydroxyl acrylamide) (pHEAAm), poly(vinyl alcohol), poly(ethylene glycol), and poly(acrylic acid) were examined for preparation of high refractive index film based on titanium oxide nanoparticle (TiNP) dispersed polymer composite. The hydrogen bonding sites in these hydrophilic polymers would improve the dispersibility of inorganic nanoparticles in the polymer matrix. As a result, pHEAAm exhibited higher compatibility with titanium oxide nanoparticles (TiNPs) than other water-soluble polymers. Transparent hybrid films were prepared by mixing pHEAAm with TiNPs and drop casting the mixture onto a glass plate. The refractive indices of the films were in good agreement with calculated values. The compatibility of TiNPs with pHEAAm was dependent on the surface characteristics of TiNPs. TiNPs with the highest observed compatibility could be hybridized with pHEAAm at concentrations of up to 90 wt%, and the refractive index of the corresponding film reached 1.90. The high compatibility of TiNPs with pHEAAm may be related to the hydrophilicity and amide and hydroxyl moieties of pHEAAm, which cause hydrogen bond formation on the TiO? surface. The obtained thin film was slightly yellow due to the color of the original TiNP dispersion; however, the transmittance of the film was higher than 80% in the wavelength range from 480 to 900 nm.

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Smart composite films of nanometric thickness based on copper-iodine coordination polymers. Toward sensors.

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