Synthesis, Solution, and Solid State Properties of Homological Dialkylated Naphthalene Diimides-A Systematic Review of Molecules for Next-Generation Organic Electronics.

This systematic study aimed at finding a correlation between molecular structure, solubility, self-assembly, and electronic properties of a homological series of N-alkylated naphthalene diimides (NDIs). NDIs are known for their n-type carrier mobility and, therefore, have potential in the field of organic electronics, photovoltaics, and sensors. For the purpose of this study, nine symmetrical N,N'-dialkylated naphthalene diimides (NDIC3-NDIC11) were synthesized in the reaction of 1,4,5,8-naphthalenetetracarboxylic dianhydride with alkylamines ranging from propyl- to undecyl-. The NDIs were characterized by spectroscopic (NMR, UV-Vis, FTIR), microscopic, and thermal methods (TGA and DSC), and X-ray diffraction (XRD). Our experimental study, extensively referring to findings reported in the literature, indicated that the NDIs revealed specific trends in spectroscopic and thermal properties as well as solubility and crystal morphology. The solubility in good solvents (chloroform, toluene, dichlorobenzene) was found to be the highest for the NDIs substituted with the medium-length alkyl chains (NDIC5-NDIC8). Systematic FTIR and XRD studies unraveled a distinct parity effect related to the packing of NDI molecules with odd or even numbers of methylene groups in the alkyl substituents. The NDIs with an even number of methylene groups in the alkyl substituents revealed low-symmetry (P1-) triclinic packing, whereas those with an odd number of carbon atoms were generally monoclinic with P21/c symmetry. The odd-even parity effect also manifested itself in the overlapping of the NDIs' aromatic cores and, hence, the π-π stacking distance (dπ-π). The odd-numbered NDIs generally revealed slightly smaller dπ-π values then the even-numbered ones. Testing the NDIs using standardized field-effect transistors and unified procedures revealed that the n-type mobility in NDIC6, NDIC7, and NDIC8 was 10- to 30-fold higher than for the NDIs with shorter or longer alkyl substituents. Our experimental results indicate that N,N'-alkylated NDIs reveal an optimum range of alkyl chain length in terms of solution processability and charge transport properties.

Tunable-wavelength nanosecond laser tailoring of plasmon resonance spectra of gold nanoparticle colloids.

Metal nanoparticles have applications across a range of fields of science and industry. While there are numerous existing methods to facilitate their large-scale production, most face limitations, particularly in achieving reproducible processes and minimizing undesirable impurities. Common issues are varying particle sizes and aggregates with unfavorable spectral properties. Researchers are currently developing methods to separate or modify nanoparticle sizes and shapes post-synthesis and to eliminate impurities. One promising approach involves laser light irradiation and enables the changing of nanoparticle sizes and shapes while controlling crucial spectral parameters. In this work, we present a novel extension of this method by irradiating nanoparticle colloids with variable-wavelength nanosecond laser pulses on both sides of the extinction band. Our results demonstrate the use of gradual laser wavelength tuning to optimize the photothermal reshaping of gold nanorods and achieve precise control over the plasmon resonance band. By irradiating both sides of the plasmon resonance band, we execute a multistep tuning process, controlling the band's width and spectral position. A statistical analysis of SEM images reveals differences in the nanorod morphology when irradiated on the long- or short-wavelength side of the plasmon resonance band. The fine-tuning of plasmonic spectral properties is desirable for various applications, including the development of sensors and filters and the exploitation of the photothermal effect. The findings of this study can be extended to other plasmonic nanostructures.