Dyes and Pigments

Phenothiazines are a class of molecules that have been applied in antipsychotic therapy, photodynamic therapy, dyes, sunscreen, and more recently light-harvesting for energy applications. In the present study, the photochemical properties of phenothiazine aggregates were used for oxidative catalysis and synthesis of gold nanoparticles with potential applications in Boolean logic operations. Phenothiazines have the peculiar photochemical property, which is the stabilization of the photochemically-generated radical cation in their supramolecular aggregates. The phenothiazine radical cations exhibit pink color related to a broad visible spectral band with a peak at 520 nm. In the present study, the pair radical cation/reduced form of two phenothiazines, 10H-phenothiazine (PHT) and 3,7-bis (phenylamino) phenothiazine-5-iodide, named here phenoaniline (PHA) were photochemically generated characterized by absorbance with a peak at the range of 520-550 nm, direct and spin-trapping EPR measurements. The radical cation and separated from the reduced form using the resin styrene-divinylbenzene copolymer containing iminodiacetate ions (Chelex 100). The radical cation entrapped in the resin remained stable and could be used for catalytic oxidation processes. The reduced form remained in aqueous solution and had its reducing properties used to produce gold nanoparticles. Reduced PHT produced gold nanoparticles with dimensions around 7 nm that were arranged in monodispersed supramolecular aggregates of ~60 nm, stabilized by oligomerized phenothiazine, whereas PHA formed anisotropic gold nanoparticles. The supramolecular aggregates of AuNP PHT showed the potential to be applied in Boolean logic systems using CTAB dispersion and citrate reaggregation.

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The supporting information contains data on optimization, 1H and 13C NMR Spectra of Compounds, NMR Spectra of Protonated 3a, Absorption and Emission Spectra of Compounds 3, Acidochromism studies of 3a, Absorption Spectra of non-Protonated and Protonated Compounds 3, Determination of pKa Value of 3a Titration Experiment (Absorption), Titration Experiment (Fluorescence Quenching), and Data of Quantum Chemical Calculations

The detailed synthetic procedure of TDBA-TPDICz and TRZ-TPDICz. 1H NMR data, 13C NMR data, and high resolution mass spectrometry (HRMS) data. Cyclic voltammetry data. Computational data of TPDICz-Ph, TDBA-TPDICz and TRZ-TPDICz. TGA variation graph. LTPL graph of synthesized materials. RTPL data in different polar solvents and DBFPO:20 wt% doped film. Device structure and energy diagram are available in Supporting Information.

supporting information

The NMR dates and X-ray crystal structure

the raw data of this manuscript

Supporting Information

strcutural parameters of all modelized molecules

This file contains the Electronic Supplementary data (ESI) for "Highly effective nicotinonitrile derivatives based thermally activated delayed fluorescence emitter with asymmetric molecular architecture for high performance organic light-emitting diodes". This files consists additional calculation and photophysical data of emitters and OLEDs.