„NOWE PÓŁPRZEWODNIKI ORGANICZNE I NIEORGANICZNE O KONTROLOWANEJ STRUKTURZE NADCZĄSTECZKOWEJ CHARAKTERYZUJĄCE SIĘ ZMIENNYMI WŁAŚCIWOŚCIAMI LUMINESCENCYJNYMI, ELEKTROCHROMOWYMI I FOTOKATALITYCZNYMI ORAZ WYKAZUJĄCE AKTYWNOŚĆ BIOLOGICZNĄ”
„NEW ORGANIC AND INORGANIC SEMICONDUCTORS OF CONTROLLED SUPRAMOLECULAR ORGANIZATION EXHIBITING TUNABLE LUMINESCENT, ELECTROCHROMIC AND PHOTOCATALYTIC PROPERTIES AND BIOLOGICAL ACTIVITY”
Grant NCN OPUS 2022/45/B/ST5/02120
Konsorcjum z Instytutem Chemii Fizycznej PAN
Kierownik projektu prof. Adam Proń
Okres realizacji: 23.01.2023 – 22.03.2026
Przyznana kwota: 2 191 120 zł (w tym 1 271 240 zł dla PW)
Abstract: Three types of functional materials will be studied: i) donor-acceptor type organic semiconductors; ii) nanocrystals of inorganic semiconductors capped with inert, insulating ligands; iii) hybrid nanomaterials consisting of inorganic nanocrystals functionalized with organic semiconductor ligands. New organic donor-bridge-acceptor (DBA) triad-type compounds will be designed and tested as thermally activated delayed fluorescence (TADF) luminophores or as new systems capable of generating the formation of a pair of radical-anion and radical-cation (qubits) via photoexcitation. DFT-assisted design of these triads will be performed in which favorable orientation of pi-orbitals of donor and acceptor units should induce charge transfer not only through chemical bonds but also through space. To reach this effect, rigid scaffolds such as derivatives of carbazole, fluorene and 1,3-phenylenediamine will be designed to which D and A units will be covalently bound. In the case of triads capable of generating charge separation, comparative investigations of compounds with two types of linking bridges, namely conjugated (dithienobenzothiadiazole) and nonconjugated (piperazine derivatives), will be performed. In parallel, semiconducting alternating copolymers of the following type (-D-pi-A-pi-D-) and (-D-pi-A-pi-), exhibiting near infrared (NIR) electrochromism, will be synthesized and investigated (D = derivatives of diimides, tetrazine, heptazine, diketopyrrolopyrrole, thienopyrroledione, A = derivatives of carbazole, dithienopyrrole, dialkoxy-substituted benzothiophene, phenoxazine). Detailed spectroscopic, electrochemical and spectroelectrochemical of all synthesized compounds will be performed and completed by the determination of their NIR electrochromic parameters. Large part of the research will be devoted to the resolution of 3D and 2D supramolecular structures and to the determination of their mutual relation. In the case of single crystals classical X-ray diffraction techniques will be used. Thin layers will be investigated in the Bragg-Brentano reflection mode, completed by omega-scans with the goal to determine the degree of the orientation of the deposited molecules (macromolecules). For the investigations of monolayers (or multilayers consisting of few monolayers) deposited on different substrates complementary microscopic techniques will be applied, namely scanning tunneling microscopy and atomic force microscopy. In some cases polarization modulation‐infrared reflection‐absorption spectroscopy technique will be used which allows for the molecules tilt angle. Hydrophilic and hydrophobic binary M(I)2X and ternary M(I)M(III)X2 (M(I) = Ag, Cu, M(III) = In, Fe, Al, X = S, Se, Te) semiconductors as well as their alloys with ZnS and ZnSe will be fabricated by classical and ultrasound- or microwave-assisted methods. Their inorganic cores will be characterized by X-ray powder diffraction, EDS and HRTEM. Hydrophobic primary ligands, as well as hydrophilic ligands introduced in the ligand exchange procedure, will be identified and characterized by XPS, IR and NMR. Optical studies of these nanoparticles, involving absorption, excitation and emission spectra, determination of the photoluminescence quantum yields as well as lifetimes, will be carried out confronted with DFT calculations. Hydrophobic and hydrophilic toxic metals-free nanocrystals (Ag-In-S and Ag-In-Zn-S) will be used as new visible light photocatalysts in the reactions of carbonyl compounds hydrogenation carried out in nonaqueous media with thiols as hydrogen donors and in aqueous media with water as a hydrogen donor. Photocatalytic tests of hydrogenation in water will also be performed for furfural and glucose – the main products of the transformation of biomass. Alloyed Ag-In-Zn-S nanocrystals surface-functionalized with doxorubicine and bisacridine will be tested in anticancer therapy as luminescent drug nanocarriers, selectively recognizing tumor cells (in vitro and in vivo tests). For Ag-In-Zn-S nanocrystals capped with organic semiconductor ligands detailed charge and energy transfer studies will be performed with special emphasis of the up-conversion processes of new type. Ternary nonstoichiometric nanocrystals of chalcopyrite family (Cu-Fe-S) exhibiting enhanced Seebeck coefficient and capped with organic semiconductor ligands will be investigated as a new family of solution processable hybrid (organic/inorganic) thermoelectric materials.
