izvor podataka: poirot

Naziv

Zelena sinteza organopaladijevih foto-osjetljivih spojeva

Green Synthesis of Organopalladium Photosensitizers

Opis projekta

Zelena kemija je na čelu aktualnih zbivanja raznih istraživačkih područja u kemiji. Jedan od njezinih glavnih ciljeva je razvijanje učinkovitih preparativnih metoda za različite vrste postojećih i novih kemikalija bez korištenja otapala i uz nisku potrošnju energije. Izvedivost ovog temeljnog koncepta zelene kemije bit će pokazana na sintezi organopaladijevih kompleksa te će većina sintetskih koraka u ovom projektu biti provedena reakcijama u čvrstom stanju, upotrebom metoda ubrzanog starenja i mehanokemije. Prvu mehanosintezu organopaladijevih spojeva aktivacijom C-H veze paladijevim(II) acetatom nedavno je objavila naša grupa. Valja napomenuti da je aktivacija C-H veze od iznimne važnosti u sintetskoj organskoj kemiji. U okviru ovog projekta predlažemo razvijanje i primjenu metoda u čvrstom stanju za sintezu niza ciklopaladiranih aromatskih azo spojeva. Interes za organopalladijeve komplekse s konjugiranim C=C and N=N vezama proizlazi iz njihove jake apsorpcije i emisije svijetla u području niskih energija što ih kvalificira kao dobre kandidate za biomolekulske obilježivače. U tom pogledu, njihov afinitet prema ciljanim amino kiselinama, kratkim peptidima i nukleobazama istražit će se UV-vis and fluorescentnom spektroskopijom. Shodno navedenom, dodatna korist od predloženog projekta bit će niz novih kromogenih i fluorogenih kemosenzora. Struktura produkata u čvrstom stanju odredit će se rendgenskom difrakcijom, NMR, Raman i IR spektroskopijama. Mehanizam ciklopaladacije u čvrstom stanju istražit će se u realnom vremenu in situ praćenjem reakcija Raman spektroskopijom, te u otopini UV-vis i NMR spektroskopijama uz ESI spektrometriju masa. Optička svojstva kompleksa u čvrstom stanju i otopini odredit će se UV-vis and fluoroscentnom spektroskopijom. Eksperimentalni rezultati racionalizirat će se teorijskim istraživanjima da bi se objasnila izomerija kompleksa, priroda njihovih elektronskih prijelaza te da bi se dobila dodatna potvrda za mehanizam ciklopaladacije.

Green chemistry is at the forefront of current developments of various research areas in chemistry. One of its major objectives is to develop efficient solvent-free and low-energy preparative methods for various classes of existing and new chemicals. The feasibility of this green-chemistry concept will be demonstrated on the synthesis of organopalladium complexes and the majority of synthetic steps in this project will be performed in the solid state by methods of accelerated aging and mechanochemistry. The first mechanosynthesis of organopalladium compounds via C-H bond activation, which is of exceptional importance in organic synthesis, by palladium(II) acetate has been recently reported by our group. Within this project we propose to develop and implement the solid-state methods for the synthesis of a series of cyclopalladated aromatic azo compounds. Interest in such complexes with conjugated C=C and N=N bonds arises from their strong absorption and emission in the low energy region, which qualifies them as good candidates for the biomolecular labels. In this regard, their affinity to target amino acids, short peptides and nucleobases will be studied by UV-vis and fluorescence spectroscopies. Consequently, an additional benefit of this project will be a series of new chromogenic and fluorogenic chemosensors. The solid-state structures of the products will be determined by X-ray diffraction, NMR, Raman and IR spectroscopies. The cyclopalladation mechanism in the solid state will be studied by in situ monitoring of the reactions using Raman spectroscopy, and in the solution by UV-vis and NMR spectroscopies along with the ESI mass spectrometry. The optical characteristics of complexes will be evaluated by UV-vis and fluorescence spectroscopies. The experimental results will be rationalized by theoretical studies in order to explain isomerism of complexes, the nature of their electronic transitions and to obtain additional support for the cyclopalladation mechanism.

Ključne riječi

mechanochemistry, aging, C-H bond activation, organopalladium, mechanism, spectroscopy, non-invasive chromogenic and fluorogenic chemosensors

Znanstveno-istraživački projekti

GREENSENS

IP-2014-09-7984

15.10.2015

14.10.2019

nije evidentirano

HRK 624.000,00

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