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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Reactivity and photochemistry of copper halide complexes / Reaktivitet och fotokemi hos kopparhalidkomplex

Wicksell Chuainukun, Needa Athitaya January 2021 (has links)
This paper deals with 3-picoline, 4-picoline, 3,4-lutidine and 3,5-lutidine complexes of copper(I) iodide (CuI(3-pic), CuI(4-pic), CuI(3,4-lut) and (CuI(3,5-lut)). The experimental investigation was divided into several parts. Firstly, the synthesis and characterization of the compounds both as powder and as thin films. Secondly, the photoluminescence study. Thirdly, the observation of ligand exchange reaction by vapor diffusion, and lastly, the determination of the lifetime by time-resolved photoluminescence of respective compound.  All studied copper(I)-iodide-substituted pyridine compounds were emissive both as powders and thin films. The synthesis of the tetranuclear cluster powders yields both cluster and polymeric forms of structure. The pXRD of the powders CuI(3-pic), CuI(4-pic), and CuI(3,5- lut) confirmed to be as polymeric structures, hence the CuI(3-pic) showed thermochromism behavior. The structure of CuI(3,4-lut) is still unconfirmed. The most effective method for the synthesis of the thin films was the SILAR method.  The photoluminescence spectra of respective thin films differ from their corresponding powders, and the structure of the compounds as thin films is yet unexplored. The emission of CuI(3-pic), CuI(4-pic), and CuI(3,4-lut) as thin films were similar 480nm, hence the emission of CuI(3,5-lut) thin film lays on 518 nm. Therefore, the ligand exchange reaction was performed on the CuI(3-pic) thin film with 3,5-lutidine as the exchanging ligand.  The ligand exchange reaction of CuI(3-pic) thin film by vapor diffusion of 3,5-lutidine results in a spectrum shift from the emission spectrum of CuI(3-pic) to the spectrum of CuI(3,5-lut). This indicates a successful ligand exchange reaction by vapor diffusion.  The lifetimes of the investigated compounds which have their best fit of mono-exponential function were between 2,2 μs and 9,52 μs. The lifetimes were determined on the thin films with time-resolved photoluminescence. The ligand exchange reaction was also observed by time- resolved photoluminescence which reveals some stable lifetimes during the reaction that can indicate the formation of intermediates. In contrast, the measured lifetimes during the ligand exchange reaction have their best fit of bi-exponential function which can be due to reaction conditions during the measurement or the homogeneity of the thin films. / Denna uppsats behandlar 3-pikolin, 4-pikolin, 3,4-lutidin och 3,5-lutidin komplex av koppar(I) jodid (CuI(3-pic), CuI(4-pic), CuI(3,4-lut) och (CuI(3,5-lut)). Den experimentella undersökningen delades in i olika delar. Först, syntesen och karakteriseringen av föreningarna både som pulver och som tunn film. Sedan studerades fotoluminiscensen av respektive förening. Därefter genomförde en ligand-utbytes-reaktion genom förgasning och slutligen bestämde livstiden av föreningarnas exciterade tillstånd.  Alla koppar(I) jodid föreningar som studerade gav upphov till emission både som pulver och som tunn film. Syntesen av tetranukleära kluster i pulverform resulterade i både kluster och polymer struktur. pXRD av pulvren CuI(3-pic), CuI(4-pic) och CuI(3,5-lut) bekräftade dess struktur som polymera strukturer. Däremot visade CuI(3-pic) termokromism. Strukturen för CuI (3,4-lut) kunde inte obekräftas. Den mest effektiva metoden för syntes av tunn film i det här fallet är med SILAR-metoden.  Fotoluminescensspektra för respektive tunn film skiljer sig från deras motsvarande pulverform och strukturen på tunn film är fortfarande outforskat. Emission av CuI(3-pic), CuI(4-pic) och CuI(3,4-lut) som tunn film var ungefär lika ~480 nm medan för CuI(3,5-lut) så var det på 518 nm. Med denna kontrast utfördes ligand-utbyte-reaktionen på tunn film av CuI(3-pic) med 3,5- lutidin.  Ligand-utbyte-reaktionen av CuI(3-pic) på tunn film via förgasning av 3,5-lutidin resulterar i en spektrumförskjutning från spektrumet av CuI(3-pic) till spektrumet av CuI(3,5-lut). Detta indikerar i en lyckad ligand-utbyte-reaktion.  Livslängderna för de undersökta föreningarna vilket har sin bästa passning i mono- exponentiell funktion var mellan 2,2 μs och 9,52 μs. Livstiderna bestämdes på de tunn film med ”time-resolved photoluminescence”. Ligand-utbyte-reaktionen observerades också med ”time- resolved photoluminescence” som avslöjar några stabila livstider under reaktionen vilket kan indikera bildning av intermedianer. De uppmätta livstiderna under ligand-utbyte-reaktionen har däremot sin bästa passning av bi-exponentiell funktion vilket kan bero på reaktionsförhållanden under mätningen och tunn filmernas homogenitet.

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