magistrsko delo
Filip Kóša (Author), Amalija Golobič (Mentor), Helena Prosen (Thesis defence commission member), Marta Kasunič (Thesis defence commission member)

Abstract

V okviru magistrskega dela sem z metodo rentgenske difrakcije na monokristalu določil kristalne strukture osmih hibridnih organsko-anorganskih morfolinijevih spojin, in sicer dveh jodidoplumbatov z oznakama Pb(1) in Pb(2) in formulama (C$_4$H$_{10}$NO)$_2$PbI$_4$ in (C$_4$H$_{10}$NO)PbI$_3$, treh jodidobizmutatov z oznakami Bi(1), Bi(2) in Bi(3) in formulami (C$_4$H$_{10}$NO)$_2$(H$_3$O)BiI$_6$·H$_2$O, (C$_4$H$_{10}$NO)$_4$Bi$_4$I$_{16}$·6H$_2$O in (C$_4$H$_{10}$NO)$_4$(BiI$_6$)(I$_3$) ter treh jodidoantimonatov z oznakami Sb(1), Sb(2) in Sb(3) ter formulami (C$_4$H$_{10}$NO)$_2$SbI$_5$, (C$_4$H$_{10}$NO)$_4$Sb$_4$I$_{16}$·2(CH$_3$CN) in (C$_4$H$_{10}$NO)$_4$(I$_3$)SbI$_6$. V literaturi do sedaj še ni bilo opisane nobene strukture oziroma spojine kakega morfolinijevega jodidobizmutata ali jodidoantimonata. Skupno vsem obravnavanim spojinam je, da nastopa morfolinijev kation v obliki stola in da je na anorganski del strukture povezan preko vodikovih N–H···I vezi, van der Waalsovih pa tudi ionskih vezi in tako spojine spadajo med strukturne hibride oziroma hibridne materiale tipa II. Anorganskemu delu struktur je skupno to, da je centralni ion (Pb$^{2+}$, Bi$^{3+}$ oz. Sb$^{3+}$) povsod obdan s šestimi jodido ligandi v obliki popačenega oktaedra. Spojini Bi(2) in Sb(3) sta izostrukturni in obe edini vključujeta poleg koordinacijskega aniona še dodatni trijodidni anion. Koordinacijski anion je v teh dveh strukturah enojedrni BiI$_6^{3−}$ oz. SbI$_6^{3−}$. Tak enojedrni anion je še v Bi(1) strukturi, ki vključuje še oksonijeve ione in molekule vode. Spojini Bi(2) in Sb(2) vključujeta centrosimetrične štirijedrne anione Bi$_4$I$_{16}^{4–}$ oz. Sb$_4$I$_{16}^{4–}$, v katerih so oktaedri povezani preko skupnih robov, ter molekule topila, ki je v primeru Bi(2) voda in v primeru Sb(2) acetonitril. Anioni v spojinah Sb(1) in Pb(2) so 1D neskončne verige. V Sb(1) se oktaedri povezujejo v verige preko skupnih oglišč in v Pb(2) preko skupnih ploskev. V Pb(1) strukturi pa se oktaedri povezujejo preko oglišč v 2D neskončne plasti. Kljub vsej pestrosti v primeru struktur, ki sem jih določil, pa med njimi ni nobene, kjer bi se oktaedri povezovali preko vseh oglišč oktaedrov v 3D neskončen anion, torej ne gre za hibridne perovskite v ožjem osnovnem pomenu besede perovskit. Spojine so bile okarakterizirane še z rentgensko praškovno difrakcijo, elementno CHN analizo in termično analizo. V vseh spojinah pride do razpada organskega dela hibridne strukture v intervalu med 190 in 270 °C. Pri vseh spojinah pri termičnem razpadu zapusti spojino tudi precej svinca, bizmuta oziroma antimona.

Keywords

hibridni organsko-anorganski materiali;morfolin;jodidoplumbati;jodidobizmutati;jodidoantimonati;rentgenska strukturna analiza;magistrska dela;

Data

Language: Slovenian
Year of publishing:
Typology: 2.09 - Master's Thesis
Organization: UL FKKT - Faculty of Chemistry and Chemical Technology
Publisher: [F. Kóša]
UDC: 544.1:543.442.3(043.2)
COBISS: 225311235 Link will open in a new window
Views: 85
Downloads: 28
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Other data

Secondary language: English
Secondary title: Crystal structures of organic-inorganic hybrid iodidoplumbates, iodidobismuthates, and iodidoantimonates
Secondary abstract: In my master's thesis, I determined the crystal structure of eight hybrid organic-inorganic morpholinium compounds using X-ray diffraction on a single crystal. These include two iodidoplumbates labeled Pb(1) and Pb(2) with the formulas (C$_4$H$_{10}$NO)$_2$PbI$_4$ and (C$_4$H$_{10}$NO)PbI$_3$, three iodidobismuthates labeled Bi(1), Bi(2), and Bi(3) with the formulas (C$_4$H$_{10}$NO)$_2$(H$_3$O)BiI$_6$·H$_2$O, (C$_4$H$_{10}$NO)$_4$Bi$_4$I$_{16}$·6H$_2$O and (C$_4$H$_{10}$NO)$_4$(BiI$_6$)(I$_3$), as well as three iodidoantimonates labeled Sb(1), Sb(2), and Sb(3) with the formulas (C$_4$H$_{10}$NO)$_2$SbI$_5$, (C$_4$H$_{10}$NO)$_4$Sb$_4$I$_{16}$·2(CH$_3$CN) and (C$_4$H$_{10}$NO)$_4$(I$_3$)SbI$_6$. No structure or compound of any morpholinium iodidobismuthate or iodidoantimonate has been described in the literature to date. The discussed compounds have in common that the morpholinium cation occurs in a chair conformation and is connected to the inorganic part of the structure via hydrogen N–H···I bonds, van der Waals interactions, and also ionic bonds, thus classifying the compounds as structural hybrids or hybrid materials of type II. Common to the inorganic part of the structures is that the central ion (Pb$^{2+}$, Bi$^{3+}$ or Sb$^{3+}$) is surrounded by six iodido ligands in the form of a distorted octahedron. Bi(3) and Sb(3) are isostructural, and both of them include an additional triiodide anion besides the mononuclear coordination anion (BiI$_6^{3−}$ or SbI$_6^{3−}$). The Bi(1) structure also contains the same mononuclear anion besides oxonium ions and water molecules. Bi(2) and Sb(2) contain centrosymmetric tetranuclear Bi$_4$I$_{16}^{4–}$ or Sb$_4$I$_{16}^{4–}$, in which the octahedra are connected via shared edges, and solvent molecules, which are water in the case of Bi(2) and acetonitrile in the case of Sb(2). The anions in Sb(1) and Pb(2) are 1D infinite chains. In Sb(1), the octahedra are linked into chains via shared vertices and in Pb(2) via shared faces. In Pb(1), the octahedra are connected via vertices into 2D infinite layers. Despite the diversity of the structures I have determined, there is none among them where the octahedra are connected via all vertices into a 3D infinite anion, so they are not hybrid perovskites in the basic sense of the term perovskite. The compounds were also characterized by X-ray powder diffraction, elemental CHN analysis, and thermal analysis. In all compounds, the organic part of the hybrid structure decomposes in the interval between 190 to 270 °C. During the thermal decomposition, a significant amount of lead, bismuth, and antimony is released from the compounds.
Secondary keywords: hybrid organic-inorganic materials;morpholine;iodidobismuthate;iodidoantimonate;X-ray structural analysis;Kristalna struktura;Jodove spojine;Univerzitetna in visokošolska dela;
Type (COBISS): Master's thesis/paper
Study programme: 1000375
Embargo end date (OpenAIRE): 1970-01-01
Thesis comment: Univ. v Ljubljani, Fak. za kemijo in kemijsko tehnologijo, smer Kemija
Pages: 1 spletni vir (1 datoteka PDF (83 str.))
ID: 25746836