Strukturno i računalno istraživanje supramolekulskih interakcija u odabranim koordinacijskim spojevima kobalta(II) i nikla(II) s 3-klorpentan-2,4-dionatom i piridinoksimima

master's thesis

• Title (english): Structural and computational study of supramolecular interactions in selected cobalt(II) and nickel(II) coordination compounds with 3-chloropentane-2,4-dionato and pyridineoximes
• Author: Toni Lijić
• Mentor: Marijana Đaković (mentor)
• Mentor: Ivan Kodrin (mentor)
• Committee member: Marijana Đaković (predsjednik povjerenstva)
• Committee member: Ivan Kodrin (član povjerenstva)
• Committee member: Iva Juranović Cindrić (član povjerenstva)
• Committee member: Morana Dulić (član povjerenstva)
• Committee member: Dominik Cinčić (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2019-02-26, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry

Abstract

Pripravljeni su 3-klorpentan-2,4-dionatni (Cl-acac) koordinacijski spojevi nikla(II) i kobalta(II) s nizom
piridinoksimskih liganada: (3-piridilaldoksim (3-oxpy), 4-piridilaldoksim (4-oxpy), metil-3-
piridilketoksim (3-moxpy), metil-4-piridilketoksim (4-moxpy), fenil-4-piridilketoksim (4-phoxpy)).
Otopinskom sintezom priređeno je šest novih koordinacijskih spojeva [Ni(Cl-acac)2(3-oxpy)2], [Ni(Clacac)
2(3-moxpy)2], [Ni(Cl-acac)2(4-oxpy)2], [Ni(Cl-acac)2(4-moxpy)2], [Co(Cl-acac)2(4-moxpy)2] i
[Ni(Cl-acac)2(4-phoxpy)2] te mehanokemijskom sintezom još četiri koordinacijska spoja, [Co(Clacac)
2(4-phoxpy)2], [Co(Cl-acac)2(4-oxpy)2], [Ci(Cl-acac)2(3-moxpy)2] i [Co(Cl-acac)2(3-oxpy)2]. Svi
priređeni spojevi okarakterizirani su infracrvenom spektroskopijom te difrakcijom rentgenskog zračenja
u polikristalnom uzorku. Rentgenskom strukturnom analizom, metodom difrakcije rentgenskog zračenja
u jediničnom kristalu, određene su kristalne strukture sedam koordinacijskih spojeva te su DFT
pristupom modelirane geometrije svih koordinacijskih spojeva i izračunate vrijednosti elektrostatskog
potencijala mogućih donora i akceptora vodikove veze. Predložene su granične vrijednosti razlika
elektrostatskih potencijala mogućih akceptora vodikove veze pri kojima selektivno nastaje određeni
supramolekulski motiv.

Abstract (english)

Whithin this thesis, a series of coordination compounds of Co(II) and Ni(II) with 3-chloropentane-2,4-
dionato ligands (3-Clacac) and pyridyleoxime ligands (3-pyridylealdoxime (3-oxpy), 4-
pyridylaldoxime (4-oxpy), methyl-3-pyridylketoxime (3-moxpy), methyl-4-pyridylketoxime (4-
moxpy), phenyl-4-pyridylketoxime (4-phoxpy)) were prepared, namely [Ni(Cl-acac)2(3-oxpy)2],
[Ni(Cl-acac)2(3-moxpy)2], [Ni(Cl-acac)2(4-oxpy)2], [Ni(Cl-acac)2(4-phoxpy)2], [Co(Cl-acac)2(4-
phoxpy)2] via solution and [Co(Cl-acac)2(3-oxpy)2], [Co(Cl-acac)2(3-moxpy)2], [Co(Cl-acac)2(4-
oxpy)2], [Co(Cl-acac)2 (4-phoxpy)2] via mechanochemical synthetic route. All synthesised compounds
were characterized by infrared spectroscopy and powder X-ray diffraction, and altogether seven newly
crystal structures were determined by single crystal X-ray analysis. In the next step, DFT approach was
used for modelling coordination geometry of the structurally characterized coordination compounds,
from which the electrostatic potential (ESP) values for all good hydrogen bond donors and acceptors
were then calculated. The ESP differences between competing hydrogen bond acceptor sites were used
for proposing boundary values within which specific supramolecular motifs occur.

• Keywords: DFT; elektrostatski potencijal; kobalt(II); koordinacijski spojevi; kristalna struktura; nikal(II); oksimi; supramolekulska kemija; vodikova veza
• Keywords (english): cobalt(II); coordination compounds; crystal structure; DFT; electrostatic potential; hydrogen bond; nickel(II); oximes; supramolecular chemistry
• Language: croatian
• URN:NBN: urn:nbn:hr:217:949101
• Study programme: Title: Graduate university studies in chemistry; specializations in: Research programme; Course: Research programme; Study programme type: university; Study level: graduate; Academic / professional title: magistar/magistra kemije (magistar/magistra kemije)
• Type of resource: Text
• File origin: Born digital
• Access conditions: Open access; Embargo expiration date: 2021-02-26
• Created on: 2019-04-02 09:43:53