Strukturno i kvantno-kemijsko istraživanje tetranuklearnih kompleksa Ni(II)

master's thesis

• Title (english): Structural and Quantum Chemical Investigation of Tetranuclear Nickel (II) Complexes
• Author: Karlo Sović
• Mentor: Tomica Hrenar (mentor)
• Mentor: Marina Cindrić (mentor)
• Committee member: Marina Cindrić (predsjednik povjerenstva)
• Committee member: Tomica Hrenar (član povjerenstva)
• Committee member: Snežana Miljanić (član povjerenstva)
• Committee member: Zlatko Mihalić (član povjerenstva)
• Committee member: Višnja Vrdoljak (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2016-03-23, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry

Abstract

Nikal(II) u kompleksnim spojevima [Ni4L4(R1OH)n(R2OH)4-n] (n=0–4, R1=CH3–, R2=C2H5–) s ONO tridentatnim ligandima tvori kubansku strukturu Ni4O4 čija simetrija bitno utječe na magnetska svojstva dotičnih kompleksa. Četiri koordinacijska mjesta u kompleksu popunjena su molekulama otapala (metanol ili etanol), po jedno na svakom ionu Ni(II), a njihova zastupljenost ovisi o uvjetima sinteze. Kompleksni spojevi nikla priređeni su solvotermalnim reakcijama Ni(OAc)2∙4H2O, Schiffove baze (L) i metanola odnosno etanola.
U okviru ovog diplomskog rada istražen je utjecaj otapala na tijek kemijskih reakcija te strukture dobivenih kompleksa, provođenjem kvantno-kemijskih računâ korištenjem teorije funkcionala gustoće i Grimmeove D3 korekcije za disperzne sile. Izračunom vibracijskih frekvencija izračunate su i standardne Gibbsove energije stvaranja kompleksa prema kojima je određena njihova relativna stabilnost. Uz to je provedena i simulacija molekularne dinamike na najstabilnijem tetranuklearnom kompleksu Ni(II) kako bi se detaljnije ispitala kemodinamika kubanske strukture Ni4O4.

Abstract (english)

Nickel(II) complexes of type [Ni4L4(R1OH)n(R2OH)4-n] (n=0–4, R1=CH3–, R2=C2H5–) with ONO tridentate ligands form a cubane-like Ni4O4 structure whose symmetry considerably dictates the magnetic properties of described complexes. Four coordination sites in complex are bonded with solvent molecules (methanol or ethanol) and their ratio depends on the conditions of synthesis. Previously mentioned Ni(II) complexes were synthesized via solvothermal reactions of Ni(OAc)2∙4H2O, Schiffs base and methanol or ethanol.
In this thesis the solvent effect on synthetic route and structure properties of complexes was examined by quantum-chemical calculations based on density field theory along with the newest revision of Grimmes D3 correction for dispersion interactions. In addition, standard Gibbs free energies of formation of respective complexes were calculated from theoretically determined vibrational frequencies and used to describe relative stabilities of examined Ni(II) complexes. Furthermore, simulation of molecular dynamics was performed on the most stable tetranuclear nickel(II) complex so that the motion of cubane-like Ni4O4 structure can be in detail described.

• Keywords: tetranuklearni kompleksi Ni(II); jednomolekulski magneti; DFT; molekularna dinamika
• Keywords (english): tetranuclear Ni(II) complexes; DFT; molecular dynamics
• Language: croatian
• URN:NBN: urn:nbn:hr:217:050425
• 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: 2018-03-23
• Created on: 2017-03-23 09:25:27