Strukturno i kvantno-kemijsko istraživanje bis(3-piridil)diiminâ kao akceptorâ halogenske veze

master's thesis

• Title (english): Structural and quantum chemical investigation of bis(3-pyridyl)diimines as halogen bond acceptors
• Author: Tomislav Piteša
• Mentor: Vladimir Stilinović (mentor)
• Mentor: Ivan Ljubić (mentor)
• Committee member: Vladimir Stilinović (predsjednik povjerenstva)
• Committee member: Zlatko Mihalić (član povjerenstva)
• Committee member: Gordan Horvat (član povjerenstva)
• Committee member: Dominik Cinčić (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2018-02-12, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry

Abstract

Pripravljeno je i strukturno okarakterizirano šest novih kokristala politopičnih donora (triju polihalogeniranih benzenskih derivata) i akceptora (dvaju bis(3-piridil)diimina) halogenske veze. U svim kokristalima piridinski atom dušika bio je akceptor halogenske veze, dok je iminski to bio samo u tri. Uz to, u četiri kokristala prisutna je i halogenska veza čiji je akceptor negativno područje atoma joda (prsten oko kovalentne veze) povezanog halogenskom vezom s piridinskim atomom dušika. Pripravljeni kokristali i halogenske veze okarakterizirani su i kvantno-kemijski te je ustanovljeno da je halogenska veza s piridinskim jača od one s iminskim atomom dušika kao akceptorom, kako u plinskoj fazi tako i u kokristalima. Također je objašnjena opažena razlika u supramolekulskom ponašanju donora, kao i dvojaka (donorsko-akceptorska) svojstva atoma joda u molekulama donora, otkrivajući dosad neopažene antagonističke i agonističke sprege među višestrukim halogenskim vezama.

Abstract (english)

Six new cocrystals of polytopic halogen bond donors (three polyhalogenated benzene derivatives) and acceptors (two bis(3-pyridyl)diimines) were synthesized and structurally characterized. In all cocrystals, the pyridine nitrogen atom was a halogen bond acceptor, while imine nitrogen atom was acceptor in three of them. Also, in four cocrystals, halogen bond with negative region of iodide atom (involved in halogen bond with pyridine nitrogen atom) as acceptor site was present. The cocrystals and the halogen bonds were characterized by means of quantum-chemical calculations, revealing that the halogen bond with pyridine is stronger then the one with the imine nitrogen atom as the acceptor, both in the gas phase and the solid state. Observed differences in supramolecular behaviour of donors, as well as ambivalent (donor-acceptor) properties of iodine atom in the donor molecules, were elucidated, revealing so far unseen antagonistic and agonistic couplings between multiple halogen bonds.

• Keywords: halogenska veza; kristalno inženjerstvo; politopični donori i akceptori; teorija funkcionala gustoće
• Keywords (english): crystal engeneering; density functional theory; halogen bonds; politopic donors and acceptors
• Language: croatian
• URN:NBN: urn:nbn:hr:217:036844
• 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: 2020-02-12
• Created on: 2018-02-21 15:57:53