Utjecaj supstituenata na delokalizaciju pi-elektrona kod različito supstituiranih 2,5-dihidroksikinona i njihovih aniona

master's thesis

• Title (english): Substituent effects on pi-electron delocalisation of variously subsituted 2,5-dihydroxyquinones and their anions
• Author: Vedran Vuković
• Mentor: Krešimir Molčanov (mentor)
• Committee member: Vladimir Stilinović (predsjednik povjerenstva)
• Committee member: Vladislav Tomišić (član povjerenstva)
• Committee member: Zlatko Mihalić (član povjerenstva)
• Committee member: Gordan Horvat (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2018-07-06, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry

Abstract

Kinoni su kemijski spojevi koji sadrže 1,4-dioksocikloheksa-2,5-diensku jezgru. Korisni su u kemijskoj
i farmaceutskoj industriji te imaju ulogu prijenosnika elektrona u središnjem energijskom
metabolizmu. 2,5-dihidroksikinon, njegovi derivati (3,6-dinitro, 3,6-dikloro, 3,6-dibromo) i njihovi
anioni zanimljivi su iz perspektive kristalnog inženjerstva jer stvaraju predvidive stupiće pomoću
π-interakcija, kao i drugi kinonski derivati. Male promjene u strukturi kinonskog prstena dovode
do velikih promjena u kristalnom pakiranju i fizičkim svojstvima poput p𝐾a. Različitost opaženih
stvojstava posljedica je razlika u raspodjeli gustoće naboja. Eksperimentalnim i teorijskim metodama
određena je gustoća naboja 2,5-dihidroksikinonatnog dianiona, 3,6-dikloro-2,5-dihidroksikinona i
njenog dianiona. Napravljena je topološka analiza gustoće naboja pomoću koje su karakterizirana
svojstva atoma i veza u istraživanim spojevima. Rezultati su uspoređeni s dosadašnjim spoznajama o
3,6-dikloro-2,5-dihidroksikinonatnom monoanionu i 3,6-dinitro-2,5-dihidroksikinonatnom dianionu
temeljenim na njihovim gustoćama naboja.

Abstract (english)

Quinones are chemical compounds containing a 1,4-dioxocyclohexa-2,5-diene ring. They are widely
used in chemical and pharmaceutical industry and play a key role in the central energy metabolism
as electron transfer mediators. 2,5-dihydroxyquinone, its derivatives (3,6-dinitro, 3,6-dichloro, 3,6-
dibromo) and their anions are interesting from a crystal engineering point of view because they
form small columns via π-interactions, like other quinone derivatives. Small changes in quinone
ring makeup lead to large differences in crystal packing and physical properties like p𝐾a. The
variation in observed properties is a consequence of diverse charge density distributions. Charge
densities of 2,5-dihydroxyquinonate dianion, 3,6-dichloro-2,5-dihydroxyquinone and its dianion
were determined using an experimental and a theoretical approach. Topological analysis of charge
density was used to characterise atom and bond properties in investigated compounds. The results
were compared with available data on 3,6-dichloro-2,5-dihydroxyquinonatne monoanion and 3,6-
dinitro-2,5-dihydroxyquinonate dianion based on their charge densities.

• Keywords: gustoća naboja; kinoni; rentgenska strukturna analiza; topološka analiza
• Keywords (english): charge density; quinones; X-ray structure analysis; topological analysis
• Language: croatian
• URN:NBN: urn:nbn:hr:217:276687
• 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: 2020-07-06
• Created on: 2018-07-11 12:51:25