Halogenpiridinijevi kvarterni kationi kao donori halogenske veze

doctoral thesis

• Title (english): Quaternary halogenopyridinium cations as halogen bond donors
• Author: Luka Fotović
• Mentor: Vladimir Stilinović (mentor)
• Committee member: Biserka Prugovečki (predsjednik povjerenstva)
• Committee member: Krešimir Molčanov (član povjerenstva)
• Committee member: Josip Požar (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2022-02-18, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry
• Universal decimal classification (UDC): 54 - Chemistry. Crystallography. Mineralogy

Abstract

U ovome istraživanju, uvođenjem različitih (alifatskih) supstituenata na piridinski dušikov atom
halogenpiridina (osobito meta izomera) pripravljeno je te strukturno, termički i spektroskopski
okarakterizirano 49 novih soli protoniranih i N-alkiliranih halogenpiridina. Usporedbom
halogenskih veza u strukturama N-alkil-3-jodpiridinijevih jodida utvđeno da postoji trend da
što je duži ugljikovodični lanac supstituiran na dušikov atom jodpiridinskog prstena to su kraće
halogenske veze C−I⋯I−. Ustanovljeno je da afinitet prema halogenskoj vezi opada s veličinom
halogenidnog aniona kao akceptora, odnosno slijedi isti trend kao i u slučaju vodikove veze.
Analizom raspodjele naboja na halogenpiridinijevim kationima utvrđeno je da i protoniranje i
N-metiliranje halogenpiridina dovode do značajnog povećanja elektrostatskog potencijala σšupljine halogena što uvelike povećava incidenciju ostvarivanja halogenskih veza u odnosu na
neutralne halogenpiridine. To čini halogenpiridinijeve katione (jodpiridinijeve posebno)
prilično pouzdanim donorima halogenskih veza, te na taj način opravdava njihovu upotrebu u
dizajnu i sintezi supramolekulskih struktura povezanih halogenskom vezom.

Abstract (english)

In this study, 49 novel salts of halogenopyridinium cations were prepared and characterized by
single crystal X-ray diffraction, and by thermal and spectroscopic analysis methods. In the
crystal structures of N-alkyl-3-iodopyridinium iodides it is observed trend that longer chains as
N-substituents generally leading to shorter C−I⋯I− halogen bonds. Based on the trend observed
in the relative shortenings of distances of the two interactions, both halogen and hydrogen bonds
seem to be decreasing in strength with the size of the halogenide anion. Inspection of the
distribution of the charge on the cations revealed that both protonation and N-methylation of
halogenopyridines lead to a considerable increase in the electrostatic potential of the halogen
σ-hole which increase incidence of the halogen bond in the structures comprising
halogenopyridinium cations (as compared to neutral halogenopyridines). This makes
halopyridiniom cations (iodopyridinium in particularly) fairly reliable halogen bond donors for
deliberate synthesis of halogen bonded supramolecular structures.

• Keywords: halogenidni anioni; halogenpiridinijevi kationi; halogenska veza; kristalno inženjerstvo; soli; vodikova veza
• Keywords (english): crystal engineering; halogen bond; halogenide anions; halogenpyridine cations; hydrogen bond; salts
• Language: croatian
• URN:NBN: urn:nbn:hr:217:996672
• Promotion: 2022
• Project: Number: IP-2014-09-7367; Title: Kristalno inženjerstvo višekomponentinih metaloorganksih materijala povezanih halogenskom vezom: ususret supramolekulskom ugađanju strukture i svojstava; Title: Crystal engineering of multicomponent halogen bonded metal-organic materials: towards supramolecular control over structure and properties; Acronym: CrystEngMOM; Leader: Dominik Cinčić; Jurisdiction: Croatia; Funder: HRZZ; Funding stream: IP
• Project: Number: IP-2019-04-1868; Title: Nove građevne jedinke u supramolekulskom dizajnu složenih višekomponentnih molekulskih kristala temeljenih na halogenskim vezama; Title: New building blocks for the supramolecular design of complex multi-component molecular crystals based on halogen bonds; Acronym: HaloBond; Leader: Dominik Cinčić; Jurisdiction: Croatia; Funder: HRZZ; Funding stream: IP
• Study programme: Title: Doctoral study in chemistry; Study programme type: university; Study level: postgraduate; Academic / professional title: doktor/doktorica znanosti, područje prirodnih znanosti, polje kemija (doktor/doktorica znanosti, područje prirodnih znanosti, polje kemija)
• Type of resource: Text
• Extent: 93 str. ; 30 cm
• File origin: Born digital
• Access conditions: Open access
• Created on: 2022-02-23 12:18:12