Priprava kokristala koordinacijskih polimera kadmija(II): utjecaj steričkih i elektronskih efekata na nastanak i održivost njihovih struktura

master's thesis

• Title (english): Preparation of co-crystals of cadmium(II) coordination polymers: Impact of steric and electronic effects on formation and sustainability of their structures
• Author: Ozana Mišura
• Mentor: Marijana Đaković (mentor)
• Committee member: Marijana Đaković (predsjednik povjerenstva)
• Committee member: Davor Kovačević (član povjerenstva)
• Committee member: Ivan Kodrin (član povjerenstva)
• Committee member: Dominik Cinčić (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2020-02-21, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry

Abstract

U okviru ovog diplomskog rada provedena je kokristalizacija koordinacijskih polimera kadmijevih(II)
halogenida i halogenpirazina s nekoliko koformera (1,4-dicijanobenzenom, 1,4-benzokinonom, 1,3-
dinitrobenzenom). Osim mljevenja potpomognutog kapljevinom (LAG), pojedini kokristali uspješno
su priređeni i otopinskom sintezom. Nastali produkti karakterizirani su infracrvenom spektroskopijom
(IR), termičkim metodama (TG/DSC) i metodom difrakcije rendgenskih zraka u polikristalnom uzorku
(PXRD) kojom je potvrđen nastanak/izostanak kokristala. Iz podataka prikupljenih metodom
difrakcije rendgenskih zraka u monokristalnom uzorku (SCXRD) određene su molekulske i kristalne
strukture, a ostvarene međumolekulske interakcije u kristalnoj strukturi kokristala uspoređene su s
odgovarajućima u koordinacijskom polimeru. Na temelju izračunatih vrijednosti molekulskih
elektrostatskih potencijala koformera proučeni su elektronski efekti ključni za održivost kokristala u
čvrstom stanju/otopini. Ispitan je i kvantificiran mehanički odziv priređenih kokristala uslijed primjene
mehaničke sile na igličaste kristale. Stupanj savitljivosti kokristala [CdI2(I-pz)2][1,4-DCB] uspoređen
je sa stupnjem savitljivosti [CdI2(I-pz)2]n iz čega je ustanovljeno da se ugađanjem kristalne strukture
(kokristalizacijom) može modificirati (u ovom slučaju povećati) stupanj fleksibilnog odziva

Abstract (english)

Within the framework of this thesis, co-crystallization of the halide coordination polymers of
cadmium(II) and halopyrazines with several co-formers (1,4-dicianobenzene, 1,4-benzoquinone, 1,3-
dinitrobenzene) was carried out. In addition to liquid-assisted milling (LAG), some co-crystals were
also successfully prepared by solution synthesis. The resulting products were characterized by infrared
spectroscopy (IR), thermal methods (TG/DCS) and an X-ray diffraction method in a polycrystalline
sample (PXRD) confirming the formation or absence of co-crystals. Molecular and crystalline
structures were determined from the data collected by the single-crystal X-ray diffraction method
(SCXRD), and intemolecular interactions in the crystal structure of co-crystals and starting
coordination polymers were compared. From the calculated molecular electrostratic potential surfaces
values of co-formers, electronic effects crucial for the viability of co-crystals in the solid-state/solution
were studied. The mechanical response of crystals of prepared compounds due to the application of
mechanical force was investigated and quantified. The bending strain of [CdI2(I-pz)2][1,4-DCB] cocrystal
was compared with the bending strain of [CdI2(I-pz)2]n. It has been established that the degree
of flexible response can be modified (in this case increased) by tuning the crystal structure (by cocrystallization).

• Keywords: halogenska veza; kokristali; koordinacijski polimeri kadmija(II); mehanički odziv; mehanokemijska sinteza; vodikova veza
• Keywords (english): co-crystals; cadmium(II) coordination polymers; mechanical response; mechanochemical synthesis; halogen bond; hydrogen bond
• Language: croatian
• URN:NBN: urn:nbn:hr:217:292083
• 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: 2022-02-21
• Created on: 2020-03-06 12:41:16