Naslov (srp)

Struktura, priroda veze i magnetne osobine binuklearnih kompleksa Cu(II) i Ni(II) sa hidrazonskim ligandima : doktorska disertacija

Autor

Keškić, Tanja M., 1976-

Doprinosi

Zlatar, Matija, 1979-
Anđelković, Katarina, 1957-
Radanović, Dušanka, 1961-
Gruden-Pavlović, Maja, 1970-
Čobeljić, Božidar, 1983-

Opis (eng)

This thesis describes the synthesis, full characterisation and crystal structure of the complexes[CuL 1Cl]BF4 (1), [CuL 1Cl]NO3 (2), [Cu2L 12Cl2](BF4 )2 (3) and [Ni 2L 12 (μ-1,1-N3 )2 (N3 )2]⋅6H2 O (4),obtained in the reaction of the corresponding Cu(II) and Ni(II) ions and the ligand(E)-N,N,N-trimethyl-2-oxo-2-(2-(1-(pyridin-2-yl)ethylidene)hydrazinyl)ethan-1-aminium chloride(HL 1Cl) and complexes [Ni 2L 22 (μ-1,1 -N3 )2 (N3 )2]∙2H2 O (5a) and [Ni 2L 22 (μ-1,1 -N3 )2 (N3 )2]∙4H2 O (5b)obtained in the synthesis of Ni(II) ions and the ligand (E)-N,N,N-2-oxo-2-(2-(1-(thiazol-2-yl)ethylidene)hydrazinyl)ethan-1-aminium chloride, (HL 2Cl). All mentioned complexes werecharacterized in detail. Solid-state characterisation was carried out by infrared spectroscopy,elemental and X-ray structural analysis, and magnetic susceptibility was also measured for complexes5a and 5b.In all complexes 1–5, the ligands HL 1Cl and HL 2Cl are tridentately coordinated via a set of NNOdonor atoms in a formally neutral, deprotonated, zwitterionic form. In the case of complexes 1 and 2,metal ions with the HL 1Cl ligand form mononuclear complex, while in the case of complexes 3 and4 with the same ligand, binuclear complex is formed. Ligand HL 2Cl with Ni(II) ions builds binuclearcomplexes 5a and 5b. Complexes 5a and 5b were obtained from the same solution, with complex 5afound only in trace amounts.DFT calculations were performed for all complexes, the results of which were in accordance withthe experimental data. DFT calculations showed that in the case of mononuclear complexes 1 and 2,there is a weak coordination bond between the metal ion Cu(II) and the anions BF4– i NO3–, which isof a typical ionic type. For complex 3, DFT calculations showed that the complex exists as a binuclearspecies, in which two Cu(II) ions are connected to each other by bridging Cl– ligands and that theBF4– anion is not involved in coordination with Cu(II). In the case of complex 4, DFT calculationsshowed that independently of the applied functionals, ferromagnetic coupling exists between themetal centers. In complexes 5a and 5b, the calculated magnetic interaction according to the DFTapproach with meta-hybrid M06-2X and doubly hybrid B2PLYP and PWPB95 functionals shows thatin all cases, the model systems based on 5b have lower energy level than those based on 5a. Also, inthe case of the optimized structures 5a* and 5b* (at the BP86-D4/TZP level of theory), the optimizedstructure 5b* has a lower energy state. For complexes 5a and 5b, a temperature-dependent magneticsusceptibility was also measured, which showed that intramolecular interactions between Ni(II)centers are ferromagnetic in nature

Opis (srp)

U ovoj disertaciji opisana je sinteza, detaljna karakterizacija i kristalna struktura kompleksnihjedinjenja [CuL 1Cl]BF4 (1), [CuL 1Cl]NO3 (2), [Cu2L 12Cl2](BF4 )2 (3) i[Ni 2L 12 (μ-1,1-N3 )2 (N3 )2]⋅6H2 O (4), dobijenih u reakciji odgovarajućih Cu(II) i Ni(II) jona i liganda(E)-N,N,N-trimetil-2-okso-2-(2-(1-(piridin-2-il) etiliden(hidrazinil)etan-1-aminijum-hlorida (HL 1Cl)i kompleksa [Ni2L 22 (μ-1,1 -N3 )2 (N3 )2]∙2H2 O (5a) i [Ni 2L 22 (μ-1,1 -N3 )2 (N3 )2]∙4H2 O (5b) dobijenih usintezi Ni(II) jona i liganda (E)-N,N,N-trimetil-2-okso-2-(2-(1-(tiazol-2-il)etiliden)hidrazinil)etan-1-aminijum-hlorida, (HL 2Cl). Navedeni kompleksi (1–5) detaljno su okarakterisani. Karakterizacija učvrstom stanju rađena je pomoću IC spektroskopije, elementalne i rendgenske strukturne analize, dokje za komplekse 5a i 5b izmerena i magnetna susceptiblinost.Kod svih kompleksa 1–5 ligandi HL 1Cl i HL 2Cl koordinovani su tridentatno preko NNOdonorskih atoma u deprotonovanom, formalno neutralnom, cviter-jonskom obliku. U slučajukompleksa 1 i 2 metalni joni sa ligandom HL1Cl grade mononuklearne komplekse, dok u slučajukompleksa 3 i 4 sa istim ligandom formiraju se binuklearni kompleski. Ligand HL 2Cl sa jonima Ni(II)gradi binuklearne komplekse 5a i 5b. Kompleksi 5a i 5b dobijeni su iz istog rastvora pri čemu jekompleks 5a pronađen samo u tragovima.Za sve komplekse urađeni su DFT proračuni, čiji rezultati su bili u skladu sa podacimadobijenim eksperimentalnim putem. DFT proračuni su pokazali da u slučaju mononuklearnihkompleksa 1 i 2, postoji slaba koordinativna veza između centralnog metalnog jona Cu(II) i anjonaBF4– i NO3–, koja je izrazitog jonskog karaktera. Kod kompleksa 3 DFT proračuni su pokazali dakompleks postoji kao binuklearna vrsta, kod koje su dva Cu(II) jona međusobno povezana mosnimCl– ligandima i da BF4– anjon nije uključen u koordinaciju sa Cu(II). Kod kompleksa 4, DFT proračunipokazali su da nezavisno od primenjenih funkcionala, između metalnih centara postoji feromagnetnokuplovanje. U kompleksima 5a i 5b izračunata magnetna interakcija prema DFT pristupu sa meta-hibridnim M06-2X i dvostruko hibridnim B2PLYP i PWPB95 funkcionalima pokazuje da u svimslučajevima, model sistemi zasnovani na 5b imaju niže energije od onih zasnovanih na 5a. Takođe, iu slučaju optimizovanih struktura 5a* i 5b* (na BP86-D4/TZP nivou teorije), optimizovana struktura5b* ima nižu energiju. Za komplekse 5a i 5b urađeno je i merenje temperaturno zavisne magnetnesusceptibilnosti, koje je pokazalo da su intramolekulske interakcije između Ni(II) centaraferomagnetne.

Opis (srp)

Hemija - Neorganska hemija / Chemistry - Inorganic chemistry Datum odbrane: 02.11.2023.

Jezik

srpski

Datum

2023

Licenca

Ovo delo je licencirano pod uslovima licence
Creative Commons CC BY-NC-ND 3.0 AT - Creative Commons Autorstvo - Nekomercijalno - Bez prerada 3.0 Austria License.

http://creativecommons.org/licenses/by-nc-nd/3.0/at/legalcode

Predmet

OSNO - Opšta sistematizacija naučnih oblasti, Metali

kompleksi d-metala, hidrazonski ligandi, kristalna struktura, magnetne osobine, teorija funkcionala gustine, računarska hemija

OSNO - Opšta sistematizacija naučnih oblasti, Metali

d-metal complexes, hydrazone ligands, crystal structure, magnetic properties, density functional theory, computational chemistry