Aproksimacije funkcionala gustine u proučavanju energija spinskih stanja kompleksa prelaznih metala.

Many fascinating features of coordination chemistry originate from the fact that small changes in metal ion environment can induce big changes in the properties of the compounds. Moreover, most transition-metal (TM) ions with partially filled d-shells can manifest different spin multiplicity in the ground state that is, different spin states. The identity of the ground spin state and the analysis and description of close lying states of different multiplicity is of crucial importance for the understanding of the microscopic origin of the reactivity, electrochemistry and photochemistry in biomolecules, industrial catalysis and in spin crossover compounds. However, elucidating the role and effect of different spin states on the properties of a system, and even determining which spin state occurs naturally, is challenging task both from an experimental and theoretical point-of-view...Mnoge fascinantne osobenosti koordinacione hemije potiču od činjenice da male promene u okruženju centralnog metala mogu izazvati velike promene u svojstvima jedinjenja. Štaviše, većina jona prelaznih metala (TM) sa delimično popunjenim d-orbitalama može manifestovati različit spinski multiplicitet u osnovnom stanju, tj. različita spinska stanja. Identitet osnovnog spinskog stanja i analiza i opis bliskih spinskih stanja različitog multipliciteta su od ključnog značaja za razumevanje mikroskopskog porekla reaktivnosti, elektrohemijskih osobina, fotohemijskog ponašanja biomolekula, industrijske katalize i spin-crossover (SCO) jedinjenja. Međutim, razjašnjavanje uloge i efekta različitih spinskih stanja na osobine sistema, pa čak i samo određivanje osnovnog spinskog stanja je komplikovan zadatak sa eksperimentalne kao i teorijske tačke gledišta..

Supplementary data for article: Stepanovic, S.; Angelone, D.; Gruden-Pavlović, M.; Swart, M. The Role of Spin States in the Catalytic Mechanism of the Intra- and Extradiol Cleavage of Catechols by O-2. Organic and Biomolecular Chemistry 2017, 15 (37), 7860–7868. https://doi.org/10.1039/c7ob01814b

Supplementary material for: [https://doi.org/10.1039/c7ob01814b]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/2536

Supplementary material for the article: Ajdačić, V.; Stepanović, S.; Zlatović, M.; Gruden, M.; Opsenica, I. M. Decarbonylative Dibromination of 5-Phenylthiophene-2-Carbaldehyde with Bromine. Synthesis (Germany) 2016, 48 (24), 4423–4430. https://doi.org/10.1055/s-0035-1562615

Supplementary material for: [http://dx.doi.org/10.1055/s-0035-1562615]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/2361

Supplementary data for the article: Andjelković, L.; Stepanović, S.; Vlahović, F.; Zlatar, M.; Gruden, M. Resolving the Origin of the Multimode Jahn-Teller Effect in Metallophthalocyanines. Physical Chemistry Chemical Physics 2016, 18 (42), 29122–29130. https://doi.org/10.1039/c6cp03859j

Supplementary material for: [https://doi.org/10.1039/c6cp03859j]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/2344

Spin state relaxation of iron complexes: The case for OPBE and S12g

The structures of nine iron complexes that show a diversity of experimentally observed spin ground states were optimized and analyzed using the Density Functional Theory (DFT). An extensive validation study of the new S12g functional was performed, with a discussion concerning the influence of the environment, geometry and its overall performance based on a comparison with the well-proven OPBE functional. The OPBE and S12g functionals gave the correct spin ground state for all investigated iron complexes. Since S12g performs remarkably well, it could be considered a reliable tool for studying the energetics of the spin state in complicated transition metal systems

Supplementary data for the article: Popović-Djordjević, J.; Stepanović, S.; Došen-Mićović, L.; Ivanović, E.; Ivanović, M. D. High-Yielding Method for Preparation of Carbocyclic or N-Containing Heterocyclic β-Keto Esters Using in Situ Activated Sodium Hydride in Dimethyl Sulphoxide. Green Chemistry Letters and Reviews 2016, 9 (1), 61–68. https://doi.org/10.1080/17518253.2016.1145744

Supplementary material for: [https://doi.org/10.1080/17518253.2016.1145744]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/115

The Irony of Manganocene: An Interplay between the Jahn-Teller Effect and Close-Lying Electronic and Spin States

Although the unusual structural, magnetic,electronic, and spin characteristics of manganocene hasintrigued scientists for decades, a unified explanation andrationalization of its properties has not yet been provided.Results obtained by Multideterminantal Density Functional Theory (MD-DFT), Energy Decomposition Analysis (EDA), and Intrinsic Distortion Path (IDP) methodologies indicate how this uniqueness can be traced back tothe manganocene’s peculiar electronic structure, mainly,the degenerate ground state and close-lying electronic andspin states.This is the peer-reviewed, authors’ version of the article: Stepanović, S., Zlatar, M., Swart, M.,& Gruden, M. (2019). The Irony of Manganocene: An Interplay between the Jahn-Teller Effect and Close-Lying Electronic and Spin States. Journal of Chemical Information and Modeling, American Chemical Society (ACS), 59(5), 1806-1810. [https://doi.org/10.1021/acs.jcim.8b00870]This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Chemical Information and Modeling, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see [https://doi.org/10.1021/acs.jcim.8b00870]The published version: [http://cer.ihtm.bg.ac.rs/handle/123456789/2894]Supplementary data: [https://cer.ihtm.bg.ac.rs/handle/123456789/4446

Supplementary data for article: Stepanović, S.; Anđelković, L.; Zlatar, M.; Anđelković, K. K.; Gruden-Pavlović, M.; Swart, M. Role of Spin State and Ligand Charge in Coordination Patterns in Complexes of 2,6-Diacetylpyridinebis(Semioxamazide) with 3d-Block Metal Ions: A Density Functional Theory Study. Inorganic Chemistry 2013, 52 (23), 13415–13423. https://doi.org/10.1021/ic401752n

Supporting information for: [https://doi.org/10.1021/ic401752n]Related to published version: [http://cherry.chem.bg.ac.rs/handle/123456789/1448

The role of spin states in the catalytic mechanism of the intra- and extradiol cleavage of catechols by O-2

Iron-dependent enzymes and biomimetic iron complexes can catalyze the ring cleavage of very inert, aromatic compounds. The mechanisms of these transformations and the factors that lead either to extradiol cleavage or intradiol cleavage have not been fully understood. By using density functional theory we have elucidated the mechanism of the catalytic cycle for two biomimetic complexes, and explained the difference in the experimentally obtained products.Supplementary material: [ http://cherry.chem.bg.ac.rs/handle/123456789/2981

Selective Photo-Induced Oxidation with O-2 of a Non-Heme Iron(III) Complex to a Bis(imine-pyridyl)iron(II) Complex

Non-heme iron(II) complexes of pentadentate N4Py (N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) type ligands undergo visible light-driven oxidation to their iron(III) state in the presence of O-2 without ligand degradation. Under mildly basic conditions, however, highly selective base catalyzed ligand degradation with O-2, to form a well-defined pyridyl-imine iron(II) complex and an iron(III) picolinate complex, is accelerated photochemically. Specifically, a pyridyl-CH2 moiety is lost from the ligand, yielding a potentially N4 coordinating ligand containing an imine motif. The involvement of reactive oxygen species other than O-2 is excluded; instead, deprotonation at the benzylic positions to generate an amine radical is proposed as the rate determining step. The selective nature of the transformation holds implications for efforts to increase catalyst robustness through ligand design.Supplementary material: [http://cherry.chem.bg.ac.rs/handle/123456789/2984