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dc.creatorBaranac-Stojanović, Marija
dc.creatorStojanović, Milovan
dc.date.accessioned2019-04-05
dc.date.available2020-01-15
dc.date.issued2019
dc.identifier.issn1463-9076
dc.identifier.urihttp://cherry.chem.bg.ac.rs/handle/123456789/2863
dc.description.abstractThe effect of two types of dibenzo-fusion of pentalene in the singlet and triplet states on its molecular energies and magnetically induced ring currents was examined via density functional calculations. The isomerization energy decomposition analysis (IEDA) together with the calculated aromaticity indices (NICS(1) zz , HOMA and FLU π ), estimation of resonance energies (RE) and extra cyclic resonance energies (ECRE) via the NBO method, and the NICS-XY-scans revealed that the π-electronic system is the most important factor controlling the molecular energies. The [a,f] topology features greater delocalization, which results in two opposing effects: larger ECRE, but weaker π-bonding. The latter is mainly responsible for the higher energy of [a,f]-dibenzopentalene (DBP) (ΔE iso = 21.7 kcal mol -1 ), with the other effects being σ-orbital and electrostatic interactions. The reversal of energetic stability in the triplet states (ΔE iso = -10.8 kcal mol -1 ) mainly comes from the reduced Pauli repulsion in [a,f]-DBP, which stabilizes the unpaired spin density over the central trimethylenemethane subunit vs. the central pentalene subunit in [a,e]-DBP. Although the [a,e] topology only reduces the diatropic and paratropic currents of the elementary subunits, benzene and pentalene, the [a,f] topology also creates strong global paratropicity involving the benzene rings. Both DBP isomers are characterized by global and smaller semi-global and local diatropic currents in the triplet state.
dc.publisherRoyal Society of Chemistry
dc.relationinfo:eu-repo/grantAgreement/MESTD/Basic Research (BR or ON)/172020/RS//
dc.rightsembargoedAccess
dc.sourcePhysical Chemistry Chemical Physics
dc.subjectCascade carbopalladation reaction
dc.subjectExcited-state aromaticity
dc.subjectChemical-shifts nics
dc.subjectGround-state
dc.subjectElectron delocalization
dc.subjectQuantum contributions
dc.subjectAntiaromaticity
dc.subjectBenzene
dc.subjectRing
dc.subjectDerivatives
dc.titleThe effect of two types of dibenzoannulation of pentalene on molecular energies and magnetically induced currents
dc.typearticle
dc.rights.licenseARR
dcterms.abstractСтојановић, Милован; Баранац-Стојановић, Марија;
dc.citation.volume21
dc.citation.issue6
dc.citation.spage3250
dc.citation.epage3263
dc.identifier.wos000459584900041
dc.identifier.doi10.1039/c8cp07875k
dc.citation.rankM21~
dc.description.otherThis is the peer-reviewed version of the following article: Baranac-Stojanović, M.; Stojanović, M. The Effect of Two Types of Dibenzoannulation of Pentalene on Molecular Energies and Magnetically Induced Currents. Physical Chemistry Chemical Physics 2019, 21 (6), 3250–3263. [https://doi.org/10.1039/c8cp07875k]
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dc.identifier.scopus2-s2.0-85061118631
dc.identifier.fulltexthttp://cherry.chem.bg.ac.rs/bitstream/id/6622/10.1039@C8CP07875K.pdf


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