Population and QTAIM Analysis of Metalloporphyrin–Fullerene Supramolecular Complexes

Kolokoltsev, Yevgeniy; Sanders, David P.; Basiuk, Vladimir A.

doi:10.1166/jctn.2015.3785

Cited by 6 publications

(4 citation statements)

References 25 publications

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“…The energy of the porphyrin–fullerene non‐covalent interaction has been calculated by many authors for different porphyrins and by different methods . The results of the calculation depend strongly on the method used.…”

Section: Resultsmentioning

confidence: 99%

Photocurrent in Multilayered Assemblies of Porphyrin–Fullerene Covalent Dyads: Evidence for Channels for Charge Transport

et al. 2016

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Specially designed porphyrin-fullerene dyads have been synthesized to verify literature predictions based on quantum chemistry calculations that certain porphyrin-fullerene dyads are able to self-arrange into specific structures providing channels for charge transport in a bulk mass of organic compound. According to AFM and SEM data, the newly synthesized compounds were indeed prone to some kind of self-arrangement, although to a lesser degree than was expected. A dispersion corrected DFT study of the molecular non-covalent interactions performed at the DFT-D3 (B3LYP, 6-31G*) level of theory showed that the least energy corresponded to head-to-head dimers, with close contacts of porphyrin-porphyrin and fullerene-fullerene fragments, thus providing a unit building block of the channel for charge transport. Experimental proof for the existence of channels for charge transport was obtained by observing a photocurrent in a simple photovoltaic cell.

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Section: Resultsmentioning

confidence: 99%

Photocurrent in Multilayered Assemblies of Porphyrin–Fullerene Covalent Dyads: Evidence for Channels for Charge Transport

et al. 2016

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“…All quantum chemical calculations were performed with the Gaussian suite of programs at uωB97XD/6–311++G(2d,2p) level . Since formation of a H

\dots

O hydrogen bond (HB) precedes formation of a HO covalent bond, we employed ωB97XD functional that is able to properly describe both weak and strong interactions . Presence of species with unpaired electrons required employment of unrestricted methods (uωB97XD).…”

Section: Methodsmentioning

confidence: 99%

Mechanistic insights on how hydroquinone disarms OH and OOH radicals

Nakarada

Petković

2017

Int J of Quantum Chemistry

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Phenol derivatives are distinguished as successful free radical scavengers. We present a detailed analysis of hydroxyl hydrogen abstraction from hydroquinone by hydroxyl and hydroperoxyl radical with emphasis on changes that take place in the vicinity of the transition state. Quantum theory of atoms in molecules is employed to elucidate the sequence of positive and negative charge transfer by studying selected properties of the three key atoms (the transferring hydrogen, the donor atom, and the acceptor atom) along intrinsic reaction path. The presented results imply that in both reactions, which are examples of proton coupled electron transfer, proton, and electron get simultaneously transferred to the radical oxygen atom. The fact that the hydrogen's charge and volume do not monotonously change in the vicinity of the transition state in the product valley results from the adjacency of the proton and the electron to the donor and the acceptor oxygen atoms. Obtaining a detailed understanding of mechanisms by which free radicals are disarmed is of paramount importance given the effects of those highly reactive species on biological systems. A comprehensive analysis of hydroxyl hydrogen abstraction from hydroquinone by hydroxyl and hydroperoxyl radicals, based on changes of selected electronic properties of the three most relevant atoms (hydrogen donor, hydrogen acceptor, and the hydrogen itself), along the reaction coordinate, can be obtained by first-principles calculations. K E Y W O R D S density functional theory, free radical scavenging, hydroquinone, proton coupled electron transfer, quantum theory of atoms in molecules 1 | I N TR ODU C TI ONDue to their ability to cause oxidative stress in living organisms, free radicals are held responsible for aging process. Although certain natural products have antioxidative properties, scientists still search for efficient tools to trap those extremely reactive species. Phenol derivatives are wellknown antioxidants [1,2] that terminate radical chain reactions by donating a hydroxyl hydrogen atom. Hydrogen atom could also be abstracted from either of phenolic CAH bonds, although such processes are characterized with higher energy barrier due to lower acidity of the transferring atom.In addition to hydrogen transfer, free radicals can be blocked through formation of an adduct with the scavenger.Hydrogen transfer can, in principle, proceed via several reaction mechanisms [3][4][5][6] due to the fact that hydrogen atom consists of two entities-a proton and an electron. They can be transferred either simultaneously or separately, and the process might also involve solvent molecules. All those mechanisms are known as formal hydrogen transfer (FHT). [6] (i) If hydrogen transfer takes place in a single elementary step, it can be either hydrogen atom transfer (HAT) when the proton and the electron are transferred from one species to another as one entity, or proton-coupled electron transfer (PCET) if the proton and the electron travel separately between different parts of molec...

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“…Topological analysis of the electron density following the AIM theory was also used to investigate the noncovalent interaction mechanism of MP and fullerene (C 60 ) . According to the sign of the Laplacian of ρ ( ∇ 2 ρ ) calculated, it was found that all the interatomic interactions between fullerene and MP are closed shell interactions.…”

Section: Quantum Chemical Studies and Potential Applicationsmentioning

confidence: 99%

“…The BD is defined as the quotient between the total energy and the electronic density at the BCP; BD = H BCP / ρ BCP . The authors showed that the complexes containing FeP, MnP, and CoP would present transit closed shell interactions because BD < 0 . These interactions are considerably stronger than the pure closed shell ones that are van der Waals.…”

Section: Quantum Chemical Studies and Potential Applicationsmentioning

confidence: 99%

Quantum chemical studies of porphyrin‐ and expanded porphyrin‐based systems and their potential applications in nanoscience. Latin America research review

Cárdenas-Jirón

Borges-Martínez

Mera‐Adasme

et al. 2018

Int J of Quantum Chemistry

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Porphyrins and expanded porphyrins are fascinating molecular structures, and its wide applicability in different fields of the nanoscience has produced an extensive number of scientific publications. The purpose of this article is to review the research performed on porphyrins and expanded porphyrins in the Latin American region at a theoretical level of quantum chemistry using different methodologies available. The present review is organized considering the most important applications that these molecular systems have found. In this way, we classify the reported works in the following fields studied by the nanoscience: molecular electronics, dye‐sensitized solar cells, and photodynamic therapy. Because of its relevance, we also highlight other reports focused on the topological analysis of the electron density and aromaticity. Current investigation on these topics applied to porphyrin‐ and expanded porphyrin‐based systems and the future perspective in this field are presented.

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Population and QTAIM Analysis of Metalloporphyrin–Fullerene Supramolecular Complexes

Cited by 6 publications

References 25 publications

Photocurrent in Multilayered Assemblies of Porphyrin–Fullerene Covalent Dyads: Evidence for Channels for Charge Transport

Photocurrent in Multilayered Assemblies of Porphyrin–Fullerene Covalent Dyads: Evidence for Channels for Charge Transport

Mechanistic insights on how hydroquinone disarms OH and OOH radicals

Quantum chemical studies of porphyrin‐ and expanded porphyrin‐based systems and their potential applications in nanoscience. Latin America research review

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