Inverted thermochemistry of “norbornadiene–quadricyclane” molecular system inside fullerene nanocages

Sabirov, Denis Sh.; Terentyev, Anton O.; Shepelevich, Igor S.; Булгаков, Р. Г.

doi:10.1016/j.comptc.2014.07.003

Cited by 19 publications

(16 citation statements)

References 70 publications

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“…Previously, we systematically studied the polarizability of fullerene derivatives and stressed its crucial role for chemistry and materials science . For example, it reflects the features of interacting fullerene adducts with irradiation in organic solar cells , and molecular switches or screening atoms and small molecules trapped inside the fullerene cages. , Expectedly, the polarizability of fullerenes was invoked to analyze the chemical properties of these species. This field has been intensively explored, and there are approaches based on the analysis of polarizability ellipsoids of fullerenes, , site-specific polarizabilities associated with the molecular moieties, , and the use of the polarizability of the molecule in total. , Below, we focus on the applications of the minimum-polarizability principle to the fullerene-based systems with astrochemical relevance.…”

Section: Astrochemical Applications Of Polarizabilitymentioning

confidence: 99%

Polarizability in Astrochemical Studies of Complex Carbon-Based Compounds

Sabirov,

Tukhbatullina,

Shepelevich

2022

ACS Earth Space Chem.

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This Review summarizes the grounds and applications of polarizability to the astrochemical studies on carbon-based compounds, including polycyclic aromatic hydrocarbons and fullerenes. Polarizability is useful for the analysis of physicochemical processes (interactions with positrons, molecular collisions, quenching, and dielectric screening) and chemical reactions. The idea of a combined use of minimum-polarizability and minimum-energy principles for searching for novel candidates for interstellar/circumstellar detection is considered. Insights into the astrochemistry of fullerenes and helicenes coming from their polarizability are discussed.

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Section: Astrochemical Applications Of Polarizabilitymentioning

confidence: 99%

Polarizability in Astrochemical Studies of Complex Carbon-Based Compounds

Sabirov,

Tukhbatullina,

Shepelevich

2022

ACS Earth Space Chem.

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“…[199][200][201] In 2007, a monopoledipole interaction approach was applied to study dielectric properties of giant multi-shell carbon nano-onions [202][203][204] and then double-shell C 60 @C 240 nano-onion was studied by DFT in Zope's work. 48 Later, polarizabilities of endofullerenes with encapsulated noble gas atoms, [205][206][207] simple molecules (H 2 O or CH 4 ), 55,208,209 and relatively large hydrocarbons (norbornadiene and quadricyclane) 57 were calculated.…”

Section: Endofullerene Polarizabilitymentioning

confidence: 99%

“…This is observed for DFT-calculated mean polarizability and its depression for NHe@C 60 complex. 212 Such a complex has been synthesized recently 213 and contains the N/He inside, which exist in a free state only in specic conditions. Thus, very high depression (|Da| > a X ) may be due to the stabilization effect of the fullerene on this complex.…”

Section: Endofullerene Polarizabilitymentioning

confidence: 99%

Polarizability as a landmark property for fullerene chemistry and materials science

Sabirov

2014

RSC Adv.

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“…The latter is formed in a photochemical intramolecular cycloaddition from NBD (see Figure a). This system has been proposed to hold great potential for solar energy harvesting and storage already half a century ago. − Recently, it has attracted renewed attention − also inspired by the idea that the energy release could not only be triggered catalytically but also electrochemically, thereby enabling the development of a “energy storing solar cell” …”

Section: Introductionmentioning

confidence: 99%

Anchoring of a Carboxyl-Functionalized Norbornadiene Derivative to an Atomically Defined Cobalt Oxide Surface

Schwarz

Mohr

et al. 2017

J. Phys. Chem. C

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We have investigated the anchoring of the molecular energy carrier norbornadiene (NBD) to an atomically defined oxide surface. To this end, we synthesized a carboxyl-functionalized NBD derivative, namely 1-(2′-norbornadienyl)pentanoic acid (NBDA), and deposited it by physical vapor deposition (PVD) under ultrahigh vacuum (UHV) conditions onto a well-ordered Co3O4(111) film grown on Ir(100). In addition, we performed a comparative growth study with benzoic acid (BA) under identical conditions which was used as a reference. The interaction and orientation of NBDA and BA with the oxide surface were monitored in situ during film growth by isothermal time-resolved infrared reflection–absorption spectroscopy (TR-IRAS), both below and above the multilayer desorption temperature. The thermal behavior and stability of the films were investigated by temperature-programmed IRAS (TP-IRAS), with help of density functional (DF) calculations. BA binds to Co3O4(111) under formation of a symmetric chelating carboxylate with the molecular plane oriented nearly perpendicular to the surface. At low temperature (130 K), intact BA physisorbs in form of dimers on top of the saturated monolayer. Upon annealing to 155 K, a reordering transition is observed, in which BA in the multilayer adopts a more flat-lying orientation. The BA multilayer desorbs at 220 K, whereas the surface-anchored BA monolayer is stable up to 400 K. At higher temperature (400–550 K), desorption and decomposition are observed. Very similar to BA, NBDA binds to Co3O4(111) by formation of a symmetric chelating carboxylate. In the multilayer, which desorbs at 240 K, hydrogen-bonded NBDA dimers are formed. Upon PVD of NBDA at 300 K, only a surface anchored carboxylate is stable. The anchored NBDA film shows a characteristic restructuring behavior as a function of coverage. At low coverage the NBDA, adopts a flat-lying structure in which the norbornadiene unit interacts with the Co3O4 surface. With increasing coverage, the norbornadiene units detach from the oxide and the NBDA adopts an upright-standing orientation. Similar to BA, the anchored film is stable up to 400 K and decomposes in the temperature region between 400 and 550 K, leaving behind hydrocarbon residues on the oxide surface.

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Inverted thermochemistry of “norbornadiene–quadricyclane” molecular system inside fullerene nanocages

Cited by 19 publications

References 70 publications

Polarizability in Astrochemical Studies of Complex Carbon-Based Compounds

Polarizability in Astrochemical Studies of Complex Carbon-Based Compounds

Polarizability as a landmark property for fullerene chemistry and materials science

Anchoring of a Carboxyl-Functionalized Norbornadiene Derivative to an Atomically Defined Cobalt Oxide Surface

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