Aromaticity controls the excited-state properties of host–guest complexes of nanohoops

George, Gibu; Stasyuk, Olga A.; Voityuk, Alexander A.; Stasyuk, Anton J.; Solà, Miquel

doi:10.1039/d2nr04037a

Cited by 12 publications

(37 citation statements)

References 69 publications

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“…Furthermore, it is important to note that the binding energy of 2Y 3 N@C 80 ⊂OPP is significantly larger than that of the 2C 60 @OPP and 2C 70 @OPP systems, indicating that OPP exhibits higher stability in encapsulating C 80 -based metallofullerenes. Apparently, the design of efficient fullerene receptors mainly relies on favorable dispersion interactions in an attempt to maximize the contact surface between the fullerene and the host molecule. − The incorporation of Y 3 N@C 80 into the complex system increases the π–π contact area, thereby enhancing the host–guest interactions. In order to provide more information about the suitability of the OPP cavity, the binding of Y 3 N@C 80 and [11]CPP was calculated and the relative stability of the complexes studied in this work was compared.…”

Section: Resultsmentioning

confidence: 99%

Theoretical Study on a Supramolecular Dimeric Structure Constructed by Metallofullerene Y₃N@C₈₀ and Figure-of-Eight Nanoring

Liu

Zhang

2023

ACS Omega

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A new supramolecular complex with a dimeric structure (2Y3N@C80⊂OPP) constructed by metallofullerene Y3N@I h-C80 and figure-of-eight molecular nanoring of oligoparaphenylene (OPP) was investigated using dispersion-corrected density functional theory (DFT-D3). The interactions between the Y3N@I h-C80 guest and the OPP host were studied theoretically at the B3LYP-D3/6-31G(d)∼SDD level. By analyzing geometric characteristics and host–guest binding energies, it is revealed that the OPP is an ideal host molecule for the Y3N@I h-C80 guest. Typically, the OPP can well induce the orientation of the endohedral Y3N cluster on the plane of nanoring. Meanwhile, the configuration of the dimeric structure demonstrates that OPP presents excellent elastic adaptability and shape flexibility during the encapsulation of Y3N@I h-C80. Highly accurate binding energy suggests that 2Y3N@C80⊂OPP (∼−443.82 kJ mol–1 at the ωB97M-V/def2-QZVPP level of theory) is an extremely stable host–guest complex. Thermodynamic information indicates that the formation of the 2Y3N@C80⊂OPP dimer is thermodynamically spontaneous. Furthermore, electronic property analysis reveals that this dimeric structure has a strong electron-attracting ability. Energy decomposition and real-space function analyses of host–guest interactions reveal the characteristics and nature of the noncovalent interactions in the supramolecules. These results provide theoretical support for the design of new host–guest systems based on metallofullerene and nanoring.

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Section: Resultsmentioning

confidence: 99%

Theoretical Study on a Supramolecular Dimeric Structure Constructed by Metallofullerene Y₃N@C₈₀ and Figure-of-Eight Nanoring

Liu

Zhang

2023

ACS Omega

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“…For the macrocycles with furanylene-acetylene repeat units (with alternating formal 4n and [4n+2] π-electron systems) discussed in the section on Type I-CA, the pronounced differences in the emission properties depending on the ring size indicate Type II-CA for those macrocycles with a formal 4n π-electron system. 52 In a host-guest complex of a fullerene and a macrocycle composed of benzene-fused pyrrolo [3,2-b]pyrrole units with Type II-CA, 70 Baird aromaticity is believed to play a role in rendering the locally excited state at the macrocycle the lowest excited state of the complex. The photoresponsive behaviour of a borole fused with aromatic units may also be explained by Type II-CA.…”

Section: Concealed Antiaromaticity Revealable In Redox Reactions (Typ...mentioning

confidence: 99%

Concealed antiaromaticity

Glöcklhofer

2023

Preprint

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The literature reports numerous molecules claimed to be antiaromatic because of a formal 4n pi-electron system. However, this neglects the actual local aromaticity of the molecules, which often feature multiple subunits with [4n+2] pi-electrons besides the formal 4n pi-electron system. This has led to considerable criticism from those who believe that the term antiaromatic should not be used for any molecule with a formal 4n pi-electron system but should be reserved for truly antiaromatic molecules. To reconcile the different viewpoints, the concept of concealed antiaromaticity is introduced here. Concealed antiaromaticity acknowledges that many molecules claimed to be antiaromatic are not truly antiaromatic, but they can exhibit behaviour under certain conditions that would normally be expected for antiaromatic molecules. Three types of concealed antiaromaticity are distinguished based on the conditions under which the molecules can behave like antiaromatic molecules: concealed antiaromaticity revealable in redox reactions (Type I-CA), upon photoexcitation (Type II-CA), and in intermolecular interactions (Type III-CA). The concept of concealed antiaromaticity will enable the rational design of molecules that show the desirable properties of antiaromatic molecules under the different conditions, with broad applications from organic electronics to supramolecular architectures, while avoiding the low stability of truly antiaromatic molecules.

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“…According to the DFT results obtained with the Tamm‐Dancoff approximation (TDA), such complexes show different behavior upon photoexcitation, depending on the degree of aromaticity of the nanoring. In particular, the electron transfer in [ 4 ] DHPP⊃C 60 occurs from the nanoring to C 60 , while in [ 4 ] PP⊃C 60 the electron transfer from C 60 to [ 4 ] PP is almost barrierless and characterized by ultrafast kinetics [24] …”

Section: Introductionmentioning

confidence: 99%

“…In particular, the electron transfer in [4]DHPP�C 60 occurs from the nanoring to C 60 , while in [4]PP�C 60 the electron transfer from C 60 to [4]PP is almost barrierless and characterized by ultrafast kinetics. [24] In this work, we report a theoretical study of electronic and photoinduced electron transfer (PET) properties of the [4]DHPP �C 60 and [4]DHPP�C 60 complexes. We study in detail how electronic structure of monomeric units of the [4]PP and [4]DHPP nanorings and their mutual orientation affect the ground and excited state properties of inclusion complexes.…”

Section: Introductionmentioning

confidence: 99%

Excited State Processes in Supramolecular Complexes of Cyclic Dibenzopyrrolopyrrole Isomers with C₆₀ Fullerene

George

Stasyuk

Voityuk

et al. 2023

Chemistry A European J

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An approach to modulating the properties of carbon nanorings by incorporating pyrrolo[3,2‐b]pyrrole units is of particular interest due to the combined effect of heteroatom and antiaromatic character on electronic properties. The inclusion of units other than phenylene leads to the formation of stereoisomers. In this work, we computationally study how the spatial orientation of monomeric units in the ring affects the properties of cyclic dibenzopyrrolo[3,2‐b]pyrroles and their complexes with C60 fullerene. For [4]PP and [4]DHPP, the most symmetrical AAAA isomer is the most stable and forms stronger interactions with fullerene than the isomers where one or two monomeric units are flipped, mostly due to less Pauli repulsion. π‐Electron delocalization in the monomeric unit is crucial for directing the electron transfer (from or to nanoring). The energy of excited states with charge transfer depends on the HOMO–LUMO gap, which varies from one stereoisomer to another only for [4]DHPP⊃C60 with aromatic 1,4‐dihydropyrrolo[3,2‐b]pyrrole units. The rates of electron transfer and charge recombination reactions are relatively weakly dependent of the spatial isomerism of nanorings.

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Aromaticity controls the excited-state properties of host–guest complexes of nanohoops

Abstract: π-Conjugated organic molecules have exciting applications, as materials for batteries, solar cells, light emitting diodes, etc. Among these systems, antiaromatic compounds are of particular interest because of their smaller HOMO–LUMO...

Cited by 12 publications

References 69 publications

Theoretical Study on a Supramolecular Dimeric Structure Constructed by Metallofullerene Y₃N@C₈₀ and Figure-of-Eight Nanoring

Theoretical Study on a Supramolecular Dimeric Structure Constructed by Metallofullerene Y₃N@C₈₀ and Figure-of-Eight Nanoring

Concealed antiaromaticity

Excited State Processes in Supramolecular Complexes of Cyclic Dibenzopyrrolopyrrole Isomers with C₆₀ Fullerene

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Aromaticity controls the excited-state properties of host–guest complexes of nanohoops

Abstract: π-Conjugated organic molecules have exciting applications, as materials for batteries, solar cells, light emitting diodes, etc. Among these systems, antiaromatic compounds are of particular interest because of their smaller HOMO–LUMO...

Cited by 12 publications

References 69 publications

Theoretical Study on a Supramolecular Dimeric Structure Constructed by Metallofullerene Y3N@C80 and Figure-of-Eight Nanoring

Theoretical Study on a Supramolecular Dimeric Structure Constructed by Metallofullerene Y3N@C80 and Figure-of-Eight Nanoring

Concealed antiaromaticity

Excited State Processes in Supramolecular Complexes of Cyclic Dibenzopyrrolopyrrole Isomers with C60 Fullerene

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Theoretical Study on a Supramolecular Dimeric Structure Constructed by Metallofullerene Y₃N@C₈₀ and Figure-of-Eight Nanoring

Theoretical Study on a Supramolecular Dimeric Structure Constructed by Metallofullerene Y₃N@C₈₀ and Figure-of-Eight Nanoring

Excited State Processes in Supramolecular Complexes of Cyclic Dibenzopyrrolopyrrole Isomers with C₆₀ Fullerene