Synthesis and Photophysical Properties of Hexabenzocoronene‐Tetrabenzoporphyrin Architectures

Ruppel, Michael; Gazetas, Lampros‐Pascal; Lungerich, Dominik; Jux, Norbert

doi:10.1002/ejoc.202000860

Cited by 9 publications

(5 citation statements)

References 82 publications

(24 reference statements)

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“…The product was isolated as a dark green solid in 81% yield (0.565 g; 0.431 mmol). [48][49][50] Synthesis of 1Pb. In a flame-dried Schlenk tube, Pb(OAc) 2 x3H 2 O (22 mg; 57 µmol, 15 equiv) was dissolved in DMF (1.0 mL) under N 2 and heated to 135 °C for 5 min.…”

Section: Methodsmentioning

confidence: 99%

Time-resolved imaging and analysis of the electron beam-induced formation of an open-cage metallo-azafullerene

et al. 2023

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The bottom-up synthesis of strained hollow cage structures, such as fullerenes, using traditional thermal or photochemical methods remains one of the most challenging tasks in organic chemistry. Here, we demonstrate the synthetic use of an electron beam by in-depth single-molecule atomic resolution time-resolved transmission electron microscopy studies to induce the formation of an elusive doubly-holed fullerene-porphyrin cage structure from a well-defined benzoporphyrin precursor deposited on graphene. Through real-time imaging, we analyze the hybrid's peculiar ability to host up to two Pb atoms and subsequently gain insights into the dynamics of the Pb-Pb binding motif in this exotic metallo-organic cage structure. Through density functional theory calculations and image simulations, we conclude that the much slower secondary electrons, which accumulate in the irradiated area's periphery, can also initiate chemical reactions. Consequently, designing advanced carbon nanostructures by e-beam lithography will depend on the understanding and limitations of molecular radiation chemistry.

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Section: Methodsmentioning

confidence: 99%

Time-resolved imaging and analysis of the electron beam-induced formation of an open-cage metallo-azafullerene

et al. 2023

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Section: Methodsmentioning

confidence: 99%

Cinematographic imaging and analysis of the electron beam-induced formation of an endohedral metalloporphyrin-fullerene hybrid

Hölzel

Lee

Amsharov

et al. 2022

Preprint

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The bottom-up synthesis of strained hollow cage structures, such as fullerenes, using traditional thermal or photochemical methods remains one of the most challenging tasks in organic chemistry. Here, we demonstrate the synthetic use of an electron beam by in-depth single-molecule atomic resolution time-resolved transmission electron microscopy studies to induce the formation of an elusive doubly-holed fullerene-porphyrin cage structure from a well-defined benzoporphyrin precursor deposited on graphene. Through real-time imaging, we analyze the hybrid's peculiar ability to host up to two Pb atoms and subsequently gain insights into the dynamics of the Pb–Pb binding motif in this exotic metallo-organic cage structure. Through density functional theory calculations and image simulations, we conclude that the much slower secondary electrons, which accumulate in the irradiated area's periphery, can also initiate chemical reactions. Consequently, designing advanced carbon nanostructures by e-beam lithography will depend on the understanding and limitations of molecular radiation chemistry.

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“…Although known for decades, , it was only with the development of an efficient synthesis of hexa- peri -hexabenzocoronene (known as HBC) by Müllen and co-workers that HBC-based nanographenes became readily amenable to synthesis. − Early on, in an effort to assess electronic communication between the HBC and porphyrin unit, Jux and co-workers synthesized the first directly linked HBC-porphyrin conjugate . Subsequently, they reported several systems bearing multiple HBC or porphyrin units. − Guldi and co-workers further studied the interactions between HBC-porphyrin conjugates and fullerenes in both noncovalently linked supramolecular complexes and covalent-linked HBC-porphyrin-fullerene conjugates. − Currently, several other nanographene-porphyrin conjugates are known; − however, to our knowledge, introducing a nanographene unit into the core of a porphyrinic framework remains an unmet synthetic challenge.…”

Section: Introductionmentioning

confidence: 99%

Nanographene-Fused Expanded Carbaporphyrin Tweezers

He,

Lee,

Zong

et al. 2023

J. Am. Chem. Soc.

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A nanographene-fused expanded carbaporphyrin (5) and its BF 2 complex (6) were synthesized. Single-crystal X-ray structures revealed that 5 and 6 are connected by two hexa-peri-hexabenzocoronene (HBC) units and two dipyrromethene or BODIPY units, respectively. As prepared, 5 and 6 both show nonaromatic character with figure-of-eight carbaoctaphyrin (1.1.1.0.1.1.1.0) cores and adopt tweezers-like conformations characterized by a partially confined space between the two constituent HBC units. The distance between the HBC centers is >10 Å, while the dihedral angles between the two HBC planes are 30.5 and 35.2°for 5 and 6, respectively. The interactions between 5 and 6 and fullerene C 60 were studied both in organic media and in the solid state. Proton NMR spectral titrations of 5 and 6 with C 60 revealed a 1:1 binding mode for both macrocycles. In toluene-d 8 , the corresponding binding constants were determined to be 1141 ± 17 and 994 ± 10 M −1 for 5 and 6, respectively. Single-crystal X-ray diffraction structural analyses confirmed the formation of 1:1 fullerene inclusion complexes in the solid state. The C 60 guests in both complexes are found within triangular pockets composed of two HBC units from the tweezers-like receptor most closely associated with the bound fullerene, as well as an HBC unit from an adjacent host. Femtosecond transient absorption measurements revealed subpicosecond ultrafast charge separation between 5 (and 6) and C 60 in the complexes. To the best of our knowledge, the present report provides the first example wherein a nanographene building block is incorporated into the core of a porphyrinic framework.

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Synthesis and Photophysical Properties of Hexabenzocoronene‐Tetrabenzoporphyrin Architectures

Cited by 9 publications

References 82 publications

Time-resolved imaging and analysis of the electron beam-induced formation of an open-cage metallo-azafullerene

Time-resolved imaging and analysis of the electron beam-induced formation of an open-cage metallo-azafullerene

Cinematographic imaging and analysis of the electron beam-induced formation of an endohedral metalloporphyrin-fullerene hybrid

Nanographene-Fused Expanded Carbaporphyrin Tweezers

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