Molecular Quantum Rings Formed from a 
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-Conjugated Macrocycle

Judd, Chris J.; Nizovtsev, Anton S.; Plougmann, Rikke; Kondratuk, Dmitry V.; Anderson, Harry L.; Besley, Elena; Saywell, Alex

doi:10.1103/physrevlett.125.206803

Cited by 24 publications

(27 citation statements)

References 41 publications

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“… 1 − 7 Novel porphyrinoid nanostructures have been designed and synthesized by linking the Zn–porphyrins with butadiyne linkers or with larger conjugated bridges. 7 − 14 Similar polycyclic aromatic hydrocarbon (PAH) nanostructures 15 , 16 as well as planar porphyrinoid nanostructures consisting of arrays or sheets of fused porphyrinoid moieties have also been synthesized. 17 − 23 The conjugated nanostructures have appealing topologies with peculiar conjugation pathways, unexpected aromatic character and current-density pathways.…”

Section: Introductionmentioning

confidence: 99%

“… 13 , 24 − 33 The synthesized molecules have been spectroscopically characterized with the aim to understand how the aromatic nature changes when increasing the length of the conjugation pathway. 14 , 34 The synthesis of polycyclic aromatic hydrocarbon (PAH) nanostructures, porphyrinoid nanorings, porphyrinoid nanobelts, and crossing nanorings of porphyrinoids can also be seen as a generalization of the synthesis of carbon nanostructures. 35 , 36 …”

Section: Introductionmentioning

confidence: 99%

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Magnetically Induced Current Densities in Zinc Porphyrin Nanoshells

et al. 2022

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The molecular structures of porphyrinoid cages were obtained by constructing small polyhedral graphs whose vertices have degree-4. The initial structures were then fully optimized at the density functional theory (DFT) level using the generalized gradient approximation. Some of polyhedral vertices were replaced with Zn–porphyrin units and their edges were replaced with ethyne or butadiyne bridges or connected by fusing two neighboring Zn–porphyrin units. Molecule 1 is an ethyne-bridge porphyrinoid nanotube, whose ends are sealed with a Zn–porphyrin. Molecule 2 is the corresponding open porphyrinoid nanotube. Molecule 3 is a clam-like porphyrinoid cage, whose shells consist of fused Zn–porphyrins, and the two halves are connected via butadiyne bridges. Molecule 4 is a cross-belt of fused Zn–porphyrins, and molecule 5 is a cross-belt of Zn–porphyrins connected with butadiyne bridges. The magnetically induced current density of the optimized porphyrinoid cages was calculated for determining the aromatic character, the degree of aromaticity and the current-density pathways. The current-density calculations were performed at the DFT level with the gauge—including magnetically induced currents (GIMIC) method using the B3LYP hybrid functional and def2-SVP basis sets. Calculations of the current densities show that molecule 2 sustains a paratropic ring current around the nanotube, whereas sealing the ends as in molecule 1 leads to an almost nonaromatic nanotube. Fusing porphyrinoids as in molecules 3 and 4 results in complicated current-density pathways that differ from the ones usually appearing in porphyrinoids. The aromatic character of molecules 4 and 5 changes upon oxidation. The neutral molecule 4 is antiaromatic, whereas the dication is nonaromatic. Molecule 5 is nonaromatic, and its dication is aromatic.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Magnetically Induced Current Densities in Zinc Porphyrin Nanoshells

et al. 2022

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“…the shape with interior and exterior sites and the endless π‐conjugation), has attracted intense attention in recent years [2–7] . Synthetic strategies in solution have been developed to produce (shape‐persistent) conjugated macrocycles, which have demonstrated novel catalytic and photophysical properties, and exhibited great potential in applications from drug discovery to organic electronics [8–14] …”

Section: Methodsmentioning

confidence: 99%

On‐Surface Synthesis of Giant Conjugated Macrocycles

Fan

Sun

et al. 2021

Angew Chem Int Ed

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We have achieved an on-surface synthesis of giant conjugated macrocycles having a diameter of % 7 nm and consisting of up to 30 subunits. The synthesis started with a debrominative coupling of the molecular precursors on a hot Ag(111) surface, leading to the formation of arched oligomeric chains and macrocycles. These products were revealed by scanning tunneling microscopy in combination with density functional theory to be covalent oligomers. These intermediates also display C-Ag organometallic bonds between parallel molecular subunits due to site-selective debromination and the asymmetric molecular conformation. Subsequent cyclodehydrogenation at higher temperatures steered the final conjugation of the macrocycles. Our findings provide a novel design strategy toward p-conjugated macrocycles and open up new opportunities for the precise synthesis of organic nanostructures.

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“…[3][4][5][6][7][8] Butadiyne-linked, zinc porphyrin nanorings are synthetic conjugated supramolecular nanosystems with distinctive topologies, such as cyclic (nested) rigid or flexible structures, 9 and have a rich energy level structure, which has been rationalised in terms of Hückel theory. [10][11][12] Their electronic excitations display highly nonlocal character [13][14][15][16] giving them a resemblance to naturally occurring, bacteriochlorophyll-based, systems such as B800 and B850 in LH2, [17][18][19] and as such represent important model systems for the study of exciton dynamics.…”

Section: Introductionmentioning

confidence: 99%