A Fully Conjugated Planar Heterocyclic [9]Circulene

Pedersen, Stephan K.; Eriksen, Kristina; Ågren, Hans; Minaev, B. F.; Karaush-Karmazin, Nataliya; Hammerich, Ole; Baryshnikov, Gleb V.; Pittelkow, Michael

doi:10.1021/jacs.0c05898

Cited by 33 publications

(28 citation statements)

References 43 publications

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“…The structure of [9]circulene's macrocyclic core is perfectly planar, while tetrahydro [10]circulene adopts a V-shaped cis form with unilaterally directed hydrogen atoms on four bridging sp 3 carbon atoms. The angle between the mean plane of the two carbazoles is 73.7° [99]. According to the ACID plots of [9]circulene 51, the diatropic ring currents appear in the outer rim (blue arrows in Figure 18), while the 9-membered hub ring sustains paratropic currents (red arrows in Figure 18) similar to those of the hetero [8]circulenes presented above.…”

Section: Heterocyclic[9]-and [10]circulenesmentioning

confidence: 63%

“…Until recently, the synthetic efforts of heterocyclic [n]circulenes covered up to eight aromatic rings (n = 8), while the higher hetero[n]circulenes (n > 8) have been predicted only by quantum chemical modeling [95,97]. In 2020, the first synthesis of a fully aromatic [9]circulene, formally a diazatrioxa [9]circulene 51, along with a tetrahydrodiazatetraoxa [10]circulene 52, was reported by Pittelkow's group (Figure 17) [99]. The structure of [9]circulene's macrocyclic core is perfectly planar, while tetrahydro [10]circulene adopts a V-shaped cis form with unilaterally directed hydrogen atoms on four bridging sp 3 According to the ACID plots of [9]circulene 51, the diatropic ring currents appear in the outer rim (blue arrows in Figure 18), while the 9-membered hub ring sustains paratropic currents (red arrows in Figure 18) similar to those of the hetero [8]circulenes presented above.…”

Section: Heterocyclic[9]-and [10]circulenesmentioning

confidence: 99%

“…ACID plots. Blue arrows-local diatropic currents, red arrows-paratropic currents.The NICS(0) (top number) and NICS(1) (bottom number in italics) indices in the[9]circulene and[10]circulene calculated by the GIAO/B3LYP/6-311++G(d,p) method[99].…”

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confidence: 99%

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Aromaticity of Heterocirculenes

2021

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This review summarizes the results on the aromaticity of a series of synthesized and hypothetical neutral heterocirculene molecules and their double charged ions. The aromaticity of heterocirculenes is a direct reflection of their electronic structure responsible for the specific optoelectronic and photophysical properties. We show how the presence of a heteroatom in the outer macrocycle affects the aromaticity of hetero[8]circulenes. In addition, we also describe the change in aromaticity and strain energy for a series of the “lower” (n < 8) and “higher” (n > 8) hetero[n]circulenes. It was demonstrated that the loss of planarity with increased strain leads to an increased antiaromaticity of the lower hetero[n]circulenes, whereas higher hetero[n]circulenes demonstrate a more pronounced aromatic nature because of the small departure from planarity of each heteroarene ring in hetero[n]circulene molecule. Finally, we discuss the aromatic nature of the first examples of π-extended hetero[8]circulenes.

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Section: Heterocyclic[9]-and [10]circulenesmentioning

confidence: 63%

Section: Heterocyclic[9]-and [10]circulenesmentioning

confidence: 99%

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Aromaticity of Heterocirculenes

2021

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“…Advances in the synthesis and quantum chemical simulations of heterocirculenes are summarized in reviews [11][12][13][14]. In 2020, the first synthesis of a fully aromatic [9]circulene, formally a diazatrioxa [9]circulene, along with a tetrahydro-diazatetraoxa [10]circulene was reported by the Pittelkow's group (Figure 1) [15].…”

Section: Introductionmentioning

confidence: 99%

Crystal structure and Hirshfeld surfaces analysis of Heterocyclic-and circulenes

2022

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The crystal structure of the new diazatrioxa[9]circulene and tetrahydro-diazatetraoxa[10]circulene which represent the first synthesized representatives of “higher” hetero[n]circulenes with n>8, was analyzed in details. Hirshfeld surface analyses, the dnorm surfaces and two-dimensional fingerprint plots were used to verify the contributions of the different intermolecular interactions within the crystal structure of diazatrioxa[9]circulene and tetrahydro-diazatetraoxa[10]circulene. The Hirshfeld surface analysis of the crystal structure clarifies that the most important contribution for crystal packing is from H∙∙∙H and C∙∙∙H intermolecular interactions for both circulenes. The shape-index surface shows that in the case of diazatrioxa[9]circulene two sides of the molecules are involved with the same contacts in neighbouring molecules and curvedness plots show flat surface patches that are characteristic of planar stacking. Such face-to-face structural organization provides the main charge transfer pathway in [9]circulene. In the case of [10]circulene, the area involved in the same contacts is much less, however, two types of intermolecular packing modes can form such flat surface patches at curvedness plots which is useful for more efficient charge transfer.

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“…In contrast, most of hetero[8]circulenes have been shown to be planar, thus representing for a new kind of 2D materials with tunable functions and properties [7,8] . Very recently, hetero[9]circulene containing two pyrrole and three furan units has been reported to be a planar molecule as well [9] . Despite such developments, the synthetic strategy to address hetero[n]circulene analogues has been limited.…”

Section: Introductionmentioning

confidence: 99%

Improved Synthesis of ortho‐Phenylene‐bridged Cyclic Tetrapyrroles and Oxidative Fusion Reactions Toward Substituted Tetraaza[8]circulenes

Morimoto

Chen

Matsuo

et al. 2021

Chemistry An Asian Journal

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Hetero[8]circulenes have emerged as novel functionalized heteronanographenes that show various promising functions such as bright fluorescence, charge transporting, and redox reactivities. One of the effective synthetic strategy is the fold‐in type oxidative fusion reaction of ortho‐phenylene‐bridged cyclic tetrapyrroles, whose construction, however, is not well‐sophisticated in terms of reproducibility and possibility for versatile derivatization. In this paper, a “reverse” coupling strategy has been developed, which enabled synthesis of opp‐type low symmetric analogues of cyclic tetrapyrroles. Oxidative fusion reaction conditions to afford tetraaza[8]circulenes have also been reinvestigated and improved. Substituent effects of cyclic tetrapyrroles and tetrabenzotetraaza[8]circulenes are studied for solid‐state structures and packing structures, redox potentials, and optical properties.

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A Fully Conjugated Planar Heterocyclic [9]Circulene

Cited by 33 publications

References 43 publications

Aromaticity of Heterocirculenes

Aromaticity of Heterocirculenes

Crystal structure and Hirshfeld surfaces analysis of Heterocyclic-and circulenes

Improved Synthesis of ortho‐Phenylene‐bridged Cyclic Tetrapyrroles and Oxidative Fusion Reactions Toward Substituted Tetraaza[8]circulenes

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