Cyclopentadienylruthenium π Complexes of Subphthalocyanines: A “Drop‐Pin” Approach To Modifying the Electronic Features of Aromatic Macrocycles

Caballero, Esmeralda; Fernández-Ariza, Javier; Lynch, Vincent M.; Romero‐Nieto, Carlos; Rodríguez‐Morgade, M. Salomé; Sessler, Jonathan L.; Guldi, Dirk M.; Torres, Tomás

doi:10.1002/anie.201206111

Cited by 46 publications

(61 citation statements)

References 42 publications

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“…Taking into account the SubPz cone-shape, restricted rotation of the peripheral substituents would split each signal in two. [11,12] The same conclusion can be inferred from the 1 H NMR spectra of all the other hexaaryl-SubPzs 2 b-g ( Figure S4 a-S9 a in the Supporting Information).…”

Section: Introductionsupporting

confidence: 70%

Peripheral Arylation of Subporphyrazines

Higashino

Rodríguez‐Morgade

Osuka

et al. 2013

Chemistry A European J

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Peripherally hexaarylated subporphyrazines (SubPzs) have been prepared through a Pd-catalyzed, CuTC-mediated coupling of a hexaethylsulfanylated subporphyrazine with arylboronic acids. The introduced aryl substituents strongly influence the electronic properties of the subporphyrazine through effective conjugative interaction. Aryl rings endowed with π-electron-donating groups at the para positions produce a remarkable perturbation of the electron density of the SubPz macrocycle. This is reflected through significant redshifts of the SubPz CT and Q-bands, together with increase of the molar absorptivity of the former, with respect to those exhibited by the hexaphenyl-SubPz 2 a. Moreover, the trend in the first SubPz reduction potentials correlates with the Hammett constants (σp ) corresponding to the para substituents of the aryl. The domed, extended SubPz π-system self-assembles in the solid state to form a dimeric capsule that houses a solvent molecule.

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Section: Introductionsupporting

confidence: 70%

Peripheral Arylation of Subporphyrazines

Higashino

Rodríguez‐Morgade

Osuka

et al. 2013

Chemistry A European J

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“…Angewandte Zuschriften 2 www.angewandte.de hydrogen atoms indicated a more significant shielding effect of the diatropic ring current on the endo side than on the exo side. Such an effect was also suggested by Torres and coworkers and by us upon comparison of the chemical shifts of hydrogen atoms residing on the endo and exo sides of the SubPc units in the pentamethylcyclopentadienylruthenium complex of SubPcs [13] and a core-modified SubPc analogue. [14] However, dynamic molecular motions of the probing moieties are inherent to these systems, such as rotation of the Cp* ligand.…”

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confidence: 72%

Cyclophanes Containing Bowl‐Shaped Aromatic Chromophores: Three Isomers of anti‐[2.2](1,4)Subphthalocyaninophane

2015

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The connection of bowl-shaped aromatic boron subphthalocyanines with anti-[2.2]paracyclophane resulted in the first observation of electronic communication between convex and concave surfaces. Three isomers of anti-[2.2]-(1,4)subphthalocyaninophane, described as concave-concave (CC), convex-concave (CV), and convex-convex (VV) according to the orientation of the subphthalocyanine units, were synthesized and characterized by various spectroscopic techniques, including 1 H NMR, electronic absorption, fluorescence, and magnetic circular dichroism spectroscopy and Xray crystallography, together with molecular-orbital calculations. On going from the CC system to CV and further to VV, the Q band broadened and finally split as a result of throughspace expansion of the conjugated systems, which were also reproduced theoretically.

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“…They demonstrated differences in electron-transfer abilities and ringcurrent effects between the convex and concave surfaces. [14,15] Herein, we present a novel approach to a highly distorted SubPc analogue. Not only does this analogue have unique properties, but we were also able to investigate its convex and concave conjugated surfaces.…”

mentioning

confidence: 99%

A Core‐Expanded Subphthalocyanine Analogue with a Significantly Distorted Conjugated Surface and Unprecedented Properties

et al. 2014

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The introduction of a seven-membered-ring unit in the place of a five-membered-ring unit in the structure of subphthalocyanine resulted in significant distortion of the bowl-shaped structure of the conjugated molecule as well as the following unprecedented properties: the preferential formation of the axially fluoro substituted species, the fluttering-dynamic-motion-induced rapid exchange of P and M enantiomers, markedly split Q-band absorption, and a clear difference in the ring-current effects arising from the convex and concave surfaces.

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Cyclopentadienylruthenium π Complexes of Subphthalocyanines: A “Drop‐Pin” Approach To Modifying the Electronic Features of Aromatic Macrocycles

Cited by 46 publications

References 42 publications

Peripheral Arylation of Subporphyrazines

Peripheral Arylation of Subporphyrazines

Cyclophanes Containing Bowl‐Shaped Aromatic Chromophores: Three Isomers of anti‐[2.2](1,4)Subphthalocyaninophane

A Core‐Expanded Subphthalocyanine Analogue with a Significantly Distorted Conjugated Surface and Unprecedented Properties

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