Chirality Enhancement of Porphyrin Supramolecular Assembly Driven by a Template Preorganization Effect

Gaeta, Massimiliano; Raciti, Domenica; Randazzo, Rosalba; Gangemi, Chiara M. A.; Raudino, Antonio; D’Urso, Alessandro; Fragalà, Maria Elena; Purrello, Roberto

doi:10.1002/ange.201806192

Cited by 6 publications

(2 citation statements)

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“…Charged porphyrins as such are water soluble; however, because of their hydrophobic skeleton, they tend to undergo uncontrolled self‐aggregation in water. Several templates, including polyelectrolytes, inorganic molecules and macrocycles have been employed to control the self‐assembly processes.…”

Section: Figurementioning

confidence: 99%

Long‐Range Chiral Induction by a Fully Noncovalent Approach in Supramolecular Porphyrin–Calixarene Assemblies

Gaeta

Sortino

Randazzo

et al. 2020

Chemistry A European J

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Section: Figurementioning

confidence: 99%

Long‐Range Chiral Induction by a Fully Noncovalent Approach in Supramolecular Porphyrin–Calixarene Assemblies

Gaeta

Sortino

Randazzo

et al. 2020

Chemistry A European J

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“…Chiral porphyrin-based architectures can be obtained from either chiral or achiral platforms [ 11 , 15 , 16 , 17 ]. If in the former case the stereochemical course of the self-assembly process is dictated by the chiral functionalities anchored on the periphery of the macrocycle [ 18 , 19 ], in the other, the interaction of achiral monomers with chiral external effectors, such as hydrodynamic directional forces [ 20 , 21 ], magnetic fields [ 22 ], or chiral molecular templates [ 23 , 24 , 25 , 26 , 27 , 28 , 29 ] drives the formation of specific suprastructures with chiroptical properties. The literature has an abundance of examples that use both approaches to constructing chiral porphyrin assemblies, which, taken together, evidence the complexity and the variety of experimental factors determining the supramolecular chirality of the final systems both in solution [ 11 ] and in the solid state [ 30 ].…”

Section: Introductionmentioning

confidence: 99%

The Self-Aggregation of Porphyrins with Multiple Chiral Centers in Organic/Aqueous Media: The Case of Sugar- and Steroid-Porphyrin Conjugates

et al. 2020

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An overview of the solvent-driven aggregation of a series of chiral porphyrin derivatives studied by optical methods (UV/Vis, fluorescence, CD and RLS spectroscopies) is herein reported. The investigated porphyrins are characterized by the presence in the meso-positions of glycol-, steroidal- and glucosteroidal moieties, conferring amphiphilicity and solubility in aqueous media to the primarily hydrophobic porphyrin platform. Aggregation of the macrocycles is driven by a change in bulk solvent composition, forming architectures with supramolecular chirality, steered by the stereogenic centers on the porphyrin peripheral positions. The aggregation behavior and chiroptical properties of the final aggregated species strongly depend on the number and stereogenicity of the ancillary groups that dictate the mutual spatial arrangement of the porphyrin chromophores and their further organization in larger structures, usually detectable by different microscopies, such as AFM and SEM. Kinetic studies are fundamental to understand the aggregation mechanism, which is frequently found to be dependent on the substrate concentration. Additionally, Molecular Mechanics calculations can give insights into the intimate nature of the driving forces governing the self-assembly process. The critical use of these combined methods can shed light on the overall self-assembly process of chirally-functionalized macrocycles, with important implications on the development of chiral porphyrin-based materials.

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Chiral Metal Nanoparticle Superlattices Enabled by Porphyrin‐Based Supramolecular Structures

2021

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Herein, we show that chiral metal nanoparticle superlattices can be produced through coassembly of achiral metal nanoparticles and porphyrin‐based organic molecules. This chirality transfer from molecules to nanoparticle superstructures across three orders of magnitude in length scale is enabled by the hetero chain‐chain van der Waals interactions. As far as we know, these are the first chiral nanoparticle assemblies based on chirality transfer through weak van der Waals forces. The dimensionality of the nanoparticle superlattices (1D chiral chains, 2D chiral sheets (cones), and 3D chiral particles) can be controlled based on a same synthetic chiral porphyrin molecule. Metalation of these porphyrin molecules with zinc cations results in the switching of molecular packing from J‐type to H‐type, which thereby produces 1D chiral nanoparticle chains. Functionalization of these zinc porphyrins with oleylamine can induce the assembly of nanoparticles into 2D chiral nanoparticle sheets.

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Chirality Enhancement of Porphyrin Supramolecular Assembly Driven by a Template Preorganization Effect

Cited by 6 publications

References 50 publications

Long‐Range Chiral Induction by a Fully Noncovalent Approach in Supramolecular Porphyrin–Calixarene Assemblies

Long‐Range Chiral Induction by a Fully Noncovalent Approach in Supramolecular Porphyrin–Calixarene Assemblies

The Self-Aggregation of Porphyrins with Multiple Chiral Centers in Organic/Aqueous Media: The Case of Sugar- and Steroid-Porphyrin Conjugates

Chiral Metal Nanoparticle Superlattices Enabled by Porphyrin‐Based Supramolecular Structures

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