Self‐Organization of Polar Porphyrinoids

Babu, Sukumaran Santhosh; Bonifazi, Davide

doi:10.1002/cplu.201402047

Cited by 28 publications

(27 citation statements)

References 102 publications

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“…Such a solvent‐assisted molecular assembly of l ‐/ d ‐phenylalanine amide allowed us to fabricate various nanostructures, suggesting that the polarity of the solvent plays an important role. This was similar to previously observed controlled nanomorphologies of porphyrin and other derivatives . In addition, the presence of the l ‐/ d ‐phenylalanine group in 1 and 2 favors the induction of chirality in the molecule as shown by CD spectroscopy in Figure and the SEM results, showing twisted needles and thread‐like nanostructures which support chirality.…”

Section: Resultssupporting

confidence: 90%

Solvent‐Tuned Self‐Assembled Nanostructures of Chiral l/d‐Phenylalanine Derivatives of Protoporphyrin IX

et al. 2015

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Protoporphyrin IX is a naturally occurring amphiphilic porphyrin with a rigid hydrophobic nonpolar core and two polar propionic acid substitutions on the porphyrin ring. This molecule can be modified on the hydrophilic group, which can lead to strengthened π–π-stacking and spontaneous self-assembly into novel nanostructures. Herein, we use l- phenylalanine and d-phenylalanine to modify protoporphyrin IX, and use the two derivatives for solvophobic-controlled self-assembly. Both derivatives possess two important features: 1) the aromatic core of the porphyrin for dispersive interactions and 2) a chiral amino acid to maximize the influence of chirality on selfassembly. These derivatives lead to the formation of a variety of nanostructure morphologies, such as spheres, nanofibers, lamellar structures, and thread-like and spherical shells. Solution-based self-assembly was determined by UV/Vis, fluorescence, and circular dichroism spectroscopy, and the formed nanostructures were characterized by scanning electron microscopy (SEM). Such engineered porphyrin derivatives could have potential applications in energy transport and storage, supramolecular chemistry, materials science, and medicine.

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Section: Resultssupporting

confidence: 90%

Solvent‐Tuned Self‐Assembled Nanostructures of Chiral l/d‐Phenylalanine Derivatives of Protoporphyrin IX

et al. 2015

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“…The general influence of fluorinated alcohols (for example 1,1,1,3,3,HFIP,o r2 ,2 , on protein folding has been apointofstudy by various research groups over the last 60 years. [26] Their exceptional ability to induce and stabilizet he formation of a-helical structures in even short peptides could be potentially utilized to alter the hydrogen-bonding arrangementi nb is(amido-corroles).…”

Section: Nuclearmagnetic-resonance Studymentioning

confidence: 99%

“…[1] During recent years, many examples of non-discrete porphyrin-based aggregates, formed throughh ydrogen bonding, p-stacking, metal-ligand, or hydrophobic interactionsh ave been proposed for this purpose. [2,3] Corroles [4][5][6][7] are younger and less symmetrical analogues of porphyrins, af eature which is reflected in am arkedly lowera ctivity in the study of their self-assembly processes. Some noteworthy instances of self-assembling corroles [8] include octabromoc orroles, [9] corroles bearing PO(OH) 2 functionalities, [10] amphiphilic corrole-sodium salts, [11] alongw ith corrole amino acid conjugates.…”

Section: Introductionmentioning

confidence: 99%

Covalently Linked Bis(Amido‐Corroles): Inter‐ and Intramolecular Hydrogen‐Bond‐Driven Supramolecular Assembly

Orłowski

Cichowicz

Staszewska‐Krajewska

et al. 2019

Chemistry A European J

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Four bis‐corroles linked by diamide bridges were synthesized through peptide‐type coupling of a trans‐A2B‐corrole acid with aliphatic and aromatic diamines. In the solid state, the hydrogen‐bond pattern in these bis‐corroles is strongly affected by the type of solvent used in the crystallization process. Although intramolecular hydrogen bonds play a decisive role, they are supported by intermolecular hydrogen bonds and weak N−H⋅⋅⋅π interactions between molecules of toluene and the corrole cores. In an analogy to mono(amido‐corroles), both in crystalline state and in solutions, the aliphatic or aromatic bridge is located directly above the corrole ring. When either ethylenediamine or 2,3‐diaminonaphthalene are used as linkers, incorporation of polar solvents into the crystalline lattice causes a roughly parallel orientation of the corrole rings. At the same time, both NHCO⋅⋅⋅NH corrole hydrogen bonds are intramolecular. In contrast, solvation in toluene causes a distortion with one of the hydrogen bonds being intermolecular. Interestingly, intramolecular hydrogen bonds are always formed between the –NHCO– functionality located further from the benzene ring present at the position 10‐meso. In solution, the hydrogen‐bonds pattern of the bis(amido‐corroles) is strongly affected by the type of the solvent. Compared with toluene (strongly high‐field shifted signals), DMSO and pyridine disrupt self‐assembly, whereas hexafluoroisopropanol strengthens intramolecular hydrogen bonds.

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“…[45,46] In this work, we demonstrate the basic working principle on the prototypal tasks of finding diverse sets of dimers of urea, [47,48] porphin (see Fig. 1 for the structure), [20,49,50] and benzene [51][52][53][54] (see Supporting Information for benzene dimers) and we compare our results to aggregate structures known from the literature. In the case of porphin, we discuss the dependence of the UV-vis absorption spectra on the actual aggregate geometries in detail.…”

Section: Introductionmentioning

confidence: 99%

A program for automatically predicting supramolecular aggregates and its application to urea and porphin

et al. 2018

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Not only the molecular structure but also the presence or absence of aggregates determines many properties of organic materials. Theoretical investigation of such aggregates requires the prediction of a suitable set of diverse structures. Here, we present the open-source program EnergyScan for the unbiased prediction of geometrically diverse sets of small aggregates. Its bottom-up approach is complementary to existing ones by performing a detailed scan of an aggregate's potential energy surface, from which diverse local energy minima are selected. We crossvalidate this approach by predicting both literature-known and heretofore unreported geometries of the urea dimer. We also predict a diverse set of dimers of the less intensely studied case of porphin, which we investigate further using quantum chemistry. For several dimers, we find strong deviations from a reference absorption spectrum, which we explain using computed transition densities. This proof of principle clearly shows that EnergyScan successfully predicts aggregates exhibiting large structural and spectral diversity. © 2018 Wiley Periodicals, Inc.

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Self‐Organization of Polar Porphyrinoids

Cited by 28 publications

References 102 publications

Solvent‐Tuned Self‐Assembled Nanostructures of Chiral l/d‐Phenylalanine Derivatives of Protoporphyrin IX

Solvent‐Tuned Self‐Assembled Nanostructures of Chiral l/d‐Phenylalanine Derivatives of Protoporphyrin IX

Covalently Linked Bis(Amido‐Corroles): Inter‐ and Intramolecular Hydrogen‐Bond‐Driven Supramolecular Assembly

A program for automatically predicting supramolecular aggregates and its application to urea and porphin

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