Central metal ion determined self-assembly of intrinsically chiral porphyrins

Feldborg, Lise N.; Saletra, Wojciech J.; Iavicoli, Patrizia; Amabilino, David B.

doi:10.1142/s108842461100394x

Cited by 12 publications

(11 citation statements)

References 39 publications

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“…[21][22][23] The ability of metalloporphyrins to coordinate with axial ligands containing nitrogen, oxygen or sulfur atoms gives a great variety of self-assembled superstructures, with facility to tune their optical and electronic properties, as is the case of many zinc (II) metalloporphyrins that form stable supramolecules in non-polar media when they self-assemble through coordinating ligands. 24,25 The coordination of zinc porphyrins with axial nitrogen derivative ligands, such as imidazolyl or pyridyl groups afford the formation of well-organized macromolecules in the form of cyclic structures, [26][27][28][29] or linear polymers 30,31 and oligomers. [32][33][34] The coordination between zinc(II) and pyridyl ligands has a relatively large association constant (~10 3 M -1 ) 35,36 and usually does not disturb the photoexcited state of the metalloporphyrin.…”

Section: Introductionmentioning

confidence: 99%

Bottom-Up Hierarchical Self-Assembly of Chiral Porphyrins through Coordination and Hydrogen Bonds

et al. 2015

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A series of chiral synthetic compounds is reported that show intricate but specific hierarchical assembly because of varying positions of coordination and hydrogen bonds. The evolution of the aggregates (followed by absorption spectroscopy and temperature-dependent circular dichroism studies in solution) reveal the influence of the proportion of stereogenic centers in the side groups connected to the chromophore ring in their optical activity and the important role of pyridyl groups in the self-assembly of these chiral macrocycles. The optical activity spans two orders of magnitude depending on composition and constitution. Two of the aggregates show very high optical activity even though the isolated chromophores barely give a circular dichroism signal. Molecular modeling of the aggregates, starting from the pyridine-zinc(II) porphyrin interaction and working up, and calculation of the circular dichroism signal confirm the origin of this optical activity as the chiral supramolecular organization of the molecules. The aggregates show a broad absorption range, between approximately 390 and 475 nm for the transitions associated with the Soret region alone, that spans wavelengths far more than the isolated chromophore. The supramolecular assemblies of the metalloporphyrins in solution were deposited onto highly oriented pyrolitic graphite in order to study their hierarchy in assembly by atomic force microscopy. Zero and one-dimensional aggregates were observed, and a clear dependence on deposition temperature was shown, indicating that the hierarchical assembly took place largely in solution. Moreover, scanning electron microscopy images of porphyrins and metalloporphyrins precipitated under out-ofequilibrium conditions showed the dependence of the number and position of chiral amide groups in the formation of a fibrillar nanomaterial. The combination of coordination and hydrogen bonding in the complicated assembly of these molecules -where there is a clear hierarchy for zinc(II)-pyridyl interaction followed by hydrogen-bonding between amide groups, and then van der Waals interactions -paves the way for the preparation of molecular materials with multiple chromophore environments.

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Section: Introductionmentioning

confidence: 99%

Bottom-Up Hierarchical Self-Assembly of Chiral Porphyrins through Coordination and Hydrogen Bonds

et al. 2015

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“…The organic phase was extracted with CH 2 Cl 2 . Removal of the solvent gave the desired product as a shiny purple solid . Yield: 278 mg (86 %).…”

Section: Methodsmentioning

confidence: 99%

“…Afterwards, the final solution was washed with as aturated aqueous solution of NaHCO 3 ,brine and distilled water.The organic phase was extracted with CH 2 Cl 2 .R emoval of the solvent gave the desired product as a shiny purple solid. [17] Yield:2 78 mg (86 %). Suitable crystals for Xray diffraction analyses of 1a were obtained after few days by dissolving it in a1 :1 mixture of CH 2 Cl 2 and CH 3 Synthesis of [Zn(PPP)] n (2 b):T he procedure was as described for 2a but with H 2 PPP.C rystals of 2b were obtained by following the procedure described for 1b.C rystallographic data were obtained as described below.F urther analyses were unfeasible due to the small amount of crystalline material.…”

Section: Methodsmentioning

confidence: 99%

“…Herein, we unify theset wo ideas towardt he analysiso ft wo Zn porphyrins containing phenoxypropanoate and methyl-2-phenoxyacetate groups( 1 and 2,r espectively)i n the four porphyrin meso positions (Scheme 1). The choice of such entities is relatedt op revious experience with related sys-tems [10,[14][15][16][17] and their anticipated rich molecular recognition capacity and tendency to crystallize.…”

Section: Introductionmentioning

confidence: 99%

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Boosting Self‐Assembly Diversity in the Solid‐State by Chiral/Non‐Chiral Zn^II‐Porphyrin Crystallization

Qian

González‐Campo

Pérez-Rodríguez

et al. 2018

Chemistry A European J

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A chiral Zn porphyrin derivative 1 and its achiral analogue 2 were studied in the solid state. Considering the rich molecular recognition of designed metalloporphyrins 1 and 2 and their tendency to crystallize, they were recrystallized from two solvent mixtures (CH Cl /CH OH and CH Cl /hexane). As a result, four different crystalline arrangements (1 a,b and 2 a,b, from 0D to 2D) were obtained. Solid-state studies were performed on all the species to analyze the role played by chirality, solvent mixtures, and surfaces (mica and HOPG) in the supramolecular arrangements. By means of combinations of solvents and substrates a variety of microsized species was obtained, from vesicles to flower-shaped arrays, including geometrical microcrystals. Overall, the results emphasize the environmental susceptibility of metalloporphyrins and how this feature must be taken into account in their design.

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“…For this purpose, chiral and achiral metalloporphyrins Zn-(R,R,R,R)-1 and Zn-2 were used ( Fig. 1) [36][37][38]. The determination of the coordination between the PS-b-P4VP and the Zn porphyrins, as well as the possible chirality transfer to the supramolecular organization of the BCP with the porphyrinic derivative compounds, will be studied in solution and in solid state by UV-vis absorption spectroscopy (UV-vis), Fluorescence spectroscopy and Circular Dichroism (CD) spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

Supramolecular block copolymers incorporating chiral and achiral chromophores for the bottom-up assembly of nanomaterials

Riba-Moliner

Gonzalez

Amabilino

et al. 2019

J. Porphyrins Phthalocyanines

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The coordination of the chiral metalloporphyrin ([5,10,15,20-[4-([Formula: see text]-2-[Formula: see text]-octadecylamidoethyloxiphenyl]porphyrin] zinc (II)) and an achiral homologue to an amphiphilic block copolymer of poly(styrene-[Formula: see text]-4-vinyl pyridine) (PS-[Formula: see text]-P4VP) have been studied in solution and as cast material. The resulting chiral dye-polymer hybrid material has been accomplished via axial coordination between the zinc (II) metal ion in the core of the porphyrin ring and the pyridyl units of the block-copolymer in a non-coordinative solvent. The supramolecular organization and possible chirality transfer to the hybrid material have been studied in solution by UV-visible absorption spectroscopy, fluorescence spectroscopy, Nuclear Magnetic Resonance and Circular Dichroism. The morphology of the chiral and achiral doped polymers has been studied in solid state by Transmission Electron Microscopy and Atomic Force Microscopy. We show that the nanostructures formed depend greatly upon the nature of the side-chains on the porphyrins, where a chiral group leads to a very homogeneous phase-separated material, perhaps indicating that chiral side groups are useful for the preparation of this type of supramolecular hybrid.

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Central metal ion determined self-assembly of intrinsically chiral porphyrins

Cited by 12 publications

References 39 publications

Bottom-Up Hierarchical Self-Assembly of Chiral Porphyrins through Coordination and Hydrogen Bonds

Bottom-Up Hierarchical Self-Assembly of Chiral Porphyrins through Coordination and Hydrogen Bonds

Boosting Self‐Assembly Diversity in the Solid‐State by Chiral/Non‐Chiral Zn^II‐Porphyrin Crystallization

Supramolecular block copolymers incorporating chiral and achiral chromophores for the bottom-up assembly of nanomaterials

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Central metal ion determined self-assembly of intrinsically chiral porphyrins

Cited by 12 publications

References 39 publications

Bottom-Up Hierarchical Self-Assembly of Chiral Porphyrins through Coordination and Hydrogen Bonds

Bottom-Up Hierarchical Self-Assembly of Chiral Porphyrins through Coordination and Hydrogen Bonds

Boosting Self‐Assembly Diversity in the Solid‐State by Chiral/Non‐Chiral ZnII‐Porphyrin Crystallization

Supramolecular block copolymers incorporating chiral and achiral chromophores for the bottom-up assembly of nanomaterials

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Boosting Self‐Assembly Diversity in the Solid‐State by Chiral/Non‐Chiral Zn^II‐Porphyrin Crystallization