Calixarene–Porphyrin Supramolecular Complexes: pH-Tuning of the Complex Stoichiometry

Costanzo, L. Di; Geremia, Silvano; Randaccio, Lucio; Purrello, Roberto; Lauceri, Rosaria; Sciotto, Domenico; Gulino, Fabio Giuseppe; Pavone, Vincenzo

doi:10.1002/1521-3773(20011119)40:22<4245::aid-anie4245>3.3.co;2-r

Cited by 19 publications

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“…The structural disorder and low occupancy of the water molecules is consistent with the drying behavior noted for the porphyrin nanosheets and other crystal structures of porphyrin ions. [16][17][18][19][20][21] Further details of the X-ray structure methods, refinement procedure (Table S1), and bond distances (Table S2) are given in the ESI. † Fig.…”

Section: Resultsmentioning

confidence: 99%

Binary ionic porphyrin nanosheets: electronic and light-harvesting properties regulated by crystal structure

et al. 2012

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Crystalline solids self-assembled from anionic and cationic porphyrins provide a new class of multifunctional optoelectronic micro- and nanomaterials. A 1 : 1 combination of zinc(II) tetra(4-sulfonatophenyl)porphyrin (ZnTPPS) and tin(IV) tetra(N-methyl-4-pyridiniumyl)porphyrin (SnTNMePyP) gives porphyrin nanosheets with high aspect ratios and varying thickness. The room temperature preparation of the nanosheets has provided the first X-ray crystal structure of a cooperative binary ionic (CBI) solid. The unit cell contains one and one-half molecules of aquo-ZnTPPS(4-) (an electron donor) and three half molecules of dihydroxy-SnTNMePyP(4+) (an electron acceptor). Charge balance in the solid is reached without any non-porphyrinic ions, as previously determined for other CBI nanomaterials by non-crystallographic means. The crystal structure reveals a complicated molecular arrangement with slipped π-π stacking only occurring in isolated dimers of one of the symmetrically unique zinc porphyrins. Consistent with the crystal structure, UV-visible J-aggregate bands indicative of exciton delocalization and extended π-π stacking are not observed. XRD measurements show that the structure of the Zn/Sn nanosheets is distinct from that of Zn/Sn four-leaf clover-like CBI solids reported previously. In contrast with the Zn/Sn clovers that do exhibit J-aggregate bands and are photoconductive, the nanosheets are not photoconductive. Even so, the nanosheets act as light-harvesting structures in an artificial photosynthesis system capable of reducing water to hydrogen but not as efficiently as the Zn/Sn clovers.

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Section: Resultsmentioning

confidence: 99%

Binary ionic porphyrin nanosheets: electronic and light-harvesting properties regulated by crystal structure

et al. 2012

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“…During the last few years, the possibility of using organic materials deposited as thin films on solid substrates has been investigated. 1,4,5 Molecules such as phthalocyanines 6 or porphyrins 7 operate as active elements because of their highly conjugated p systems, and therefore the gas-porphyrin interaction can be optically monitored. 8 However, in order to ensure the applicability of this system to atmospheric environmental pollution measurements or industrial emission studies, lower gas concentrations need to be detected, and a better stability of the response at higher temperatures may be necessary.…”

Section: Introductionmentioning

confidence: 99%

Improvement of optical gas sensing using LB films containing a water insoluble porphyrin organized in a calixarene matrix

et al. 2007

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A water insoluble porphyrin 5,10,15,20-tetrakis[3,4-bis(2-ethylhexyloxy)phenyl]-21H,23H-porphine (EHO) that is highly sensitive to low concentrations of NO 2 in nitrogen has been organized at the air-water interface using a host calix[8]arene (C8A) matrix. Different composition ratios of C8A have been studied at the air-water interface to select the optimal composition for obtaining a less aggregated porphyrin in the mixed films. An understanding of the interaction between EHO and C8A has been provided by means of a miscibility study. Mixed monolayers do not follow the additivity rule and the negative deviation from it depends on the molar fraction of the porphyrin in the mixture. Surface pressure-area (p-A) plots expressed per C8A molecule indicate the presence of the porphyrin at the air-water interface at low surface pressure while under further compression the hydrophobic EHO segregates above the C8A matrix. Brewster angle microscopy images of the mixed C8A : EHO monolayers show that the distribution of the EHO molecules at the air-water interface in the C8A matrix is more homogeneous than that observed for the pure EHO monolayer. The reflection spectra reveal the EHO aggregation in the mixed monolayers, although the C8A matrix in those films modifies such aggregation. The effect of the new organization for the EHO molecules in the mixed films is clearly manifested by the enhancement of response (faster), reproducibility (higher), sensitivity (higher) and temperature (wide range, being interesting for industrial applications) during exposure to NO 2 , in comparison with those results previously obtained for the pure EHO film.

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“…Charged water‐soluble calix[ n ]arene derivatives, owing to the cooperative effect of electrostatic forces and the intrinsic solvophobic nature of their cavities, show robust binding interactions towards species with oppositely charged moieties . As a result, calix[ n ]arenes have been successfully employed as templating agents able to drive the assembly of porphyrins in aqueous media, resulting in hierarchical noncovalent supramolecular systems with: i) an exact and tunable stoichiometry, ii) a defined dimensionality and iii) a controlled chirality . The stability and kinetic inertness of these discrete (and non‐interconvertible) supramolecular complexes has also been confirmed by XRD, diffusion NMR studies and dynamic light‐scattering experiments …”

Section: Figurementioning

confidence: 99%

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

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et al. 2020

Chemistry A European J

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Calixarene–Porphyrin Supramolecular Complexes: pH-Tuning of the Complex Stoichiometry

Cited by 19 publications

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Binary ionic porphyrin nanosheets: electronic and light-harvesting properties regulated by crystal structure

Binary ionic porphyrin nanosheets: electronic and light-harvesting properties regulated by crystal structure

Improvement of optical gas sensing using LB films containing a water insoluble porphyrin organized in a calixarene matrix

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

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