Metalloporphyrin Molecular Sieves

Goldberg, Israel

doi:10.1002/1521-3765(20001103)6:21<3863::aid-chem3863>3.3.co;2-m

Cited by 144 publications

(135 citation statements)

References 44 publications

(20 reference statements)

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“…A present limitation of porphyrin framework structures as zeolite-like materials is their fragility toward loss of occluded solvent (13,16). Typically, they collapse irreversibly upon total removal of solvent molecules.…”

Section: Discussionmentioning

confidence: 99%

See 1 more Smart Citation

Extending supramolecular fullerene-porphyrin chemistry to pillared metal-organic frameworks

Sun

Tham

Reed

et al. 2002

Proc. Natl. Acad. Sci. U.S.A.

138

121

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Porphyrins and fullerenes are spontaneously attracted to each other. This supramolecular recognition element can be exploited to produce ordered arrays of interleaved porphyrins and fullerenes. C 60⅐H2TpyP⅐Pb(NO3)2⅐1.5TCE (H2TpyP ‫؍‬ tetra-4-pyridylporphyrin; TCE ‫؍‬ 1,1,2,2-tetrachloroethane) crystallizes in the tetragonal P4͞n space group and the structure has been solved to high resolution. The Pb 2؉ ions connect the pyridylporphyrins in infinite sheets with an interlayer spacing of 12.1 Å. The fullerenes are intercalated between these layers, acting as pillars. The 6:6 ring juncture bonds of C 60 are centered over the porphyrins, bringing the layers into strict tetragonal register. This arranagement identifies the fullerene-porphyrin interaction as a structure-defining element. The same motif is seen in a related ribbon structure having C 70 intercalated into HgI 2-linked H2TpyTP. The supramolecular design principles involved in assembling these chromophores may have applications in materials science.

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Section: Discussionmentioning

confidence: 99%

“…The potential of these fragile structures to act like zeolites in separations and catalysis has stimulated intense activity in the synthesis of more robust systems (9)(10)(11)(12)(13)(14)(15)(16)(17), using labile coordinate bonds or H-bonding as the supramolecular recognition elements (18)(19)(20)(21)(22).…”

mentioning

confidence: 99%

Extending supramolecular fullerene-porphyrin chemistry to pillared metal-organic frameworks

Sun

Tham

Reed

et al. 2002

Proc. Natl. Acad. Sci. U.S.A.

138

121

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“…pores with diameters less than 20 Å) framework solids that might serve as heterogeneous catalysts. Since the early 1990s, [2,3,[20][21][22][23][24][25][26][27][28][29][30][31] much work has been done to develop porphyrin framework solids, with more recent contributions from Hupp, Paz, Huang, van der Voort, and others [4,11,19,32]. Many singlecrystal structures of porphyrinic solids contain pores filled with disordered solvates, but very few are stable to the removal of solvates.…”

Section: Introductionmentioning

confidence: 99%

Sorption and catalysis by robust microporous metalloporphyrin framework solids

Smithenry

Wilson

Nakagaki

et al. 2017

J. Porphyrins Phthalocyanines

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ABSTRACT:Two isostructural metalloporphyrin framework solids have been synthesized. Both frameworks contains manganese(III) metal complexes of trans-dicarboxylateporphyrins whose peripheralcarboxylates coordinate the edges of tetrahedral Zn 4 O +6 clusters; the two metalloporphyrins explored are Mn(III) and Co(II). The cubic interpenetrated frameworks have 72% free volume and 4 × 7 Å averaged size pores. The evacuated frameworks are robust and retain a structure open to the sorption of substrates with medium polarity. The manganese porphyrin framework catalyzes the hydroxylation of cyclic and linear alkanes with iodosylbenzene as oxidant in a size-and polarityselective manner. In addition, the catalysis was found to occur within the pores, making this a rare case of porphyrin framework solid with interior catalysis.

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“…19,20 On the other hand, zinc(II) protoporphyrin IX (ZnPP) with hydrophilic carboxyl groups at one side of the molecule was standing-up with respect to the solution surface. 20 The axial coordination behavior of the metalloporphyrin plays an important role in the molecular recognition properties in sensor applications, [21][22][23] the self-assembling of supramolecular structures [24][25][26] and monolayer formations at the air-water interface. 27,28 The surface concentration of bulky metal complexes well-oriented at the air-water interface without selfaggregation or multilayer formation is generally much lower than the metal ions attracted to a condensed surfactant layer.…”

Section: Introductionmentioning

confidence: 99%

Extended X-ray Absorption Fine Structure of Copper(II) Complexes at the Air-Water Interface by a Polarized Total-Reflection X-ray Absorption Technique

et al. 2009

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Copper(II) complexes spread on an aqueous solution surface were studied by a polarized total-reflection X-ray absorption fine structure (TR-XAFS) technique. The polarized TR-XAFS spectra at the Cu-K edge for copper(II) porphyrins and copper(II) chlorophyllin in a monolayer were measured in situ at the air-water interface. The polarization dependences of X-ray absorption near-edge structure (XANES) involving a 1sAE4pz transition allowed us to estimate the molecular orientation and the local coordination structure around the copper(II) atom in the polarization plane selectively. The extended X-ray absorption fine structure (EXAFS) region of the polarized TR-XAFS spectra for the metal complexes present at the air-water interface was successfully analyzed for the first time. The relative coordination number for the copper center evaluated from the EXAFS analysis indicated larger values in the vertical polarization than in the horizontal one, in agreement with the standing-up molecular orientation at the air-water interface estimated from the XANES region.

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Metalloporphyrin Molecular Sieves

Cited by 144 publications

References 44 publications

Extending supramolecular fullerene-porphyrin chemistry to pillared metal-organic frameworks

Extending supramolecular fullerene-porphyrin chemistry to pillared metal-organic frameworks

Sorption and catalysis by robust microporous metalloporphyrin framework solids

Extended X-ray Absorption Fine Structure of Copper(II) Complexes at the Air-Water Interface by a Polarized Total-Reflection X-ray Absorption Technique

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