Cocrystallization of binuclear iron(III) porphyrins with C60: Bending of μ-O{FeIII(octaethylporphyrin)} and the first structure of the iron(III) octaethyloxophlorin dimer

Hon Man Lee, Marilyn M. Olmstead, Garrett G. Gross, Alan L. Balch

Research output: Contribution to journalArticle

53 Citations (Scopus)

Abstract

Black crystals of C60·μ-O{FeIII(OEP)} 2·C6H6 and 2C60· {FeIII(OEPO)}2·4C6H6 suitable for single-crystal X-ray diffraction studies have been obtained by growth from benzene solutions of the appropriate binuclear metalloporphyrin and the fullerene. C60·μ-O{FeIII(OEP)} 2·C6H6 crystallizes with two molecules of μ-O{FeIII(OEP)}2, two fully ordered molecules of C60, and two molecules of benzene in the asymmetric unit. Each independent molecule of μ-O{FeIII(OEP)}2 makes close contact with two fullerene molecules. In C60·μ-O{Fe III(OEP)}2·C6H6 the Fe-O-Fe angles (150.18(11)° and 151.89(11)°) are markedly bent with a benzene molecule wedged into the opening between the two porphyrins, whereas in the triclinic and monoclinic polymorphs of μ-O{FeIII(OEP)} 2 the Fe-O-Fe angles are more nearly linear (172.16(17)° and 176.2(2)°, respectively). The structure of 2C60·{Fe III(OEPO)}2·4C6H6 consists of a centrosymmetric {FeIII(OEPO)}2 molecule in which the two macrocycles are connected to one another through axial coordination of the meso-oxygen atoms to iron ions in the neighboring porphyrin. Each molecule of {FeIII-(OEPO)}2 engages a fullerene on its two exposed faces. The basic geometry of the central core of {FeIII(OEPO)} 2 is similar to that of the previously characterized {In III(OEPO)}2, but the distortion of the two macrocycles is greater in the former due to the shorter Fe-N and Fe-O bonds.

Original languageEnglish
Pages (from-to)691-697
Number of pages7
JournalCrystal Growth and Design
Volume3
Issue number5
DOIs
Publication statusPublished - 2003 Sep 1

Fingerprint

Porphyrins
porphyrins
Dimers
Iron
dimers
iron
Molecules
Fullerenes
molecules
Benzene
fullerenes
benzene
Metalloporphyrins
octaethyloxophlorin
octaethylporphyrin
Polymorphism
oxygen atoms
Single crystals
Ions
Oxygen

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

Cite this

@article{4862a5e4f2004c38b4c5bdb41f0dd3b8,
title = "Cocrystallization of binuclear iron(III) porphyrins with C60: Bending of μ-O{FeIII(octaethylporphyrin)} and the first structure of the iron(III) octaethyloxophlorin dimer",
abstract = "Black crystals of C60·μ-O{FeIII(OEP)} 2·C6H6 and 2C60· {FeIII(OEPO)}2·4C6H6 suitable for single-crystal X-ray diffraction studies have been obtained by growth from benzene solutions of the appropriate binuclear metalloporphyrin and the fullerene. C60·μ-O{FeIII(OEP)} 2·C6H6 crystallizes with two molecules of μ-O{FeIII(OEP)}2, two fully ordered molecules of C60, and two molecules of benzene in the asymmetric unit. Each independent molecule of μ-O{FeIII(OEP)}2 makes close contact with two fullerene molecules. In C60·μ-O{Fe III(OEP)}2·C6H6 the Fe-O-Fe angles (150.18(11)° and 151.89(11)°) are markedly bent with a benzene molecule wedged into the opening between the two porphyrins, whereas in the triclinic and monoclinic polymorphs of μ-O{FeIII(OEP)} 2 the Fe-O-Fe angles are more nearly linear (172.16(17)° and 176.2(2)°, respectively). The structure of 2C60·{Fe III(OEPO)}2·4C6H6 consists of a centrosymmetric {FeIII(OEPO)}2 molecule in which the two macrocycles are connected to one another through axial coordination of the meso-oxygen atoms to iron ions in the neighboring porphyrin. Each molecule of {FeIII-(OEPO)}2 engages a fullerene on its two exposed faces. The basic geometry of the central core of {FeIII(OEPO)} 2 is similar to that of the previously characterized {In III(OEPO)}2, but the distortion of the two macrocycles is greater in the former due to the shorter Fe-N and Fe-O bonds.",
author = "Lee, {Hon Man} and Olmstead, {Marilyn M.} and Gross, {Garrett G.} and Balch, {Alan L.}",
year = "2003",
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Cocrystallization of binuclear iron(III) porphyrins with C60 : Bending of μ-O{FeIII(octaethylporphyrin)} and the first structure of the iron(III) octaethyloxophlorin dimer. / Lee, Hon Man; Olmstead, Marilyn M.; Gross, Garrett G.; Balch, Alan L.

In: Crystal Growth and Design, Vol. 3, No. 5, 01.09.2003, p. 691-697.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Cocrystallization of binuclear iron(III) porphyrins with C60

T2 - Bending of μ-O{FeIII(octaethylporphyrin)} and the first structure of the iron(III) octaethyloxophlorin dimer

AU - Lee, Hon Man

AU - Olmstead, Marilyn M.

AU - Gross, Garrett G.

AU - Balch, Alan L.

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N2 - Black crystals of C60·μ-O{FeIII(OEP)} 2·C6H6 and 2C60· {FeIII(OEPO)}2·4C6H6 suitable for single-crystal X-ray diffraction studies have been obtained by growth from benzene solutions of the appropriate binuclear metalloporphyrin and the fullerene. C60·μ-O{FeIII(OEP)} 2·C6H6 crystallizes with two molecules of μ-O{FeIII(OEP)}2, two fully ordered molecules of C60, and two molecules of benzene in the asymmetric unit. Each independent molecule of μ-O{FeIII(OEP)}2 makes close contact with two fullerene molecules. In C60·μ-O{Fe III(OEP)}2·C6H6 the Fe-O-Fe angles (150.18(11)° and 151.89(11)°) are markedly bent with a benzene molecule wedged into the opening between the two porphyrins, whereas in the triclinic and monoclinic polymorphs of μ-O{FeIII(OEP)} 2 the Fe-O-Fe angles are more nearly linear (172.16(17)° and 176.2(2)°, respectively). The structure of 2C60·{Fe III(OEPO)}2·4C6H6 consists of a centrosymmetric {FeIII(OEPO)}2 molecule in which the two macrocycles are connected to one another through axial coordination of the meso-oxygen atoms to iron ions in the neighboring porphyrin. Each molecule of {FeIII-(OEPO)}2 engages a fullerene on its two exposed faces. The basic geometry of the central core of {FeIII(OEPO)} 2 is similar to that of the previously characterized {In III(OEPO)}2, but the distortion of the two macrocycles is greater in the former due to the shorter Fe-N and Fe-O bonds.

AB - Black crystals of C60·μ-O{FeIII(OEP)} 2·C6H6 and 2C60· {FeIII(OEPO)}2·4C6H6 suitable for single-crystal X-ray diffraction studies have been obtained by growth from benzene solutions of the appropriate binuclear metalloporphyrin and the fullerene. C60·μ-O{FeIII(OEP)} 2·C6H6 crystallizes with two molecules of μ-O{FeIII(OEP)}2, two fully ordered molecules of C60, and two molecules of benzene in the asymmetric unit. Each independent molecule of μ-O{FeIII(OEP)}2 makes close contact with two fullerene molecules. In C60·μ-O{Fe III(OEP)}2·C6H6 the Fe-O-Fe angles (150.18(11)° and 151.89(11)°) are markedly bent with a benzene molecule wedged into the opening between the two porphyrins, whereas in the triclinic and monoclinic polymorphs of μ-O{FeIII(OEP)} 2 the Fe-O-Fe angles are more nearly linear (172.16(17)° and 176.2(2)°, respectively). The structure of 2C60·{Fe III(OEPO)}2·4C6H6 consists of a centrosymmetric {FeIII(OEPO)}2 molecule in which the two macrocycles are connected to one another through axial coordination of the meso-oxygen atoms to iron ions in the neighboring porphyrin. Each molecule of {FeIII-(OEPO)}2 engages a fullerene on its two exposed faces. The basic geometry of the central core of {FeIII(OEPO)} 2 is similar to that of the previously characterized {In III(OEPO)}2, but the distortion of the two macrocycles is greater in the former due to the shorter Fe-N and Fe-O bonds.

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