X-ray structural and imidazole-binding studies of nickel .beta.-oxoporphyrins

Connick, Patricia A.; Haller, Kenneth J.; Macor, Kathleen A.

doi:10.1021/ic00067a011

Cited by 29 publications

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“…This small variation in metal-tonitrogen bond lengths as a result of ring conformation has also been seen in [Ni(oxoOEC)]. 45,46 After oxidation to [Cu-(oxoOEC • )][SbCl 6 ], the "long" Cu-N distance to the pyrrolinone ring decreases from 2.057(5) to 2.022(3) Å, while the average "short" Cu-N distance (1.993(10) and 1.987(5) Å) to the pyrrole rings stays the same. Thus, the Cu-N bond to the pyrrolinone ring is affected more than the Cu-N bond to the pyrrole rings upon removal of an electron from the macrocycle.…”

Section: Discussionsupporting

confidence: 62%

Molecular Structures and Magnetochemistry of Two (β-Oxooctaethylchlorinato)copper(II) Derivatives: [Cu(oxoOEC)] and [Cu(oxoOEC^•)]SbCl₆

et al. 1999

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The preparation and characterization of the -oxochlorin derivative [3,3,7,8,12,13,17,18-octaethyl-(3H)-porphin-2-onato(2-)]copper(II), [Cu(oxoOEC)], and its π-cation radical derivative, [Cu(oxoOEC • )][SbCl 6 ], are described. Both compounds have been characterized by single-crystal X-ray structure determinations; IR, UV/vis/near-IR, and EPR spectroscopies; and temperature-dependent magnetic susceptibility measurements. Crystals of [Cu-(oxoOEC)] have two crystallographically distinct molecules, one at a general position ([Cu(oxoOEC)]-gen) and a second at a special position ([Cu(oxoOEC)]-spe). [Cu(oxoOEC)]-gen has a S 4 -saddled conformation whereas [Cu(oxoOEC)]-spe has a modest ruffled conformation. [Cu(oxoOEC • )][SbCl 6 ] shows a cofacial dimeric unit in the solid state, with a mean plane separation of 3.41 Å and a lateral shift of 5.47 Å. Crystal data for [Cu-(oxoOEC)]: monoclinic, space group C2/c, Z ) 12, a ) 38.404(8) Å, b ) 14.692(6) Å, c ) 16.977(11) Å, ) 101.46(2)°. Crystal data for [Cu(oxoOEC • )][SbCl 6 ]: triclinic, space group P1 h, Z ) 2, a ) 13.063(1) Å, b ) 14.108(2) Å, c ) 11.486(2) Å, R ) 93.77(3)°, ) 102.17(1)°, γ ) 74.07(1)°. The EPR spectrum of [Cu-(oxoOEC • )][SbCl 6 ] in frozen dichloromethane at 77 K shows the characteristics of a dimeric copper(II) triplet state. Two broad, concentration-dependent near-IR "dimer bands" appear at 1285 and 1548 nm for [Cu(oxoOEC • )]-[SbCl 6 ]. Solid-state magnetic susceptibility measurements for [Cu(oxoOEC • )][SbCl 6] resulted in a large temperature dependence of the magnetic moments that can best be fit with a four-spin model. This model includes antiferromagnetic intermolecular copper-copper coupling (2J Cu-Cu ) -70 cm -1 ), antiferromagnetic radical-radical coupling (2J r-r ) -139 cm -1 ), and ferromagnetic intramolecular copper-radical coupling (2J Cu-r ) 139 cm -1 ).

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Section: Discussionsupporting

confidence: 62%

Molecular Structures and Magnetochemistry of Two (β-Oxooctaethylchlorinato)copper(II) Derivatives: [Cu(oxoOEC)] and [Cu(oxoOEC^•)]SbCl₆

et al. 1999

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“…)][SbCl 6 ], 11, 29 and in copper hydroporphyrinates. 30–32 This bond distance difference is also found in other metal complexes including [Ni(oxoOEC)], [Ni(dioxoOEiBC)], [Ni(trioxoOEHP)], 33 [Fe(oxoOEC)(Cl)], [Fe(oxoOEC . )Cl][SbCl 6 ], 12 and [Fe(dioxoOEiBC))Cl)].…”

Section: Discussionsupporting

confidence: 67%

“…These phenomena are also found in all other crystallographically characterized metallo- β -oxochlorin, metallo- β- dioxoisobacteriochlorin, and metallo- β -trioxohexahydroporphyrin complexes. 11,12,33,34 …”

Section: Discussionmentioning

confidence: 99%

Conformational distortions of π-cation radical (β-oxoporphyrin)copper(II) derivatives: [Cu(2,7,12-trioxoOEHP^·)][SbCl₆] and [Cu(2,7-dioxoOEiBC^·)][SbCl₆]

Turowska‐Tyrk

Seongjoo

Scheidt

2011

J. Porphyrins Phthalocyanines

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The preparation and characterization of two π-cation radical derivatives of copper β-oxo porphyrins is described. [3,3,8,8,13,13,17,18-Octaethyl-(3H,8H,13H)-porphine-2,7,12-trionato (2-)] copper π-cation radical, [Cu(2,7,12-trioxoOEHP.)]+, and [3,3,8,8,12,13,17,18-octaethyl-(3H,8H)-porphine-2,7-dionato(2-)] copper π-cation radical, [Cu(2,7-dioxoOEiBC.)]+, have been prepared and characterized by single-crystal X-ray determinations, UV/vis/NIR, and IR spectroscopies. Both molecules have modest distortion from the planarity and show monomeric units in the solid state. [Cu(2,7-dioxoOEiBC.)]+ shows a concentration dependent near-IR band at 1410 nm. Crystal data for [Cu(2,7,12-trioxoOEHP.)][SbCl6]: tetragonal, space group P42/n, a = 31.085 (14) Å, c = 9.410 (4) Å, V = 9093 Å3, Z = 8, T = 127 K. Crystal data for [Cu(2,7-dioxoOEiBC.)][SbCl6]: monoclinic, space group P21/n, a = 9.655 (4) Å, b = 20.592 (8) Å, c = 43.347 (17) Åβ = 89.97(1)°, V = 8618. Å3, Z = 8, T = 100 K.

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“…The coordination chemistry of bacteriochlorins in general was only sparsely studied . That of dioxobacteriochlorins (outside of tolyporphins) even less, although a Pt(II) complex of 12 was reported ; that of the dioxoisobacteriochlorins was somewhat better studied, but by no means comprehensively . Thus, the final word on this subject is certainly not yet spoken.…”

Section: Coordination Chemistrymentioning

confidence: 99%

Tolyporphin—An Unusual Green Chlorin‐like Dioxobacteriochlorin

Brückner

2017

Photochem & Photobiology

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The tolyporphins, a family of green tetrapyrrolic pigments isolated from a cyanobacterium-microbial ecological unit, possess unique carbohydrate-derivatized dioxobacteriochlorin frameworks. A brief overview over the history, synthesis, chemistry and biological properties of the tolyporphins forms the backdrop for highlighting the contribution by Hood et al. (Photochem. Photobiol., 2017, https://doi.org/10.1111/php.12781) who demonstrate the optical properties of tolyporphins to be more similar to those of chlorins than of bacteriochlorins. This property could be correlated with the presence of β-oxo-functionalities. The study continues to clarify the structure, properties and possible roles of these intriguing chromophores with a range of biomedical properties.

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X-ray structural and imidazole-binding studies of nickel .beta.-oxoporphyrins

Cited by 29 publications

References 0 publications

Molecular Structures and Magnetochemistry of Two (β-Oxooctaethylchlorinato)copper(II) Derivatives: [Cu(oxoOEC)] and [Cu(oxoOEC^•)]SbCl₆

Molecular Structures and Magnetochemistry of Two (β-Oxooctaethylchlorinato)copper(II) Derivatives: [Cu(oxoOEC)] and [Cu(oxoOEC^•)]SbCl₆

Conformational distortions of π-cation radical (β-oxoporphyrin)copper(II) derivatives: [Cu(2,7,12-trioxoOEHP^·)][SbCl₆] and [Cu(2,7-dioxoOEiBC^·)][SbCl₆]

Tolyporphin—An Unusual Green Chlorin‐like Dioxobacteriochlorin

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X-ray structural and imidazole-binding studies of nickel .beta.-oxoporphyrins

Cited by 29 publications

References 0 publications

Molecular Structures and Magnetochemistry of Two (β-Oxooctaethylchlorinato)copper(II) Derivatives: [Cu(oxoOEC)] and [Cu(oxoOEC•)]SbCl6

Molecular Structures and Magnetochemistry of Two (β-Oxooctaethylchlorinato)copper(II) Derivatives: [Cu(oxoOEC)] and [Cu(oxoOEC•)]SbCl6

Conformational distortions of π-cation radical (β-oxoporphyrin)copper(II) derivatives: [Cu(2,7,12-trioxoOEHP·)][SbCl6] and [Cu(2,7-dioxoOEiBC·)][SbCl6]

Tolyporphin—An Unusual Green Chlorin‐like Dioxobacteriochlorin

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Molecular Structures and Magnetochemistry of Two (β-Oxooctaethylchlorinato)copper(II) Derivatives: [Cu(oxoOEC)] and [Cu(oxoOEC^•)]SbCl₆

Molecular Structures and Magnetochemistry of Two (β-Oxooctaethylchlorinato)copper(II) Derivatives: [Cu(oxoOEC)] and [Cu(oxoOEC^•)]SbCl₆

Conformational distortions of π-cation radical (β-oxoporphyrin)copper(II) derivatives: [Cu(2,7,12-trioxoOEHP^·)][SbCl₆] and [Cu(2,7-dioxoOEiBC^·)][SbCl₆]