Nonplanar porphyrins. X-ray structures of (2,3,7,8,12,13,17,18-octaethyl- and -octamethyl-5,10,15,20-tetraphenylporphinato)zinc(II)

Journal Article · Wed Nov 21 00:00:00 EST 1990 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00180a029· OSTI ID:5289890

Barkigia, K M; Fajer, J; Renner, M W ^[1]; Berber, M D; Medforth, C J; Smith, K M ^[2]

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1. Brookhaven National Lab., Upton NY (USA)
2. Univ. of California, Davis (USA)

X-ray structures of the peripherally crowded porphyrins, (2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetraphenylporphinato)Zn(II)-3MeOH solvate (ZnOETPP{center dot}3MeOH) and (2,3,7,8,12,13,17,18-octamethyl-5,10,15,20-tetraphenylporphinato)Zn(II)-pyridine-2HCCl{sub 3} (ZnOMTPP{center dot}py{center dot}2HCCl{sub 3}) are reported. Both molecules are severly nonplanar and assume saddle shapes. {sup 1}H NMR data confirm that the conformational distortions are maintained in solution. The consequences of distorting the macrocycles are significant: optical, redox, basicity, and excited-state properties are altered in agreement with previous theoretical calculations. These results form part of an expanding body of structural information that cleary demonstrates that porphinoid skeletons are flexible and that distortions of the macrocycles can be imposed by steric interactions in vitro and in vivo. Conformational variations thus provide an attractively simple mechanism for modulating a wide range of physical and chemical properties of porphyrinic chromophores and prosthetic groups in vitro and in vivo.

• OSTI ID: 5289890
• Journal Information: Journal of the American Chemical Society; (United States), Vol. 112:24; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
PORPHYRINS
CRYSTAL STRUCTURE
EXPERIMENTAL DATA
LATTICE PARAMETERS
MONOCLINIC LATTICES
PHOTOSYNTHESIS
TRICLINIC LATTICES
X-RAY DIFFRACTION
CARBOXYLIC ACIDS
CHEMICAL REACTIONS
COHERENT SCATTERING
CRYSTAL LATTICES
DATA
DIFFRACTION
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
SCATTERING
SYNTHESIS
400201* - Chemical & Physicochemical Properties