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'Porphyrin' in keywords Facet   Publication Year 1999  [X]
Facet   section ZfN Section B  [X]
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1999[X]
1Author    Steffen Runge3, MathiasO. Senge3, Karin Ruhlandt-SengebRequires cookie*
 Title    5,10,15,20-Tetrakis(diphenylmethyl)porphyrin -A Nonplanar Porphyrin with Intermediate Degree of Ruffling  
 Abstract    The title compound was prepared by condensation of pyrrole and diphenylacetaldehyde in 16% yield. Based on spectroscopic data, the free base porphyrin exhibits a nonplanar macrocycle in solution with a degree of distortion between that of 5,10,15,20-tetracyclohexyl-porphyrin and 5,10,15,20-tetra(r-butyl)porphyrin. A crystal structure determination of the cobalt(II) complex reveals a ruffled macrocycle conformation with an average out-of-plane displacement of the m eso carbon atoms by 0.55 A. 
  Reference    Z. Naturforsch. 54b, 662 (1999); received February 17 1999 
  Published    1999 
  Keywords    Porphyrins, Steric Strain, Cobalt Porphyrins, Crystal Structure, Conformation 
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 TEI-XML for    default:Reihe_B/54/ZNB-1999-54b-0662.pdf 
 Identifier    ZNB-1999-54b-0662 
 Volume    54 
2Author    M. Athias, O. SengeRequires cookie*
 Title    Fixation o f Neutral M olecules in the Binding Cavity of Nonplanar Porphyrins -A Third Dodeca- phenylporphyrin Modification with NH -Solvent Hydrogen Bonding  
 Abstract    Reprint requests to Priv.-Doz. Dr. M. O. Senge. Fax: 0 3 0 -8 3 8 -4 2 4 8 . E-mail: mosenge@chemie.fu-berlin.de A third crystalline modification of dodecaphe-nylporphyrin is described in which the pyrrole ni­ trogen atoms are hydrogen-bonded to two etha­ nol molecules. This is the first crystallographic proof for the accessibility of nitrogen atoms in saddle-distorted free base porphyrins for hy­ drogen bonding. N o such coordination is possible in either planar or ruffled porphyrins. Thus, the possibility exists to utilize conformationally dis­ torted porphyrins for the binding of neutral m ole­ cules. 
  Reference    Z. Naturforsch. 54b, 821 (1999); received March 2 1999 
  Published    1999 
  Keywords    Porphyrins, Steric Strain, Conformational Flexi­ bility, Crystal Structure, Hydrogen Bonding 
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 TEI-XML for    default:Reihe_B/54/ZNB-1999-54b-0821_n.pdf 
 Identifier    ZNB-1999-54b-0821_n 
 Volume    54 
3Author    M. Athias, O. Senge, W. Erner, W. KalischRequires cookie*
 Title    Structure and Conformation of Tetra-meso-, O c t a -ß and Dodecasubstituted 22,24-Dihydroporphyrins (Porphyrin Dications)  
 Abstract    A comparative crystallographic analysis of the conformation of porphyrin diacids with various substituent types reveals considerable differences in the degree of nonplanarity and distortion modes. Diacids of 5,10,15,20-tetraarylporphyrins generally exhibit typical saddle-distorted macrocycles with displacements of the Cb positions in the range of 0.7-1.0 A. Adding peripheral substituents, i.e., using dodecasubstituted porphyrins for the diacid forma­ tion yields similar distortion types albeit with larger out-of-plane displacements. As a result of the combined effect of both peripheral (interaction between the Cb and Cm substituents) and core (interaction between the four inner hydrogen atoms) steric strain the maximum Cb displacements reach 1.3-1.5 A. Quite a different situation is observed for the diacids of 2,3,7,8,12,13,17,18-octaalkylporphyrins. Here, macrocycles with pair-wise displacement of neighboring pyrrole rings and significant NH pyramidalization and those with classic saddle distortion are found. Generally, octa-/?-substituted porphyrin diacids show smaller degrees of nonplanarity; Cb displacements ranged from 0.06 to 0.72 A. On the basis of the overall degree of conformational distortion (ZI24 = average deviation of the 24 macrocycles atoms from the mean plane), the three different types of porphyrin macrocycles studied differ considerably in their degree of conformational flexibility. For several porphyrin crystal structures with different counterions and/or solvate molecules were obtained. Taking into account results from the literature 2,3,7,8,12,13,17,18-octaethyl-22,24-dihydro-5,10,15.,20-tetraphenylporphy-rin (13) shows the smallest degree of flexibility (ZI24 = 0.61-0.63 A; four different X-ray structures),o while 22,24-dihydro-5,10,15,20-tetraphenylporphyrin (1) is more flexible (ZI24 = 0.42-0.52 A; four structures). The largest flexibility is observed for 2,3,7,8,12,13,18-octaethyl-22,24-dihydroporphyrin (7) (A24 = 0.02-0.33 A; four structures). 
  Reference    Z. Naturforsch. 54b, 943—959 (1999); received May 4 1999 
  Published    1999 
  Keywords    Porphyrins, Steric Strain, Porphyrin Dications, Crystal Structure, 22, 24-Dihydroporphyrins 
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 TEI-XML for    default:Reihe_B/54/ZNB-1999-54b-0943.pdf 
 Identifier    ZNB-1999-54b-0943 
 Volume    54