Porphyrinoid Macrocycles Based on Thiophene—The Octaethyltetrathiaporphyrin Dication

Abstract

7] Crystallographic data for 2 . 3py (C,,H,,CI,LiN,, M = 328.16): Monoclinic, space group P2,ln, a=1271.3(1). b =1072.8(5), c =1273.1(1)pm, / 3 = 91.81(1Y. V=1735.5(8)x 10-30m3. 2 = 4. p ,, =1.256 Mgm-'. ~(CU,,) = 3.331 mm". Data collection on an Enraf-Nonius CAD4 diffractometer with graphite monochromated Cu,, -radiation. o scans. max. 12 s per reflection, T = 150(2) K. 2604 reflections were collected (4 < 0 i 55"). of which 2185 were unique (R,,, = 0.053). The structure was solved with direct methods (SHELXTL) and was refined on F2 with all reflections (SHELXL-93). non-hydrogen atoms anisotropic, hydrogen atoms (without Hl) on calculated positions with fixed isotropic temperature factors. The parameters of the weightingschemecalculated by the program were: 0.1150,2.3053, wR2(Rl for 1949 reflections with I > Zu(1)): 0.2051 (0.0740), Goof =1.033; 204 refined parameters. The data were corrected with the program DIFABS ( R values without the DIFABS correction: 0.2283.0.0834). Relatively high temperature factors for the atoms C9 and C10 and "too short" bond lengths C8-C9 and C9-C10 indicate disorder which has not been resolved [13]. All calculations have been performed on an Micro-VAX I1 and a Dec 3000-300X [8-121 [8] Siemens SHELXTL (VMS) Vers. 5.04, Siemens-Analytical-X-Ray-lnstru-

Conjugated Macrocycles: Concepts and Applications

“…[113] Later, Sessler et al reported a series of bsubstituted sapphyrins containing one or more heteroatoms, and the monooxasapphyrin was found to form stable in-plane aromatic uranyl complexes (151; Figure 33). [114] The sulfur analogue of 22p-pentaphyrin 152 was reported by Vogel et al [115] As the synthetic methods and remarkable properties have already been reported in other reviews, [100,101,116] here we only summarize recent topics involving core-modified expanded porphyrins.…”

Konjugierte Makrocyclen: Konzepte und Anwendungen

“…[114] Das Schwefelanalogon 152 des 22p-Pentaphyrins wurde von Vogel und Mitarbeitern beschrieben. [115] Da die Synthesemethoden und die bemerkenswerten Eigenschaften bereits in anderen Übersichten erläutert wurden, [100,101,116] fassen wir hier nur die aktuellsten Ergebnisse zu kernmodifizierten expandierten Porphyrinen zusammen.…”

A Boron-Bridged Tetrathiaporphyrinogen

“…[1] These studies show that beyond the expected intermolecular forces always found in biological associations (hydrogen bonding, van der Waals forces, hydrophobic effects), stacking interactions between aromatic side chains and saccharides play an important role in stabilizing the complexes. [1,2] Besides the interactions at atomic level, change in oligosaccharide conformation on binding [3] and desolvation effects [4] are essential in determining the structural and energetic properties associated with carbohydrate recognition. Oligosaccharides observed in solution exist as an ensemble average of all possible conformations, and proteins may select oligosaccharide conformations that pre-exist in solution, or induce changes in the oligosaccharide upon binding.…”

“…[3] Their more soluble ethyl-substituted analogues have also been described, [4] as has a carbon-bridged neutral aromatic porphyrinoid based on thiophene. [5] Recently silicon-bridged silatetrathiaporphyrinogens and a phosphorusbridged phosphatetrathiaporphyrinogen have been reported.…”