Sol-gel polycondensation of tetraethyl orthosilicate (TEOS) in sugar-based porphyrin organogels: inorganic conversion of a sugar-directed porphyrinic fiber library through sol-gel transcription processes.
Sugar-appended porphyrins (1 a-e) with monosaccharide groups at their periphery have been rationally designed for a new class of gelating reagents. A few of these compounds have the tendancy to form one-dimensional aggregates stable enough to show successful gelation ability for DMF-alcohol mixed solvents. The aggregation mode in the specific columnar super structures has been evaluated in detail by UV-visible spectrometry (UV/Vis), circular dichroism (CD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). All UV-visible spectra of sugar-appended porphyrinic gels obtained from 1 a-c exhibit Soret band absorptions, which shift to lower wavelength and are significantly broadened. This phenomenon indicates that these porphyrin cores strongly interact with each other in an H-aggregate fashion, which drives the generation of a one-dimensional porphyrin-stacking array. The CD spectra of the organogels from 1 a and 1 b, which are in anomers, exhibit an almost symmetric pattern, whereas the gel from 1 c gives a completely different pattern. This implies that the gel fibrils wind themselves in a right- or left-handed fashion; this reflects chirality in the specific molecular structure of the gelators. The results from SEM for the gel fibrils are in good agreement with the CD patterns. The gel fibrils in 1 a possess left-handed helicity, whereas those in 1 b wind themselves right-handedly. Macroscopic helical morphology reflects the microscopic structure well at a molecular level, which gives structural variety of the gel fibrils, which can be defined by the sugar library. Inorganic conversion of the organic helical fibrils by a sol-gel transcription process successfully gives the helical-silica structures, which finely inherit the organic morphology. A striking observation is that a unimolecular porphyrin-stacking array is also transcribed into silica fibers when the optimized sol-gel reaction conditions are selected. A sugar-based organic-fiber library in porphyrinic gels thus provides a variety of inorganic materials through the sol-gel transcription process.
Kawano
Shin-Ichiro
S
Department of Chemistry & Biochemisry, Graduate School of Engineering, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan.
Tamaru
Shun-Ichi
S
Fujita
Norifumi
N
Shinkai
Seiji
S