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Using Crystal Optics to Demonstrate Single-Layer Localization of a Solid-State Chain Reaction

✍ Scribed by Kevin L. Pate; J. Michael McBride

Book ID: 101389352
Publisher: John Wiley and Sons
Year: 2000
Tongue: German
Weight: 190 KB
Volume: 83
Category: Article
ISSN: 0018-019X
DOI: 10.1002/1522-2675(20000906)83:9<2352::aid-hlca2352>3.0.co;2-c

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✦ Synopsis

Albert Eschenmoser on the occasion of his 75th birthday Upon warming to 225 K, single crystals of 11-bromoundecanoyl peroxide (BrUP), in which radicals have been created by photolysis at lower temperature, undergo partial decomposition by a radical chain reaction ca. 40 cycles long. FTIR allowed monitoring two chain products: CO 2 and an a-lactone that decomposes further at 260 K. When initiation is confined to alternate molecular layers by polarized photoselection, the chain reaction reduces the crystal symmetry from tetragonal to monoclinic. Desymmetrization is easily observed by optical microscopy, although it is difficult to detect by X-ray diffraction. Accurate monitoring of birefringence using a SeÂnarmont 1/4-wave plate, and comparison with FTIR kinetics, proves that the chain reaction occurs within single molecular layers 2 nm thick.

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