Bicyclo[2.2.2]octene-Based “Crab-like” Molecules:  Synthesis, Complexation, Luminescence Properties, and Solid-State Structures

• Published in: Journal of organic chemistry 2005-11, Vol.70 (24), p.9717-9726
• Main Authors: Chou, Teh-Chang, Hwa, Ching-Lun, Lin, Jin-Ju, Liao, Kung-Ching, Tseng, Jui-Chang
• Format: Article
• Language: English
• Subjects: Anthracenes - chemical synthesis; Anthracenes - chemistry; Bridged Bicyclo Compounds - chemical synthesis; Bridged Bicyclo Compounds - chemistry; Bridged Bicyclo Compounds, Heterocyclic - chemical synthesis; Bridged Bicyclo Compounds, Heterocyclic - chemistry; Chemistry; Coordination compounds; Crystallography, X-Ray; Exact sciences and technology; Hydrogen Bonding; Inorganic chemistry and origins of life; Luminescence; Models, Molecular; Molecular Conformation; Octanes - chemical synthesis; Octanes - chemistry; Preparations and properties; Stereoisomerism
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo051006f

The U-shaped, multifunctionalized tetraetheno-bridged dicyclopenta[b,i]anthracenediol 10 was synthesized to serve as a platform molecule. The molecule was prepared from the Diels−Alder adduct 5a of tricycloundecatriene 3 and bicyclo[2.2.2]octene-fused p-benzoquinone 4. Functionalization of 10 to construct crab-like molecules was achieved via the base-promoted bis-O-alkylation of two endo-oriented hydroxyl groups at termini in 10 with the following alkyl halides:  allyl, propagyl, and benzyl bromides; 1-bromo- and 1-iodo-4-(bromomethyl)benzene; 9-(bromomethyl)anthracene; 1-(bromomethyl)pyrene; and isomeric bromomethylpyridines. Single-crystal X-ray structures were obtained for bis-phenyl (21) and bis-pyrenyl (25) crabs, and for the silver(I) complex (32 and 33) crabs. The silver(I) complex 32 from bis-o-pyridyl crab 30 is a [2+2] dimeric dimetallocyclophane, and 33 from bis-m-pyridyl crab 29 is a [1+1] metallo-bridged cyclophane. The self-assembled intramolecular π-stacking of pyrenyl rings in 25 with an interplanar distance of 3.40 Å and the consequent π−π interactions were revealed by the X-ray crystal structure and its luminescence property.