Bicyclo[2.2.2]octene-based "crab-like" molecules: synthesis, complexation, luminescence properties, and solid-state structures.
[structure, reaction: see text] 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 pi-stacking of pyrenyl rings in 25 with an interplanar distance of 3.40 A and the consequent pi-pi interactions were revealed by the X-ray crystal structure and its luminescence property.
Chou
Teh-Chang
TC
Department of Chemistry and Biochemistry, National Chung Cheng University, Minshong, Chiayi 621, Taiwan. chetcc@ccu.edu.tw
Hwa
Ching-Lun
CL
Lin
Jin-Ju
JJ
Liao
Kung-Ching
KC
Tseng
Jui-Chang
JC
D000873:Anthracenes / Q000138:chemical synthesis / Q000737:chemistry; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis / Q000737:chemistry; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis / Q000737:chemistry; D018360:Crystallography, X-Ray; D006860:Hydrogen Bonding; D049449:Luminescence; D008958:Models, Molecular; D008968:Molecular Conformation; D009795:Octanes / Q000138:chemical synthesis / Q000737:chemistry; D013237:Stereoisomerism
D000873:Anthracenes; D001643:Bridged Bicyclo Compounds; D019086:Bridged Bicyclo Compounds, Heterocyclic; D009795:Octanes; C511473:dicyclopenta(b,i)anthracenediol