0000000000648405
AUTHOR
Elena Karpouk
Photochemical formation of [4.4.4](1,3,5)cyclophanes from 1,3,5-tris(3-phenylpropenoyl)benzenes
Abstract Irradiation of 1,3,5-tris(3-phenylpropenoyl)benzene ( 1a ) yields in solution a dimer 2a by a threefold head-to-head/anti [2π+2π]cycloaddition. The stereochemistry of this [4.4.4](1,3,5)cyclophane was determined by 1H and 13C NMR studies including NOE measurements and a calculation of the AA′MM′ spin pattern of the methine protons. In contrast to the solution photochemistry, which is presumably controlled by the arrangement of an excimer, the irradiation in the crystalline state leads by a topochemical control to a dimer 3a , which contains a single four-membered ring.
Guest-Host Systems of 1,3,5-Tristyrylbenzenes
(E,E,E)-1,3,5-Tris(3,4,5-trimethoxystyryl)benzene (1a) forms monoclinic crystals of the space group P21/c. Incorporation of three transoid diacetyl guest molecules between the three arms leads to triclinic crystals of the space group P1. The styryl groups, originally present in a nonsymmetrical conformation, are simultaneously transformed to a C3 arrangement. (E,E,E)-1,3,5-Tris- (3,4,5-tripropoxystyryl)benzene (1b) forms monoclinic crystals of the space group P21/c. The C3 arrangement of the styryl groups is present in the first, the unsymmetrical arrangement in the second modification. Incorporation of two acetone guests in the largest and the middle-sized angle space between the styryl ar…