Dicyano and pyridine derivatives of retinal: synthesis and vibronic, electronic, and photophysical properties.
Two new derivatives of all-trans retinal, one containing a pyridine and a cyanide substituent, all-trans-15-cyano-15'-pyridylretinal (2), and the other containing two cyanide substituents, all-trans-15,15'-dicyanoretinal (3), have been synthesized from all-trans-retinal (1) by the Knoevenagel reaction. Compound 2 crystallizes in the space group P1; compound 3 crystallizes in the space group P2(1)/n. The polyene chains are bowed. The compounds exhibit C[triple bond]N vibrations in the infrared and Raman regions and undergo irreversible oxidations. Compounds 2 and 3 display electronic absorptions with maxima located at 442 and 487 nm and emission peaks located at 583 and 500 nm, respectively. Density Functional Theory and Time Dependent Density Functional Theory calculations reveal that the electronic transition from the HOMO to the LUMO can be associated with the A(g) --> B(u) electronic transition and a peak corresponding to the HOMO --> LUMO+1 transition can be associated with the "cis-peak".
Department of Chemistry, Wichita State University, Wichita, Kansas 67260, USA.
A J
AJ
Cruz
K
K
Siam
C
C
Moore
M
M
Islam
D P
DP
Rillema