Optically active supramolecular complex formed by ionic self-assembly of cationic perylenediimide derivative and adenosine triphosphate

Abstract

Ionically self-assembled complex between a water-soluble perylenediimide (PDI) derivative, N,N'-bis(propylenetrimethylammonium)-3,4,9,10-perylenediimide (BPTA-PDI), and adenosine triphosphate (ATP) has been prepared. Absorption, emission, and circular dichroism (CD) spectroscopic techniques were used to monitor the complex formation. It was found that, upon the addition of ATP into the solution of an intrinsically achiral BPTA-PDI, the complex exhibits a unique split-type induced CD (ICD) in the pi-pi* transition region of the PDI chromophore, indicating that the molecular chirality of nucleotides is expressed in the perylene moiety through the multiple electrostatic interactions. The influences of BPTA-PDI concentration, temperature, and adenosine nucleotides bearing different numbers of phosphate groups on the chirality induction to BPTA-PDI were also investigated. On the basis of extensive investigations performed with absorption, emission, and CD spectroscopy, a possible mechanism for the formation of chiral superstructures is proposed.