title: Supramolecular clippers for controlling photophysical processes through preorganized chromophores.
abstract: A novel supramolecular clipping design for influencing the photophysical properties of functional molecular assemblies, by the preorganization (clipping) of chromophores, is described. Several chromophores end functionalized with molecular recognition units were designed. These molecular recognition units serve as handles to appropriately position these systems upon noncovalent interactions with multivalent guest molecules (supramolecular clippers). Towards this goal, we have synthesized 1,5-dialkoxynaphthalene (DAN) and naphthalenediimide (NDI) functionalized with dipicolylethylenediamine (DPA) motifs. These molecules could preorganize upon noncovalent clipping with adenosine di- or triphosphates, which resulted in preassociated excimers and mixed (cofacial) charge-transfer (CT) assemblies. Chiral guest binding could also induce supramolecular chirality, not only into the individual chromophoric assembly but also into the heteromeric CT organization, as seen from the strong circular dichroism (CD) signal of the CT transition. The unique ability of this design to influence the intermolecular interactions by changing the binding strength of the clippers furthermore makes it very attractive for controlling the bimolecular photophysical processes.
authors.affiliation: Supramolecular Chemistry Laboratory, New Chemistry Unit, Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Jakkur P.O., Bangalore, 560064 (India).
authors.forename: Mohit
authors.initials: M
authors.lastname: Kumar
authors.forename: Onumashi Afi
authors.initials: OA
authors.lastname: Ushie
authors.forename: Subi J
authors.initials: SJ
authors.lastname: George
keywords: charge transfer; excimers; molecular clippers; molecular recognition; self-assembly