title: Dipole-moment-driven cooperative supramolecular polymerization.
abstract: While the mechanism of self-assembly of π-conjugated molecules has been well studied to gain control over the structure and functionality of supramolecular polymers, the intermolecular interactions underpinning it are poorly understood. Here, we study the mechanism of self-assembly of perylene bisimide derivatives possessing dipolar carbonate groups as linkers. It was observed that the combination of carbonate linkers and cholesterol/dihydrocholesterol self-assembling moieties led to a cooperative mechanism of self-assembly. Atomistic molecular dynamics simulations of an assembly in explicit solvent strongly suggest that the dipole-dipole interaction between the carbonate groups imparts a macro-dipolar character to the assembly. This is confirmed experimentally through the observation of a significant polarization in the bulk phase for molecules following a cooperative mechanism. The cooperativity is attributed to the presence of dipole-dipole interaction in the assembly. Thus, anisotropic long-range intermolecular interactions such as dipole-dipole interaction can serve as a way to obtain cooperative self-assembly and aid in rationalizing and predicting the mechanisms in various synthetic supramolecular polymers.
authors.affiliation: †New Chemistry Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur, Bangalore 560064, India.|§Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur, Bangalore 560064, India.
authors.forename: Chidambar
authors.initials: C
authors.lastname: Kulkarni
authors.affiliation: §Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur, Bangalore 560064, India.
authors.forename: Karteek K
authors.initials: KK
authors.lastname: Bejagam
authors.affiliation: §Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur, Bangalore 560064, India.
authors.forename: Satyaprasad P
authors.initials: SP
authors.lastname: Senanayak
authors.affiliation: §Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur, Bangalore 560064, India.
authors.forename: K S
authors.initials: KS
authors.lastname: Narayan
authors.affiliation: §Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur, Bangalore 560064, India.
authors.forename: S
authors.initials: S
authors.lastname: Balasubramanian
authors.affiliation: †New Chemistry Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur, Bangalore 560064, India.
authors.forename: Subi J
authors.initials: SJ
authors.lastname: George
mesh_terms: D002254:Carbonates; D003198:Computer Simulation; D004563:Electrochemistry; D007094:Imides / Q000737:chemistry*; D015394:Molecular Structure; D010569:Perylene / Q000031:analogs & derivatives* / Q000737:chemistry; D058105:Polymerization
chemical_list: D002254:Carbonates; D007094:Imides; C510697:perylene bisimide; D010569:Perylene