Self-Assembly of a Functional Oligo(Aniline)-Based Amphiphile into Helical Conductive Nanowires.
A tetra(aniline)-based cationic amphiphile, TANI-NHC(O)C5H10N(CH3)3(+)Br(-) (TANI-PTAB) was synthesized, and its emeraldine base (EB) state was found to self-assemble into nanowires in aqueous solution. The observed self-assembly is described by an isodesmic model, as shown by temperature-dependent UV-vis investigations. Linear dichroism (LD) studies, combined with computational modeling using time-dependent density functional theory (TD-DFT), suggests that TANI-PTAB molecules are ordered in an antiparallel arrangement within nanowires, with the long axis of TANI-PTAB arranged perpendicular to the nanowire long axis. Addition of either S- or R- camphorsulfonic acid (CSA) to TANI-PTAB converted TANI to the emeraldine salt (ES), which retained the ability to form nanowires. Acid doping of TANI-PTAB had a profound effect on the nanowire morphology, as the CSA counterions' chirality translated into helical twisting of the nanowires, as observed by circular dichroism (CD). Finally, the electrical conductivity of CSA-doped helical nanowire thin films processed from aqueous solution was 2.7 mS cm(-1). The conductivity, control over self-assembled 1D structure and water-solubility demonstrate these materials' promise as processable and addressable functional materials for molecular electronics, redox-controlled materials and sensing.
School of Chemistry, University of Bristol , Bristol BS8 1TS, U.K.
O Alexander
OA
Bell
Key Laboratory of Organic Optoelectronics & Molecular Engineering, Department of Chemistry, Tsinghua University , Beijing 100084, China.
Guanglu
G
Wu
Aalto University , Department of Applied Physics, Molecular Materials, FIN-00076 Espoo, Finland.
Johannes S
JS
Haataja
School of Chemistry, University of Bristol , Bristol BS8 1TS, U.K.
Felicitas
F
Brömmel
School of Chemistry, University of Bristol , Bristol BS8 1TS, U.K.
Natalie
N
Fey
H. H. Wills Physics Laboratory, University of Bristol , Tyndall Avenue, Bristol BS8 1TL, United Kingdom.|Bristol Centre for Functional Nanomaterials, Nanoscience and Quantum Information Building, University of Bristol , Tyndall Avenue, Bristol BS8 1FD, United Kingdom.
Annela M
AM
Seddon
School of Chemistry, University of Bristol , Bristol BS8 1TS, U.K.
Robert L
RL
Harniman
H. H. Wills Physics Laboratory, University of Bristol , Tyndall Avenue, Bristol BS8 1TL, United Kingdom.
Robert M
RM
Richardson
Aalto University , Department of Applied Physics, Molecular Materials, FIN-00076 Espoo, Finland.
Olli
O
Ikkala
Key Laboratory of Organic Optoelectronics & Molecular Engineering, Department of Chemistry, Tsinghua University , Beijing 100084, China.
Xi
X
Zhang
School of Chemistry, University of Bristol , Bristol BS8 1TS, U.K.
Charl F J
CF
Faul