A comparative study of the self-assembly at a variety of surfaces of a dithiophene rotaxane 1⊂β-CD and its corresponding dumbbell, 1, by means of atomic force microscopy (AFM) imaging and scanning tunneling microscopy (STM) imaging on the micrometer and nanometer scale, respectively. The dumbbell is found to have a greater propensity to form ordered supramolecular assemblies, as a result of π-π interactions between dithiophenes belonging to adjacent molecules, which are hindered in the rotaxane. The fine molecular structure determined by STM was compared to that obtained by molecular modelling. The optical properties of both rotaxane and dumbbell in the solid state were investigated by steady-state and time-resolved photoluminescence (PL) experiments on spin-cast films and diluted solutions. The comparison between the optical features of the threaded and unthreaded systems reveals an effective role of encapsulation in reducing aggregation and exciton migration for the rotaxanes with respect to the dumbbells, thus leading to higher PL quantum efficiency and preserved single-molecule photophysics for longer times after excitation in the threaded oligomers. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Zalewski, L., Brovelli, S., Bonini, M., Mativetsky, J., Wykes, M., Orgiu, E., et al. (2011). Self-Assembled Conjugated Thiophene-Based Rotaxane Architectures: Structural, Computational, and Spectroscopic Insights into Molecular Aggregation. ADVANCED FUNCTIONAL MATERIALS, 21(5), 834-844 [10.1002/adfm.201001135].
Self-Assembled Conjugated Thiophene-Based Rotaxane Architectures: Structural, Computational, and Spectroscopic Insights into Molecular Aggregation
BROVELLI, SERGIO;MEINARDI, FRANCESCO;
2011
Abstract
A comparative study of the self-assembly at a variety of surfaces of a dithiophene rotaxane 1⊂β-CD and its corresponding dumbbell, 1, by means of atomic force microscopy (AFM) imaging and scanning tunneling microscopy (STM) imaging on the micrometer and nanometer scale, respectively. The dumbbell is found to have a greater propensity to form ordered supramolecular assemblies, as a result of π-π interactions between dithiophenes belonging to adjacent molecules, which are hindered in the rotaxane. The fine molecular structure determined by STM was compared to that obtained by molecular modelling. The optical properties of both rotaxane and dumbbell in the solid state were investigated by steady-state and time-resolved photoluminescence (PL) experiments on spin-cast films and diluted solutions. The comparison between the optical features of the threaded and unthreaded systems reveals an effective role of encapsulation in reducing aggregation and exciton migration for the rotaxanes with respect to the dumbbells, thus leading to higher PL quantum efficiency and preserved single-molecule photophysics for longer times after excitation in the threaded oligomers. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
