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Stimuli-controlled self-assembly of diverse tubular aggregates from one single small monomer.

ABSTRACT: The design and synthesis of new stimuli-responsive hydrogen-bonding monomers that display a diversity of self-assembly pathways is of central importance in supramolecular chemistry. Here we describe the aggregation properties of a simple, intrinsically C₂-symmetric enantiopure bicyclic cavity compound bearing a terminally unsubstituted ureidopyrimidinone fragment fused with a pyrrole moiety in different solvents and in the absence and presence of C₆₀ and C₇₀ guests. The tetrameric cyclic aggregate is selectively obtained in chlorinated solvents, where only part of the available hydrogen bonding sites are utilized, whereas in toluene or upon addition of C₇₀ guests, further aggregation into tubular supramolecular polymers is achieved. The open-end cyclic assemblies rearrange into a closed-shell capsule upon introduction of C₆₀ with an accompanied symmetry breaking of the monomer. Our study demonstrates that a C₆₀ switch can be used to simultaneously control the topology and occupancy of tubular assemblies resulting from the aggregation of small monomers.

SUBMITTER: Shi Q

PROVIDER: S-EPMC5394284 | biostudies-literature | 2017 Apr

REPOSITORIES: biostudies-literature

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Stimuli-controlled self-assembly of diverse tubular aggregates from one single small monomer.

Shi Qixun Q Javorskis Tomas T Bergquist Karl-Erik KE Ulčinas Artūras A Niaura Gediminas G Matulaitienė Ieva I Orentas Edvinas E Wärnmark Kenneth K

Nature communications 20170412

The design and synthesis of new stimuli-responsive hydrogen-bonding monomers that display a diversity of self-assembly pathways is of central importance in supramolecular chemistry. Here we describe the aggregation properties of a simple, intrinsically C2-symmetric enantiopure bicyclic cavity compound bearing a terminally unsubstituted ureidopyrimidinone fragment fused with a pyrrole moiety in different solvents and in the absence and presence of C60 and C70 gues ...[more]

PMID: 28401927

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Project description:A bis(squaraine) dye equipped with alkyl and oligoethyleneglycol chains was synthesized by connecting two dicyanomethylene substituted squaraine dyes with a phenylene spacer unit. The aggregation behavior of this bis(squaraine) was investigated in non-polar toluene/tetrachloroethane (98:2) solvent mixture, which revealed competing cooperative self-assembly pathways into two supramolecular polymorphs with entirely different packing structures and UV/Vis/NIR absorption properties. The self-assembly pathway can be controlled by the cooling rate from a heated solution of the monomers. For both polymorphs, quasi-equilibrium conditions between monomers and the respective aggregates can be established to derive thermodynamic parameters and insights into the self-assembly mechanisms. AFM measurements revealed a nanosheet structure with a height of 2 nm for the thermodynamically more stable polymorph and a tubular nanorod structure with a helical pitch of 13 nm and a diameter of 5 nm for the kinetically favored polymorph. Together with wide angle X-ray scattering measurements, packing models were derived: the thermodynamic polymorph consists of brick-work type nanosheets that exhibit red-shifted absorption bands as typical for J-aggregates, while the nanorod polymorph consists of eight supramolecular polymer strands of the bis(squaraine) intertwined to form a chimney-type tubular structure. The absorption of this aggregate covers a large spectral range from 550 to 875 nm, which cannot be rationalized by the conventional exciton theory. By applying the Essential States Model and considering intermolecular charge transfer, the aggregate spectrum was adequately reproduced, revealing that the broad absorption spectrum is due to pronounced donor-acceptor overlap within the bis(squaraine) nanorods. The latter is also responsible for the pronounced bathochromic shift observed for the nanosheet structure as a result of the slip-stacked arranged squaraine chromophores.

Project description:While the green production and application of 2D functional nanomaterials, such as graphene flakes, in films for stretchable and wearable technologies is a promising platform for advanced technologies, there are still challenges involved in the processing of the deposited material to improve properties such as electrical conductivity. In applications such as wearable biomedical and flexible energy devices, the widely used flexible and stretchable substrate materials are incompatible with high-temperature processing traditionally employed to improve the electrical properties, which necessitates alternative manufacturing approaches and new steps for enhancing the film functionality. We hypothesize that a mechanical stimulus, in the form of substrate straining, may provide such a low-energy approach for modifying deposited film properties through increased flake packing and reorientation. To this end, graphene flakes were exfoliated using an unexplored combination of ethanol and cellulose acetate butyrate for morphological and percolative electrical characterization prior to application on polydimethylsiloxane (PDMS) substrates as a flexible and stretchable electrically conductive platform. The deposited percolative free-standing films on PDMS were characterized via in situ resistance strain monitoring and surface morphology measurements over numerous strain cycles, with parameters extracted describing the dynamic modulation of the film's electrical properties. A reduction in the film resistance and strain gauge factor was found to correlate with the surface roughness and densification of a sample's (sub)surface and the applied strain. High surface roughness samples exhibited enhanced reduction in resistance as well as increased sensitivity to strain compared to samples with low surface roughness, corresponding to surface smoothing, which is related to the dynamic settling of graphene flakes on the substrate surface. This procedure of incorporating strain as a mechanical stimulus may find application as a manufacturing tool/step for the routine fabrication of stretchable and wearable devices, as a low energy and compatible approach, for enhancing the properties of such devices for either high sensitivity or low sensitivity of electrical resistance to substrate strain.

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Stimuli-controlled self-assembly of diverse tubular aggregates from one single small monomer.

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Stimuli-controlled self-assembly of diverse tubular aggregates from one single small monomer.

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