Self-assembly of two-component gels: stoichiometric control and component selection.
Two-component systems capable of self-assembling into soft gel-phase materials are of considerable interest due to their tunability and versatility. This paper investigates two-component gels based on a combination of a L-lysine-based dendron and a rigid diamine spacer (1,4-diaminobenzene or 1,4-diaminocyclohexane). The networked gelator was investigated using thermal measurements, circular dichroism, NMR spectroscopy and small angle neutron scattering (SANS) giving insight into the macroscopic properties, nanostructure and molecular-scale organisation. Surprisingly, all of these techniques confirmed that irrespective of the molar ratio of the components employed, the "solid-like" gel network always consisted of a 1:1 mixture of dendron/diamine. Additionally, the gel network was able to tolerate a significant excess of diamine in the "liquid-like" phase before being disrupted. In the light of this observation, we investigated the ability of the gel network structure to evolve from mixtures of different aromatic diamines present in excess. We found that these two-component gels assembled in a component-selective manner, with the dendron preferentially recognising 1,4-diaminobenzene (>70 %), when similar competitor diamines (1,2- and 1,3-diaminobenzene) are present. Furthermore, NMR relaxation measurements demonstrated that the gel based on 1,4-diaminobenzene was better able to form a selective ternary complex with pyrene than the gel based on 1,4-diaminocyclohexane, indicative of controlled and selective pi-pi interactions within a three-component assembly. As such, the results in this paper demonstrate how component selection processes in two-component gel systems can control hierarchical self-assembly.
Hirst
Andrew R
AR
Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK.
Miravet
Juan F
JF
Escuder
Beatriu
B
Noirez
Laurence
L
Castelletto
Valeria
V
Hamley
Ian W
IW
Smith
David K
DK
D000873:Anthracenes / Q000737:chemistry; D002942:Circular Dichroism; D045424:Complex Mixtures / Q000737:chemistry; D003959:Diamines / Q000737:chemistry; D005782:Gels / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D033363:Neutron Diffraction; D053838:Scattering, Small Angle; D013379:Substrate Specificity; D044366:Transition Temperature
D000873:Anthracenes; D045424:Complex Mixtures; D003959:Diamines; D005782:Gels; C501244:dendron