Comparing and Correlating Solubility Parameters Governing the Self-Assembly of Molecular Gels Using 1,3:2,4-Dibenzylidene Sorbitol as the Gelator

• Published in: Langmuir Vol. 30; no. 47; pp. 14128 - 14142
• Main Authors: Lan, Yaqi, Corradini, Maria G, Liu, Xia, May, Tim E, Borondics, Ferenc, Weiss, Richard G, Rogers, Michael A
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 02.12.2014
• Subjects: Gels - chemistry; Hydrogen Bonding; Solubility; Solvents - chemistry; Sorbitol - analogs & derivatives; Sorbitol - chemistry
• ISSN: 0743-7463; 1520-5827
• DOI: 10.1021/la5008389

Solvent properties play a central role in mediating the aggregation and self-assembly of molecular gelators and their growth into fibers. Numerous attempts have been made to correlate the solubility parameters of solvents and gelation abilities of molecular gelators, but a comprehensive comparison of the most important parameters has yet to appear. Here, the degree to which partition coefficients (log P), Henry’s law constants (HLC), dipole moments, static relative permittivities (εr), solvatochromic E T(30) parameters, Kamlet–Taft parameters (β, α, and π), Catalan’s solvatochromic parameters (SPP, SB, and SA), Hildebrand solubility parameters (δ i ), and Hansen solubility parameters (δp, δd, δh) and the associated Hansen distance (R ij ) of 62 solvents (covering a wide range of properties) can be correlated with the self-assembly and gelation of 1,3:2,4-dibenzylidene sorbitol (DBS) gelation, a classic molecular gelator, is assessed systematically. The approach presented describes the basis for each of the parameters and how it can be applied. As such, it is an instructional blueprint for how to assess the appropriate type of solvent parameter for use with other molecular gelators as well as with molecules forming other types of self-assembled materials. The results also reveal several important insights into the factors favoring the gelation of solvents by DBS. The ability of a solvent to accept or donate a hydrogen bond is much more important than solvent polarity in determining whether mixtures with DBS become solutions, clear gels, or opaque gels. Thermodynamically derived parameters could not be correlated to the physical properties of the molecular gels unless they were dissected into their individual HSPs. The DBS solvent phases tend to cluster in regions of Hansen space and are highly influenced by the hydrogen-bonding HSP, δh. It is also found that the fate of this molecular gelator, unlike that of polymers, is influenced not only by the magnitude of the distance between the HSPs for DBS and the HSPs of the solvent, R ij , but also by the directionality of R ij : if the solvent has a larger hydrogen-bonding HSP (indicating stronger H-bonding) than that of the DBS, then clear gels are formed; opaque gels form when the solvent has a lower δh than does DBS.