Multifunctional polymer bearing malonylurea groups for the fabrication of coordination complexes and supramolecular assemblies

Sun, Mengxiao; Zhou, Yun; Ye, Zhanpeng; Li, Shuangyang; Dong, Anjie; Zhang, Jianhua

doi:10.1016/j.eurpolymj.2021.110616

Cited by 2 publications

(1 citation statement)

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“…They can bind specifically and strongly towards artificial receptors like the Hamilton Wedge [ 17 , 18 , 19 ], triazines [ 20 ], and diaminopyridines [ 21 ], display self-association [ 22 , 23 , 24 ], and generate transient H-bonds networks in barbiturate-bearing polymers [ 25 , 26 ], despite their comparatively low association constant in nonpolar solvents of only 23.6 M −1 (allobarbital) [ 22 ]. When attaching them onto (macro-)molecules, unique dynamic properties via their distinctive H-bonding in functional materials can be achieved, such as in monolayers [ 27 , 28 , 29 ], in coordination complexes [ 30 , 31 ], in 3D printing [ 32 ], or as self-healing-polymers [ 25 , 26 , 32 , 33 , 34 ] in self-assembled materials [ 35 , 36 ].…”

Section: Introductionmentioning

confidence: 99%

Comparing C2=O and C2=S Barbiturates: Different Hydrogen-Bonding Patterns of Thiobarbiturates in Solution and the Solid State

Hilgeroth

Hasan

et al. 2021

IJMS

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Carbonyl-centered hydrogen bonds with various strength and geometries are often exploited in materials to embed dynamic and adaptive properties, with the use of thiocarbonyl groups as hydrogen-bonding acceptors remaining only scarcely investigated. We herein report a comparative study of C2=O and C2=S barbiturates in view of their differing hydrogen bonds, using the 5,5-disubstituted barbiturate B and the thiobarbiturate TB as model compounds. Owing to the different hydrogen-bonding strength and geometries of C2=O vs. C2=S, we postulate the formation of different hydrogen-bonding patterns in C2=S in comparison to the C2=O in conventional barbiturates. To study differences in their association in solution, we conducted concentration- and temperature-dependent NMR experiments to compare their association constants, Gibbs free energy of association ∆Gassn., and the coalescence behavior of the N-H‧‧‧S=C bonded assemblies. In Langmuir films, the introduction of C2=S suppressed 2D crystallization when comparing B and TB using Brewster angle microscopy, also revealing a significant deviation in morphology. When embedded into a hydrophobic polymer such as polyisobutylene, a largely different rheological behavior was observed for the barbiturate-bearing PB compared to the thiobarbiturate-bearing PTB polymers, indicative of a stronger hydrogen bonding in the thioanalogue PTB. We therefore prove that H-bonds, when affixed to a polymer, here the thiobarbiturate moieties in PTB, can reinforce the nonpolar PIB matrix even better, thus indicating the formation of stronger H-bonds among the thiobarbiturates in polymers in contrast to the effects observed in solution.

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