Folding and Aggregation of Oligoviologens in Water and Cucurbit[n]uril (n=7, 8) Modulation

doi:10.6023/cjoc202108025

Abstract

To study the conformations and aggregation of linear viologen radical cation-incorporated molecules in water, a series of water-soluble oligoviologens with different length and linkers were prepared. ¹H NMR experiments in deuteroxide showed that cucurbit[7]uril (CB[7]) and cucurbit[8]uril (CB[8]) encapsulate their p-xylylene linkers instead of the bipyridinium units. UV-vis absorption experiments indicated that in the aqueous solution of sodium dithionite the viologen units of the oligomers were reduced to the radical cation species which were driven to dimerize through pleated conformations, leading to the formation of trisradical cation species. Dynamic light scattering experiments revealed that the foldamer dimers further aggregated to afford nanoscale particles. Adding CB[7] decomposed all the aggregated foldamer nanoparticles through 1:1 encapsulation of the viologen radical cation units, whereas the addition of CB[8] broke the foldamers and their large aggregates through 1:2 encapsulation of the viologen radical cations. Introducing a rigid linker to the linear viologen molecule could further enhance their stacking in the radical cation state. Although the folding and dimerization of linear viologen radical cation molecules have been established in acetonitrile in the literature, this study demonstrates that in water such multiple viologen radical cation molecules not only undergo folding to form stable dimers, but also further aggregate to give rise to nanoscale particles.

Key words: folding, aggregation, radical cation, cucurbit[n]uril (n=7,8), 4,4'-bipyridinium, aqueous medium

Cite this article

Wen-Chang Peng, Hui Wang, Dan-Wei Zhang, Zhan-Ting Li. Folding and Aggregation of Oligoviologens in Water and Cucurbit[n]uril (n=7, 8) Modulation[J]. Chinese Journal of Organic Chemistry, 2022, 42(3): 863-870.

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Fig. & Tab. 5

Scheme 1. Structures of compounds 1V•2Cl, 2V•4Cl, 3V•6Cl and 2V'•4Cl

Figure 1. UV-vis absorption spectra of compounds 1V•2Cl, 2V•4Cl, 3V•6Cl and 2V4'•Cl ([BIPY]=0.20 mmol/L) in water containing sodium dithionite (0.10 mol/L), which reduces their BIPY2+ unit(s) to BIPY•+ at 25 ℃

Figure 2. Absorption spectra of (a) 2V2(•+) (0.02~0.14 mmol/L), (b) 2V2(•+)+1.0 equiv. CB[8] (0.02~0.14 mmol/L), (c) 3V3(•+) (0.01~0.09 mmol/L) and (d) 3V3(•+)+1.5 equiv. CB[8] (0.01~0.09 mmol/L) in water containing sodium dithionite (50 mmol/L) (inset: the plot of ε of the absorption band around 1000 nm vs. [BIPY])

Figure 3. Tentative representation of the structures of pleated dimers (2V2(•+))2 and (3V3(•+))2 and encapsulation complexes (2V2(•+))2$\subset$(CB[8])2 and (3V3(•+))2$\subset$(CB[8])3 Tentative representation of the structures of pleated dimers (2V2(•+))2 and (3V3(•+))2 and encapsulation complexes (2V2(•+))2$\subset$(CB[8])2 and (3V3(•+))2$\subset$(CB[8])3

Figure 4. DLS profile of the solution of 1V•+, 2V2(•+), 3V3(•+) and 2V'2(•+) in water containing sodium dithionite (50 mmol/L) in the (a) absence or presence of (b) CB[7] or (c) CB[8] ([BIPY]=0.28 mmol/L)

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紫精寡聚体的水相折叠和堆积及葫芦[n]脲(n=7, 8)调控