Tuning the Sign and Magnitude of Complexation‐Induced p K a Shifts in Cucurbit[7]uril Host‐Guest Complexes by Molecular Engineering
Abstract Cucurbiturils are popular macrocyclic receptors that bind complementary guest molecules with high affinity in aqueous environments. They are recognized for their ability to selectively bind positively charged guest molecules, including ionizable ammonium cations which frequently display muc...
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| Published in: | Israel journal of chemistry 2024-01 |
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| Main Authors: | , , , , |
| Format: | Article |
| Language: | eng |
| Online Access: | Request full text |
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| Summary: | Abstract Cucurbiturils are popular macrocyclic receptors that bind complementary guest molecules with high affinity in aqueous environments. They are recognized for their ability to selectively bind positively charged guest molecules, including ionizable ammonium cations which frequently display much higher affinity than their neutral counterparts. This selectivity for the protonated species is translated into an increase in the basicity of encapsulated guests (i. e. into complexation‐induced positive p K a shifts). However, despite being very rare, negative p K a shifts can be observed for specific guests. Following a previous work from our group reporting slightly negative p K a shifts for flavylium and chalcone dyes featuring N ‐diethylamino substituents (Δp K a =− 0.2), herein we report a systematic study on the complexation of N ‐dialkylaminochalcones with CB7. The results show that the p K a shifts of these host‐guest complexes can be rationally tuned by the nature of the N ‐dialkylamino groups and as well by target substitutions on the skeleton of the dye, allowing the design of a CB7 1 : 1 host‐guest complex with a Δp K a =− 0.6. |
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| ISSN: | 0021-2148 1869-5868 |