The Library
Disentangling contributions to guest binding inside a coordination cage host : analysis of a set of isomeric guests with differing polarities
Tools
Mozaceanu, Cristina, Solea, Atena B., Taylor, Christopher G. P., Sudittapong, Burin and Ward, Michael D. (2022) Disentangling contributions to guest binding inside a coordination cage host : analysis of a set of isomeric guests with differing polarities. Dalton Transactions, 51 (40). pp. 15263-15272. doi:10.1039/D2DT02623F ISSN 1477-9226.
|
PDF
WRAP-Disentangling-contributions-to-guest-binding-inside-a-coordination-cage-host-analysis-of-a-set-of-isomeric-guests-with-differing-polarities-Ward-2022.pdf - Published Version - Requires a PDF viewer. Available under License Creative Commons Attribution 4.0. Download (2718Kb) | Preview |
Official URL: http://dx.doi.org/10.1039/D2DT02623F
Abstract
Binding of a set of three isomeric guests (1,2-, 1,3- and 1,4-dicyanobenzene, abbreviated DCB) inside an octanuclear cubic coordination cage host H (bearing different external substitutents according to solvent used) has been studied in water/dmso (98 : 2) and CD2Cl2. These guests have essentially identical molecular surfaces, volumes and external functional groups to interact with the cage interior surface; but they differ in polarity with dipole moments of ca. 7, 4 and 0 Debye respectively. In CD2Cl2 guest binding is weak but we observe a clear correlation of binding free energy with guest polarity, with 1,4-DCB showing no detectable binding by NMR spectroscopy but 1,2-DCB having −ΔG = 9 kJ mol−1. In water (containing 2% dmso to solubilise the guests) we see the same trend but all binding free energies are much higher due to an additional hydrophobic contribution to binding, with −ΔG varying from 16 kJ mol−1 for 1,4-DCB to 22 kJ mol−1 for 1,4-DCB: again we see an increase associated with guest polarity but the increase in −ΔG per Debye of dipole moment is around half what we observe in CD2Cl2 which we ascribe to the fact the more polar guests will be better solvated in the aqueous solvent. A van't Hoff analysis by variable-temperature NMR showed that the improvement in guest binding in water/dmso is entropy-driven, which suggests that the key factor is not direct electrostatic interactions between a polar guest and the cage surface, but the variation in guest desolvation across the series, with the more polar (and hence more highly solvated) guests having a greater favourable entropy change on desolvation.
Item Type: | Journal Article | ||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Subjects: | Q Science > QD Chemistry | ||||||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||||||||
Library of Congress Subject Headings (LCSH): | Coordination compounds, Organometallic compounds, Organometallic chemistry -- Research, Molecules | ||||||||||||
Journal or Publication Title: | Dalton Transactions | ||||||||||||
Publisher: | Royal Society of Chemistry | ||||||||||||
ISSN: | 1477-9226 | ||||||||||||
Official Date: | 28 October 2022 | ||||||||||||
Dates: |
|
||||||||||||
Volume: | 51 | ||||||||||||
Number: | 40 | ||||||||||||
Number of Pages: | 10 | ||||||||||||
Page Range: | pp. 15263-15272 | ||||||||||||
DOI: | 10.1039/D2DT02623F | ||||||||||||
Status: | Peer Reviewed | ||||||||||||
Publication Status: | Published | ||||||||||||
Access rights to Published version: | Open Access (Creative Commons) | ||||||||||||
Date of first compliant deposit: | 10 October 2022 | ||||||||||||
Date of first compliant Open Access: | 11 October 2022 | ||||||||||||
RIOXX Funder/Project Grant: |
|
Request changes or add full text files to a record
Repository staff actions (login required)
View Item |
Downloads
Downloads per month over past year