Realization of a "Lockable" molecular switch via pH- and redox-modulated cyclization

Richmond, C. J., Parenty, A. D. C., Song, Y. -F., Cooke, G. and Cronin, L. (2008) Realization of a "Lockable" molecular switch via pH- and redox-modulated cyclization. Journal of the American Chemical Society, 130(39), pp. 13059-13065. (doi:10.1021/ja803338m)

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Abstract

A switchable organic system involving four distinct states that can be interconverted by use of both pH and redox chemistry as control parameters has been developed. The key molecules involved in this system are the phenanthridine-based heterocycles 1 -isobutyl-1,2,3,12b-tetrahydroimidazo[1,2-f]phenanthridine (TIP) and 5-[2-(isobutylamino)ethyl]phenanthridinium (AEP). These two states are interchangeable via pH control, and in addition they can also be further manipulated by oxidation or reduction to convert them to their "pH-inert" forms: 1-isobutyl-2,3-dihydro-1H-imidazo[1,2-f]phenanthridinium (DIP) and 5-[2-(isobutylamino)ethyl]-5,6-dihydrophenanthridine (AEDP), respectively. UV and H-1 NMR experiments carried out in a biphasic dichloromethane (DCM)/water solution were used for in situ structure determination. The results showed that the pH-modulated cyclization and phase-transfer process between the TIP and AEP states was essentially quantitative and repeatable without any significant loss in activity and that reduction or oxidation could be used to lock out these states against such acid-base-induced changes.

Item Type:Articles
Keywords:CHEMISTRY COMPONENTS CYCLIZATION DEVICES ELECTRON-TRANSFER IN-SITU ION LOGIC GATES MACHINE MOLECULE MOLECULES NMR ONE-POT OXIDATION PARAMETERS PH REDOX redox chemistry REDUCTION STATE Structure SWITCH SYSTEM SYSTEMS WIRES
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Cooke, Professor Graeme and Parenty, Mr Alexis and Richmond, Mr Craig and Song, Dr Yufei and Cronin, Professor Leroy
Authors: Richmond, C. J., Parenty, A. D. C., Song, Y. -F., Cooke, G., and Cronin, L.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Journal of the American Chemical Society
ISSN:0002-7863

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
400012Understanding and controlling the self assembly of nanoscale polyoxometalate clustersLeroy CroninEngineering & Physical Sciences Research Council (EPSRC)EP/C542827/1Chemistry