Redox-Induced Conformational Alteration of N,N-Diarylamides

Abstract

We constructed a novel molecular conformational alteration system with an N-aryl-N-phenylacetamide structure, in which the N-aryl group consists of a hydroquinone-p-quinone system as a redox-dependent aromatic trigger. The amide conformation depended on the oxidation state of the aryl group, and the two states (compounds 2 and 3) were reversibly converted to each other by redox reactions. Such compounds would be applied as useful structural units for external stimulus-responsive control on the shape and function of large molecules or supramolecules.

Rapid and Efficient Electrochemical Actuation in a Flexible Perylene Bisimide Dimer

“…In contrast, actuation brought about by a change in the molecular conformation is anticipated to be inherently faster. Although this idea has led to the development of several molecular actuators that accomplish a variety of motions, such as sliding, rotation, cavity expansion, pivoting, and hinge motion, − there are also certain limitations. In addition to a faster response, an efficient electrochemical actuator should also be able to produce large deformations at relatively low operating voltages, demonstrate stability across the entire electrochemical window of operation, and offer the possibility of building macroscopic actuators through a bottom-up assembly process.…”

Redox-Dependent Conformational Switching of Diphenylacetylenes

“…The most well known of these involve the use of redox active catenanes, [5][6][7][8] metal coordination compounds, [9][10][11][12][13][14][15] rotaxanes, [11,12,14,[16][17][18][19][20][21][22] π-systems, [23][24][25][26][27][28] and crowded alkenes [29]. These systems are finding increasing application in solid-state electronic devices.…”

Interactions between suitably functionalised conformationally distinct benzanilides and phospholipid monolayers

“…3,4 It is well established that N-unsubstituted benzanilides exhibit a distinct difference in conformation compared to their Nsubstituted analogues, both in solution and in the solid state. [5][6][7][8][9][10][11][12][13][14] The consequences of achieving such conformational control by simple N-substitution has been studied in a number of applications, not least: for facilitating conformational communication via stereogenic axes; 12 for controlling oligourea helicity; 15 for modifying the bioactivity of synthetic retinoids 16 and cytokinins; 17 as a molecular splint; 18 for carrying out a so-called 'impossible' macrocyclisation; 19 and for the development of fluorescent sensors. 20 It is only relatively recently that conformational preferences of small molecules have been exploited, [8][9][10][11][12][13][14][15][16] however, the importance of conformational control is well recognized in biology.…”

“…[5][6][7][8][9][10][11][12][13][14] The consequences of achieving such conformational control by simple N-substitution has been studied in a number of applications, not least: for facilitating conformational communication via stereogenic axes; 12 for controlling oligourea helicity; 15 for modifying the bioactivity of synthetic retinoids 16 and cytokinins; 17 as a molecular splint; 18 for carrying out a so-called 'impossible' macrocyclisation; 19 and for the development of fluorescent sensors. 20 It is only relatively recently that conformational preferences of small molecules have been exploited, [8][9][10][11][12][13][14][15][16] however, the importance of conformational control is well recognized in biology. For example, protein acylation is common, and many different cellular proteins are acylated by long chain fatty acids as a method to increase the tendency of the protein to become associated with a lipid membrane.…”

“…We believed that the extent of any interaction would depend on whether the compounds were present in the cis-or trans-conformation, which in turn would depend on the N-substitution pattern, Scheme 1. [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] As well as potentially developing a new class of membrane interactive molecule, it would be interesting to study these compounds as possible antibacterial or anaesthetic agents which were able to assert their effects by disrupting cell membranes in some way, or even as drug delivery systems where known drugs could be delivered to cells only to be released when the host molecule has docked into the cell membrane. Additionally, these molecules could be utilised in diagnostics wherein analytes which are capable of N-substitution (e.g.…”