0000000000114400
AUTHOR
J. Fraser Stoddart
Langmuir films and Langmuir-Blodgett multilayers incorporating mechanically-threaded molecules-pseudorotaxanes
This paper describes the synthesis of a π-electron rich aromatic lipid containing a polyether thread intercepted by a 1,5-dioxynaphthalene moiety. The terminus of one end of the polyether is a methoxyl group and the other a glycerol unit linked via the 2-oxo position, while the 1,3-oxo functions are covalently attached to octadecyl chains. This compound, when cospread at the air-water interface with the tetracationic cyclophane, cyclobis(paraquat-p-phenylene), and the phospholipid, dimyristoylphosphatidic acid, as its monoanion, forms self-assembled pseudorotaxanes which are self-organized into a two-dimensional supramolecular array at the interface. The electrostatic interactions between t…
Towards Organization of Molecular Machines at Interfaces. Langmuir Films and Langmuir-Blodgett Multilayers of an Acid-Base Switchable Rotaxane
In this context we investigated, for the first time, the organi-zation of a non-amphiphilic tricationic switchable rotaxaneand its dumbbell-shaped component into Langmuir films andLangmuir–Blodgett (LB) multilayers by using a cospreadingstrategy. The Langmuir films have been characterized by sur-face pressure–area (
Autonomous artificial nanomotor powered by sunlight
Light excitation powers the reversible shuttling movement of the ring component of a rotaxane between two stations located at a 1.3-nm distance on its dumbbell-shaped component. The photoinduced shuttling movement, which occurs in solution, is based on a “four-stroke” synchronized sequence of electronic and nuclear processes. At room temperature the deactivation time of the high-energy charge-transfer state obtained by light excitation is ≈10 μs, and the time period required for the ring-displacement process is on the order of 100 μs. The rotaxane behaves as an autonomous linear motor and operates with a quantum efficiency up to ≈12%. The investigated system is a unique example of an artif…
A Comparison of Shuttling Mechanisms in Two Constitutionally Isomeric Bistable Rotaxane-Based Sunlight-Powered Nanomotors
To find out how best to optimize shuttling of the macrocycle in a particular class of photochemically driven molecular abacus, which has the molecular structure of BR-I6+ in its Mark I prototype (Ashton et al., Chem. Eur. J. 2000, 6, 3558), we have synthesized and characterized a Mark II version of this kind of two-station rotaxane comprised of six molecular modules, namely (a) a bisparaphenylene[34]crown-10 electron donor macrocycle M and its dumbbell-shaped component which contains (b) a Ru(ii)-polypyridine photoactive unit P2+ as one of its stoppers, (c) a p-terphenyl-type ring system as a rigid spacer S, (d) 4,4′-bipyridinium (A12+) and (e) 3,3′-dimethyl-4,4′-bipyridinium (A22+) electr…
Controlling Multivalent Interactions in Triply-Threaded Two-Component Superbundles
We have investigated the (1)H NMR spectra, the absorption spectra, the fluorescence spectra and decays, and the electrochemical properties of i). a tritopic receptor in which three benzo[24]crown-8 macrorings are fused onto a triphenylene core, ii). a trifurcated trication wherein three dibenzylammonium ions are linked 1,3,5 to a central benzenoid core, and iii). their 1:1 adduct which constitutes a triply-threaded, two-component supramolecular bundle. X-Ray crystallography has established the precise geometry of this paucivalent recognition motif in the solid state. In addition to [N(+)-H...O] hydrogen bonding and [C-H...O] interactions between the NH(2) (+) centers on the three dibenzylam…