190366-48-4

Upstream product

• 64443-05-6 tetrakis(actonitrile)copper(I) hexafluorophosphate 
• 90030-13-0 ((C₂H₄O)2C₆H₄)NC₅H₂C₂H₂C₅H₂N(C₆H₄(C₂H₄O)2)OC₂H₄O 
• 190366-45-1 5''-{4-[9-(4-Methoxy-phenyl)-[1,10]phenanthrolin-2-yl]-butyl}-5-(3-{4-[tris-(4-tert-butyl-phenyl)-methyl]-phenoxy}-propyl)-[2,2';6',2'']terpyridine 

Relevant academic research and scientific papers

Rotaxanes incorporating two different coordinating units in their thread: Synthesis and electrochemically and photochemically induced molecular motions

Three different multicomponent molecular systems have been synthesized by means of the three-dimensional template effect of copper(I). These systems incorporate both a coordinating ring (2,9-diphenyl-1,10-phenanthroline-containing 30-membered ring) and a molecular string which consists of two different coordination sites (2,9-disubstituted-1,10-phenanthroline and 5,5″-disubstituted-2,2′:6′,2″-terpyridine unit). Each end of the string could be functionnalyzed by a small group or by a bulky stopper (tris(p-tert-butylphenyl)-(4-hydroxyphenyl)methane), leading to an unstoppered compound, to a semi-rotaxane, or to a real rotaxane. As in the case of a disymmetrical copper [2]-catenane, large reversible molecular motions have been induced both electrochemically and photochemically. The driving force of the rearrangement processes is the high stability of two markedly different coordination environments for the copper(I) and copper(II) ions. In the copper(I) state, two phenanthroline units (one of the ring, one of the string) interact with the metal ion in a tetrahedral geometry (CuI(4)), whereas in the copper(II) state, one phenanthroline belonging to the ring and the terpyridine of the string afford a five-coordinate geometry (CuII(5)). The rates of the molecular motion processes (from CuII(4) to CuII(5) and from CuI(5)) to CuI(4)) are respectively faster and slower (minutes time scale) as compared to those for the catenane species. This result could be interpreted on the basis of structural differences between the rotaxane and catenane systems.

Electrochemically induced molecular motions in copper-complexed threaded systems: From the unstoppered compound to the semi-rotaxane and the fully blocked rotaxane

A molecular assembly incorporating a coordinating ring (30-membered macrocycle) and a molecular string with two chelating sites (bidentate and terdentate ligands) has been constructed by means of the template effect of copper(I). Electrochemical oxidation of tetracoordinate copper(I) to copper(II) results in the motion of the ring and the metal ion from the bidentate to the terdentate site on the string due to the preference of copper(II) for a square base pyramidal-type geometry vs. tetrahedral. Electrochemical reduction of copper(II) to copper(I) leads to the opposite movement. In order to avoid a dethreading process (essentially due to the copper(II) complexes) during the redox cycles, one or two blocking groups [tris(p-tert-butylphenyl)(4-hydroxyphenyl)methane] have been covalently attached to the ends of the thread to afford a semi-rotaxane or a rotaxane, respectively. In the case of the rotaxane, a perfect reversibility of the motions of the ring on the thread has been demonstrated by electrochemical techniques. CNRS-Gauthier-Villars.