182802-99-9

Upstream product

• 17739-45-6 2-(2-bromoethoxy)tetrahydropyran 
• 158589-14-1 5,5''-dimethyl-2,2':6',2''-terpyridine 

Downstream Products

• 182803-04-9 5''-{4-[9-(4-Methoxy-phenyl)-[1,10]phenanthrolin-2-yl]-butyl}-5-methyl-[2,2';6',2'']terpyridine 

Relevant academic research and scientific papers

Electrochemically induced molecular motions in a copper(I) complex pseudorotaxane

A pseudorotaxane consisting of a coordinating ring, a molecular thread bearing two different coordination sites and a copper(I) ion displays electrochemically induced motions of the ring from one site to the other.

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.

Construction of interlocking and threaded rings using two different transition metals as a templating and connecting centers: Catenanes and rotaxanes incorporating Ru(terpy)2-units in their framework

This work describes a new method for the preparation of metal-containing catenanes and rotaxanes, using pure coordination chemistry, by stepwise reaction of organic fragments with two different transition metals. The key organic compound contains two terpyridine (terpy) ligands and one diphenylphenanthroline (dpp) moiety and was prepared in high yield by alkylation of 2,9-bis(hydroxyphenyl)-1,10-phenanthroline with 5-(3-methanosulfonyl-1-propyl)-5''-methyl-2,2':6',2''-terpyridine. Reaction of this polyfunctional ligand with 1 equiv of a dpp-containing 30-membered macrocycle and Cu(I) as a template led to a threaded Cu(dpp)2+-type precursor complex (P). Due to the high affinity of Cu(I) for the dpp ligands, the reaction is selective, and no competition of the terpy units for the metal takes place. Thus, this threaded complex contains two free terpy moieties suitable for a further coordination reaction. Ru(II) was used to build the stoppers or to clip the free ligands due to the high stability of Ru(terpy)22+ complexes. Compound P reacts with Ru(DMSO)4Cl2 in 1,2-dichloroethane-EtOH at 70 °C under high dilution conditions to give the desired catenate in 43% yield. A Cu coordinated rotaxane was obtained by stoppering the free ends of precursor P with 2 equiv of Ru(terpy)(acetone)3(BF4)2. In both cases the intertwined geometry of the dpp units is maintained after Ru(II) coordination. The complexes were characterized by spectroscopic methods, FAB-MS, and cyclic voltammetry. The high stability of the Ru complexes allows for the selective removal of Cu(I). Thus, reaction of the Cu-complexed rotaxane or the catenate with KCN in MeCN-H2O led to the corresponding rotaxane or catenane, respectively, in which the intertwined topography has been destroyed upon liberation of the dpp ligands. This approach opens a new way for the preparation of multicomponent species with promising photochemical properties.