183187-82-8

Upstream product

• 1603-41-4 (5-methyl-pyridin-2-yl)amine 
• 3510-66-5 2-Bromo-5-methylpyridine 
• 189195-41-3 5-methyl-2-(tri-n-butylstannyl)pyridine 
• 183187-81-7 (E)-3-Dimethylamino-1-(5-methyl-pyridin-2-yl)-propenone 
• 5308-63-4 1-(5-methyl-pyridin-2-yl)-ethanone 
• 158589-14-1 5,5''-dimethyl-2,2':6',2''-terpyridine 

Downstream Products

• 309243-30-9 5''-bromomethyl-5-{4-[tris-(4-tert-butyl-phenyl)-methyl]-phenoxymethyl}-[2,2';6',2'']terpyridine 

Relevant academic research and scientific papers

140. Trinuclear double helicates of iron(II) and nickel(II): Self-assembly and resolution into helical enantiomers

The synthesis of the linear tris[terpyridine] 1 with three tridentate binding sites is described. The reaction with metal ions of octahedral coordination geometry, such as FeII or NiII, leads to the self-assembly of trinuclear complexes [M3(I)2]6+, which display properties in agreement with a double helical structure. The trinuclear iron(II) helicate has been resolved into its enantiomers.

Synthesis of [5]rotaxanes containing Bi- and tridentate coordination sites in the axis

A new example of a linear [5]rotaxane has been synthesized by using the traditional "gathering-and-threading" approach but based on an unusual axle incorporating a symmetrical bis(bidentate) chelating fragment built on a 4,7-phenanthroline core. The stopp

Messages in molecules: Ligand/cation coding and self-recognition in a constitutionally dynamic system of heterometallic double helicates

Double helicates are known to exhibit self-recognition characteristics determined by the coordination geometry of the metal involved as well as by the topicity of the ligands. Combining tridentate (terpyridine, T) or bidentate (bipyridine, B) subunits in a tritopic strand affords a set of ligands able to assemble by pairs to form double heli cates, homo- or heterostranded, homo-or heterotopic, depending on the coordination properties of the metals in volved. The four ligand strands, BBB, TTT, BBT, and TBT form constitutionally dynamic sets of double helicates with the metal ions CuI, CuII, and ZnII; these helicates correspond to the correct coding of the BB, BT, and TT pairs for tetra-, penta-, and hexacoordinate CuI, Cu II, and Zn" cations, respectively.

Dynamic Helicates Self-Assembly from Homo- and Heterotopic Dynamic Covalent Ligand Strands

The understanding and the application of reversible covalent reactions and coordination chemistry together with the proper design of the molecular frameworks, allow to achieve not only well-defined output architectures but also different grades of complex behavior. In this work, the dynamic nature of the helical systems offers an additional level of complexity by combining self-sorting on two levels: 1) the build-up of the ligand strand constituents from their components through dynamic covalent chemistry; 2) the assembly of the helicates from the ligands and the metal cations through dynamic metallo-supramolecular chemistry. The information encoded in the ligands constituent molecule was read differently (and accurately at the same time) by metal cations that varied in the coordination algorithms. It enabled the selective formation of a specific type of helicates from a wide library of helicates formed by the possible combination of subcomponents. Ligands containing dynamic tridentate and/or bidentate binding motifs in the same strand were studied to explore the helicates self-assembly with appropriate metal cations.

Chemically induced contraction and stretching of a linear rotaxane dimer

Copper(I)-induced assembly of two self-complementary identical units, which consist of a ring that incorporates a 1,10-phenanthroline group attached to a small filament containing a second 1,10-phenanthroline (phen) group, leads quantitatively to a doubly threaded complex. Each copper(I) center is four-coordinate and is located inside a ring and bound to a phen from the macrocyle. The two other coordination sites are occupied by a phen from the filament connected to the other ring. An X-ray structure of the dicopper(I) complex unambiguously demonstrates the doubly threaded nature of the system. The molecule has C2 symmetry in the crystal. This is an extended form with a Cu ··· Cu separation of 18.3 A and an overall length close to 40 A. Further synthetic work, which utilizes the two terminal phenolic functions of the previous dicopper(I) complex, gives rise to a more complex system in which both filaments have been prolonged in opposite directions by 2,2′:6′,2″-terpyridine (terpy) motifs and bulky stoppers. The organic backbone is that of a rotaxane dimer. Although redox cycling of Cu1 to Cu11 did not lead to intramolecular rearrangement, simple chemical reactions induced large conformational changes. The rotaxane dimer was set in motion as follows. The dicopper(I) complex, which is in an extended conformation, was demetallated by using KCN. From the free ligand, the dizinc complex was formed quantitatively at room temperature. 1H NMR data show that a new conformation is obtained: each Zn11 is five-coordinate (phen + terpy), and the molecule is in a contracted conformation. This process is reminiscent of biological muscles in the sense that the two filaments of this system can be moved along one another in a gliding motion that keeps the whole system together, but which converts a stretched compound (overall length ≈83 A) into a contracted species (overall length ≈65 A, according to CPK models). The motion is quantitatively reversed by the addition of an excess of copper(I) to the dizinc complex; this regenerates the extended starting form. Although the motivation of the present contribution was to illustrate that a musclelike molecule may be stretched or contracted using electrochemistry and coordination chemistry, the main body of the work is organic synthesis. This is testified by the fact that the dicopper(I) rotaxane dimer was obtained in 23 steps from commercially available compounds.

High yield synthesis of 5,5'-dimethyl-2,2'-bipyridine and 5,5-dimethyl- 2,2':6',2-terpyridine and some bisfunctionalization reactions using N- bromosuccinimide

5,5'-Dimethyl-2,2'-bipyridine and 5,5-dimethyl-2,2':6',2-terpyridine were synthesized in multigram quantities in high yields utilizing organotin intermediates and Stille coupling procedures. The obtained ligands were dibrominated using N-bromosuccinimide.