Supramolecular ensemble containing dinuclear amine-thiolate complexes and organic components
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LOZAN, Vasile. Supramolecular ensemble containing dinuclear amine-thiolate complexes and organic components. In: Physical Methods in Coordination and Supramolecular Chemistry, 8-9 octombrie 2015, Chişinău. Chisinau, Republic of Moldova: 2015, XVIII, p. 156.
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Physical Methods in Coordination and Supramolecular Chemistry
XVIII, 2015
Conferința ""Physical Methods in Coordination and Supramolecular Chemistry""
Chişinău, Moldova, 8-9 octombrie 2015

Supramolecular ensemble containing dinuclear amine-thiolate complexes and organic components


Pag. 156-156

Lozan Vasile
 
Institute of Chemistry
 
Disponibil în IBN: 23 aprilie 2020


Rezumat

The chemistry of container molecules has developed extensively over the past two decades. Many container molecules such as calixarenes, resorcarenes, cyclodextrins, carcerands and glycourils have been invaluable in studying the fundamental principles of inclusion phenomena and consequently their use in separation science or drug delivery, as two examples of application. Importantly, the area has attracted interest in the field of supramolecular chemistry because the properties of such host–guest compounds are often different from those of their constituent components. By adjusting the size and form of the binding cavity it is often possible to complex co-ligands in unusual coordination modes, to activateand transform small molecules, or to stabilize reactive intermediates [1, 2]. One subclass are the metallated container molecules, in which metal ions and clusters are used as both a point of recognition and to give the container a well-defined structure. Such compounds also allow for an interplay of molecular recognition and transition-metal catalysis, and for the construction of more effective enzyme mimics. Of interest to the present work is the ability of metallocavitands to recognize and encapsulate difunctionalised molecules towards stabilising or enhancing the optical and electronic properties of redox- and photo-active compounds within a confined environment set up by two hemispheres.figure1 [(LNiII 2)2(acetylenedicarboxylate)]2+ 2. [(LNiII 2)2(terephtalate)]2+ 3. [(LNiII 2)2(isophtalate)]2+ 4. [(LNiII 2)2(ferrocendicarboxylate)]2+ 5. [(LNiII 2)2(naphthalene diimide dicarboxylate)]2+The complexes 1-5 were readily prepared from the reaction of the dinuclear complex [LNiII 2(μ-Cl)]+ (L=24-membered macrocyclic hexaaza-dithiophenolate ligand) and the corresponding triethylammonium dicarboxylate, prepared in situ from the acid and triethylamine in methanol in a 1:2 molar ratio, and isolated in high yield as the perchlorate or tetraphenylbora-te salts.The complexes, have been synthesized and characterised by UV/Vis-, IR-spectrosco-py, Cyclovoltamperometry, and X-ray crystallography. Each dicarboxylate dianion acts as a quadridentate bridging ligand linking two bioctahedral LM2 units via μ1,3-bridging carboxy-late functions to generate discrete dications with a central LM2(O2CR-CO2)M2L core. Magnetic susceptibility measurements on the complexes over the range 2.0 -295K reveal the presence of weak ferromagnetic exchange interactions between the NiII ions within the dinuclear subunits.