[2]Catenane consists of various functional groups and shows efficient binding towards Eu3+ and Gd3+. A cavity-bound catenated structure is also demonstrated by single crystal X-ray analysis.
Complexation of alkali and alkaline earth metal ion with the heteroditopic phen-ester, oxy-ether macrocyclic wheel (PhenMC) is established for the synthesis of interlocked molecular systems. The Single crystal X-ray structure...
A heteroditopic macrocycle, PhenMC, composed of phenanthroline ester, aromatic spacer and oxy ether moieties is explored to synthesize two new rotaxanes, RTXN1 and RTXN2 by employing different templating strategies, active metal templation and donor‐acceptor interaction respectively. In this regard, Cu(I) mediated azide‐alkyne cycloaddition reaction is adopted to achieve RTXN1 in case of active metal templation. On the other hand, a new 1 : 1 threaded complex, PRT1 (pseudorotaxane) is synthesized via π‐π stacking interaction between viologen moiety containing alkyne terminated axle and PhenMC toward the development of RTXN2 by appropriately stoppering the pseudorotaxane. All the synthesized compounds are well characterized by several methods such as ESI‐MS, ITC, UV‐Vis, 1D and 2D NMR spectroscopy, wherever applicable. Furthermore, RTXN1 has been explored toward inorganic anion binding studies by NMR titration and electrochemical methods. Subsequently, redox behavior of RTXN2 with multiple redox centers has also been described by cyclic voltammetry and UV‐Vis spectroscopic studies.
A new oxy(ether)tris(amine) macrocycle, MC has been synthesized for CuII complex formation within the cavity of the macrocyclic wheel in endotopic fashion. This complex is further reacted with the bidentate chelating ligands, 1,10-phenanthroline (L1), 2,2′-bipyridyl (L2), 4,4′-dimethyl-2,2′-bipyridyl (L3) and 5,5′-dimethyl-2,2′-bipyridyl (L4) to achieve the pseudorotaxanes PRT1–PRT4, respectively. These bis-heteroleptic complexes were characterized by the electrospray ionization mass spectrometry (ESI-MS), UV/Vis, EPR spectroscopy and Single-crystal X-ray structural analysis. Binding constants of the heteroleptic complexes were found in the range of 1.16 × 10(2) to 1.55 × 103 M(-1) in acetonitrile. Further, the double level selectivity studies of MC using different metal ions [CoII, NiII, CuII, ZnII] and a number of simple bidentate chelating ligands shows the selective formation of PRT1 that justifies the self-sorting nature of the system. Further, substitution of axles from pseudorotaxanes PRT2–PRT4 could also be achieved by L1 with nearly 100% efficiency. To corroborate the experimental studies (comparison with the crystal geometry, importance of the π–π stacking, etc.) the geometries of the pseudorotaxanes were optimized using DFT (B3LYP) in the gas phase.
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