Reversible Mechanical Interlocking of D‐Shaped Molecular Karabiners bearing Coordination‐Bond Loaded Gates: Route to Self‐Assembled [2]Catenanes |
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Authors: | Soumyakanta Prusty Dr. Shobhana Krishnaswamy Sreenivasulu Bandi Dr. Baby Chandrika Dr. Jingwei Luo Prof. Dr. J. Scott McIndoe Prof. Dr. Garry S. Hanan Prof. Dr. Dillip Kumar Chand |
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Affiliation: | 1. Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036 (India);2. Sophisticated Analytical Instrument Facility, Indian Institute of Technology Madras, Chennai 600036 (India);3. Department of Chemistry, University of Montreal, Montreal (Canada);4. Department of Chemistry, University of Victoria, Victoria (Canada) |
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Abstract: | Complexation of 1,4‐phenylenebis(methylene) diisonicotinate, L1 , with cis‐protected PdII components, [Pd( L′ )(NO3)2], in an equimolar ratio yielded binuclear complexes, 1 a – d of [Pd2( L′ )2( L1 )2](NO3)4 formulation where L′ stands for ethylenediamine (en), tetramethylethylenediamine (tmeda), 2,2′‐bipyridine (bpy), and phenanthroline (phen). The combination of 4,4′‐bipyridine, L2 , with the cis‐protected PdII units is known to yield molecular squares, 2 a – d . However, 2 b – d coexist with the corresponding molecular triangles, 3 b – d . Combination of an equivalent each of the ligands L1 and L2 with two equivalents of cis‐protected PdII components in DMSO resulted in the D ‐shaped heteroligated complexes [Pd2( L′ )2( L1 )( L2 )](NO3)4, 4 a – d . Two units of the D ‐shaped complexes interlock, in a concentration dependent fashion, to form the corresponding [2]catenanes [Pd2( L′ )2( L1 )( L2 )]2(NO3)8, 5 a – d under aqueous conditions. Crystal structures of the macrocycle [Pd2(tmeda)2( L1 )( L2 )](PF6)4, 4 b′′ , and the catenane [Pd2(bpy)2( L1 )( L2 )]2(NO3)8, 5 c , provide unequivocal support for the proposed molecular architectures. |
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Keywords: | catenane dynamic equilibrium molecular karabiners palladium self‐assembly |
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