Syntheses, Structures, and Spectroscopic Properties of 1,10‐Phenanthroline‐Based Macrocycles Threaded by PtC 8 Pt, PtC 12 Pt, and PtC 16 Pt Axles: Metal‐Capped Rotaxanes as Insulated Molecular Wires

Autor:	Nancy Weisbach, Hashem Amini, Joseph H. Reibenspies, Zuzana Baranová, John A. Gladysz, Sébastien Gauthier, Nattamai Bhuvanesh
Rok vydání:	2019
Předmět:	Steric effects 010405 organic chemistry Chemistry Phenanthroline Organic Chemistry chemistry.chemical_element General Chemistry Crystal structure Nuclear magnetic resonance spectroscopy 010402 general chemistry 01 natural sciences Catalysis 0104 chemical sciences NMR spectra database Molecular wire Crystallography chemistry.chemical_compound Cyclic voltammetry Platinum
Zdroj:	Chemistry – A European Journal. 25:15896-15914
ISSN:	1521-3765 0947-6539
DOI:	10.1002/chem.201903927
Popis:	The platinum polyynyl complexes trans-(C6 F5 )(p-tol3 P)2 Pt(C≡C)n/2 H undergo oxidative homocoupling (O2 , CuCl/TMEDA) to diplatinum polyynediyl complexes trans, trans-(C6 F5 )(p-tol3 P)2 Pt(C≡C)n Pt(Pp-tol3 )2 (C6 F5 ) (n=4, 2; 6, 5; 8, 8; 92-97 %) as reported previously. When related reactions are conducted in the presence of CuI adducts of the 1,10-phenanthroline-based macrocycles 2,9-(1,10-phenanthrolinediyl)(p-C6 H4 O(CH2 )6 O)2 (1,3-C6 H4 ) (10, 33-membered) or 2,9-(1,10-phenanthrolinediyl)(p-C6 H4 O(CH2 )6 O)2 (2,7-naphthalenediyl) (11, 35-membered), excess K2 CO3 , and I2 (oxidant), rotaxanes are isolated that feature a Pt(C≡C)n Pt axle that has been threaded through the macrocycle (2⋅10, 9 %; 5⋅10, 41 %; 5⋅11, 28 %; 8⋅10, 12 %; 8⋅11, 9 %). Their crystal structures are determined and analyzed in detail, particularly with respect to geometric perturbations and the degree of steric sp carbon chain insulation. NMR spectra show a number of shielding effects. UV/Vis spectra do not indicate significant electronic interactions between the Pt(C≡C)n Pt axles and macrocycles, although cyclic voltammetry data suggest rapid reactions following oxidation.
Databáze:	OpenAIRE
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