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: Amini H; Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas, 77842-3012, USA., Baranová Z; Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas, 77842-3012, USA., Weisbach N; Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas, 77842-3012, USA., Gauthier S; Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas, 77842-3012, USA., Bhuvanesh N; Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas, 77842-3012, USA., Reibenspies JH; Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas, 77842-3012, USA., Gladysz JA; Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas, 77842-3012, USA.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2019 Dec 10; Vol. 25 (69), pp. 15896-15914. Date of Electronic Publication: 2019 Nov 12.
DOI: 10.1002/chem.201903927
Abstrakt: The platinum polyynyl complexes trans-(C 6 F 5 )(p-tol 3 P) 2 Pt(C≡C) n/2 H undergo oxidative homocoupling (O 2 , CuCl/TMEDA) to diplatinum polyynediyl complexes trans, trans-(C 6 F 5 )(p-tol 3 P) 2 Pt(C≡C) n Pt(Pp-tol 3 ) 2 (C 6 F 5 ) (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-C 6 H 4 O(CH 2 ) 6 O) 2 (1,3-C 6 H 4 ) (10, 33-membered) or 2,9-(1,10-phenanthrolinediyl)(p-C 6 H 4 O(CH 2 ) 6 O) 2 (2,7-naphthalenediyl) (11, 35-membered), excess K 2 CO 3 , and I 2 (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.
(© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Databáze: MEDLINE
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