Cyclopentadienylruthenium π Complexes of Subphthalocyanines: A “Drop‐Pin” Approach To Modifying the Electronic Features of Aromatic Macrocycles

Abstract

Seitenwahl: Die Koordination von Cp*Ru (Cp*=C5Me5) an die konkave und konvexe π‐Oberfläche von Subphthalocyaninen ist ein neuer Ansatz zur Funktionalisierung von Subazaporphyrinen. Die konvexe Seite ist reaktiver, während die Koordination an die konkave Seite den stärkeren diatropen Einfluss auf den Cp*‐Liganden und die größere Veränderung der π‐elektronischen Eigenschaften des Makrocyclus bewirkt.

A Core‐Expanded Subphthalocyanine Analogue with a Significantly Distorted Conjugated Surface and Unprecedented Properties

“…They demonstrated differences in electron‐transfer abilities and ring‐current effects between the convex and concave surfaces 14. 15 Herein, we present a novel approach to a highly distorted SubPc analogue. Not only does this analogue have unique properties, but we were also able to investigate its convex and concave conjugated surfaces.…”

η5‐Cyclopentadienyliron(II)–[14]Triphyrin(2.1.1) Sandwich Compounds: Synthesis, Characterization, and Stable Redox Interconversion

“…However larger macrocyclic π‐conjugated systems with monovalent anionic character has been scarcely reported to date, which is due to the weak coordination ability of π‐extended Cp‐type ligands. Especially in porprhyin families, there are a few reports in this context:3 1) Cp‐Sc III ‐porphyrin,4a Cp‐Zr II ‐porphyrin,4b and Cp*‐Ru IV ‐porphycene (Cp*=pentamethylcyclopentadienyl),4c although porphyrin and porphycene are divalent ligands; and 2) β,β′‐fused monoruthenocenylporphyrins, bisferrocenoporphyrins,5a metaloporphyrcenes,5b and cyclopentadienylruthenium π complexes of subphthalocyanines,5c where that five‐membered ring moiety (pyrrole or cyclohexadiene moiety) acted as ligands. Only recently, double‐decker iron(II) complexes of dithiaethyneporphyrin6 and N‐fused porphyrin (NFP),7 where they behaved as macrocyclic tridentate ligands with a single negative charge, have been reported.…”

Real Sociedad Española de Química Prizes 2013

“…After a postdoctoral fellowship with Wolfram Schaefer at the Max Planck Institute for Biochemistry, Martinsried (1978–1980), he joined Abello/Merck Sharp & Dohme as a Senior Researcher, and was appointed to the faculty at the UAM in 1985. Torres and his research group are interested in supramolecular chemistry and molecular organic materials, in particular the synthesis of low‐symmetry phthalocyanines 1. Torres is on the International Advisory Board of ChemPlusChem…”