Nanorings with copper(ii) and zinc(ii) centers: forcing copper porphyrins to bind axial ligands in heterometallated oligomers

Abstract

The stability of copper/zinc heterometallated porphyrin complex oligomers provides information on the strength of the copper porphyrin pyridine interaction. Heterometallated nanorings were prepared by template-directed synthesis.

Constructive quantum interference in a bis-copper six-porphyrin nanoring

“…10). This result is in good agreement with published X-ray crystallography and density functional theory (DFT) data for a similar template-bound six-membered porphyrin ring for which a ring diameter of 2.5 nm was determined1424.…”

“…The distribution in D was found to be relatively narrow corresponding to a width of , whereas the distributions in J are generally found to be much wider. The centre frequency of 3.6 MHz determined for D corresponds to a Cu⋯Cu distance of 2.47 nm at g =2.05, in excellent agreement with expectations from available experimental data and DFT calculations1424.…”

“…All relevant details on the synthesis, binding studies and sample preparation are given in Supplementary Figs 1–8 and Supplementary Notes 1 and 2 for P2 || X and X||X . The synthesis of P2 || P2 has been reported elsewhere14.…”

Exploring template-bound dinuclear copper porphyrin nanorings by EPR spectroscopy

“…In this study, a ten-membered porphyrin nanoring containing two copper centers and eight zinc centers ( c -P10 Cu2 ) 17 is investigated in detail by a variety of EPR techniques. The ring is studied either in isolation or in the presence of molecular templates providing either four ( T4 ) or five ( T5 ) potential binding sites for the central metal of the porphyrin units to form the structures proposed in Fig.…”

Shadow Mask Templates for Site‐Selective Metal Exchange in Magnesium Porphyrin Nanorings

“…To test this hypothesis,w ei nserted af ive-legged template T5 [7] into am agnesium porphyrin nanoring and submitted it to the demetalation conditions.Asexpected, the uncoordinated magnesium porphyrin was cleanly demetalated whereas the template-coordinated magnesium cations remained in place (Scheme 1). [10,11] In each case,t he complex of the template with the magnesium nanoring Mg 6 -P6 was treated with 10 %a cetic acid in dichloromethane.A ll three reactions gave clean, site-selective demetalation, and the products were obtained in high yields without the need for chromatographic purification (Scheme 2). The template masking method applied to the synthesis of (H 2 )Mg 5 -P6 using the template T5.A r= 3,5-bis(trihexylsilyl)phenyl.…”