Synthesis of Five‐Porphyrin Nanorings by Using Ferrocene and Corannulene Templates

Pengpeng Liu,Yutaka Hisamune,Laura M Herz,Harry L Anderson,Martin D Peeks,Barbara Odell,Juliane Q Gong

doi:10.1002/ange.201602909

Abstract

AbstractThe smallest and most strained member of a family of π‐conjugated cyclic porphyrin oligomers was synthesized by using pentapyridyl templates based on ferrocene and corannulene. Both templates are effective for directing the synthesis of the butadiyne‐linked cyclic pentamer, despite the fact that the radii of their N5 donor sets are too small by 0.5 Å and 0.9 Å, respectively (from DFT calculations). The five‐porphyrin nanoring exhibits a structured absorption spectrum and its fluorescence extends to 1200 nm, reflecting strong π conjugation and Herzberg–Teller vibronic coupling.

Highlights

The smallest and most strained member of a family of p-conjugated cyclic porphyrin oligomers was synthesized by using pentapyridyl templates based on ferrocene and corannulene
We compared the ability of two pentadentate templates to direct the formation of this cyclic pentamer: T5Fc and T5 cor, which are based on ferrocene and corannulene cores, respectively (Figure 1, Scheme 1, and Scheme 2)
Density functional theory (DFT) geometry optimizations using Gaussian09/D.01 at the B3LYP/6-31G* level[7] with Grimmes D3 dispersion correction[8] indicate that both templates are too small for the cavity of c-P5

Summary

Introduction

The smallest and most strained member of a family of p-conjugated cyclic porphyrin oligomers was synthesized by using pentapyridyl templates based on ferrocene and corannulene. We compared the ability of two pentadentate templates to direct the formation of this cyclic pentamer: T5Fc and T5 cor, which are based on ferrocene and corannulene cores, respectively (Figure 1, Scheme 1, and Scheme 2). Synthesis of the templates T5Fc and T5 cor, with overall yields.

Results

Conclusion