ja209589x_si_002.cif (71.84 kB)
Rectangular-Shaped Expanded Phthalocyanines with Two Central Metal Atoms
dataset
posted on 2016-02-22, 05:12 authored by Osamu Matsushita, Valentina
M. Derkacheva, Atsuya Muranaka, Soji Shimizu, Masanobu Uchiyama, Evgeny A. Luk’yanets, Nagao KobayashiExpanded phthalocyanine (Pc) congeners with two Mo or
W central
metal ions and four isoindole ring moieties have been synthesized
using normal Pc formation conditions in the presence of urea. The
products have been characterized by electrochemistry; mass spectrometry
(MS); IR, electron paramagnetic resonance (EPR), NMR, electronic absorption,
and magnetic circular dichroism (MCD) spectroscopies; and X-ray analysis.
The X-ray structures have rectangular C2v symmetry and provide evidence that the central Mo
atoms are linked by a single bond and coordinated by two isoindole
nitrogen atoms and two nitrogen atoms from the amine moieties. The
electronic absorption bands extend into the 1200–1500 nm region.
This can be explained using Gouterman’s four-orbital theory.
The experimental NMR data and theoretical calculations provide evidence
for a heteroaromatic 22-π-electron conjugation system for the
ring-expanded Pc system, which satisfies Hückel’s (4n + 2)π aromaticity.