Rectangular-Shaped Expanded Phthalocyanines with Two Central Metal Atoms

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• 作者：Osamu Matsushita ; Valentina M. Derkacheva ; Atsuya Muranaka ; Soji Shimizu ; Masanobu Uchiyama ; Evgeny A. Luk鈥檡anets ; Nagao Kobayashi
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：February 22, 2012
• 年：2012
• 卷：134
• 期：7
• 页码：3411-3418
• 全文大小：510K
• 年卷期：v.134,no.7(February 22, 2012)
• ISSN：1520-5126

文摘

Expanded 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 C_2v 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鈥?500 nm region. This can be explained using Gouterman鈥檚 four-orbital theory. The experimental NMR data and theoretical calculations provide evidence for a heteroaromatic 22-蟺-electron conjugation system for the ring-expanded Pc system, which satisfies H眉ckel鈥檚 (4n + 2)蟺 aromaticity.