Energy Transfers in Monomers, Dimers, and Trimers of Zinc(II) and Palladium(II) Porphyrins Bridged by Rigid Pt-Containing Conjugated Organometallic Spacers

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• 作者：Diana Bellows ; Shawkat M. Aly ; Claude P. Gros ; Maya El Ojaimi ; Jean-Michel Barbe ; Roger Guilard ; Pierre D. Harvey
• 刊名：Inorganic Chemistry
• 出版年：2009
• 出版时间：August 17, 2009
• 年：2009
• 卷：48
• 期：16
• 页码：7613-7629
• 全文大小：1446K
• 年卷期：v.48,no.16(August 17, 2009)
• ISSN：1520-510X

文摘

A series of linear monomers (spacer−M(P)), dimers (M(P)−spacer−M′(P)), and trimers (M(P)−spacer−M′(P)−spacer−M(P)) of spacer/metalloporphyrin systems (M′ = Zn, M = Zn, Pd, P = porphyrin, and spacer = trans-Cb>6b>Hb>4b>C≡CPtLb>2b>C≡CCb>6b>Hb>4b>- (L = PEtb>3b>)) including mixed metalloporphyrin compounds, were synthesized and characterized. The Sb>1b> and Tb>1b> energy transfers Pd(P)*→Zn(P) occur with rates of 2 × 10⁹ s⁻¹, Sb>1b>, and 0.15 × 10³ (slow component) and 4.3 × 10³ s⁻¹ (fast component), Tb>1b>. On the basis of a literature comparison with a related dyad, the Pt atom in the conjugated chain slows down the transfers. The excitation in the absorption band of the trans-Cb>6b>Hb>4b>C≡CPtLb>2b>C≡CCb>6b>Hb>4b>- spacer in the 300−360 nm range also leads to Tb>1b> energy transfer (spacer* → M(P); M = Zn, Pd) with rates of 10⁴ s⁻¹.