由含刚性铂的共轭有机金属间隔基桥连的锌（II）和钯（II）卟啉的单体、二聚体和三聚体中的能量转移。

Energy transfers in monomers, dimers, and trimers of zinc(II) and palladium(II) porphyrins bridged by rigid Pt-containing conjugated organometallic spacers.

作者信息

Bellows Diana, Aly Shawkat M, Gros Claude P, El Ojaimi Maya, Barbe Jean-Michel, Guilard Roger, Harvey Pierre D

机构信息

Departement de chimie, Université de Sherbrooke, Sherbrooke, Québec, Canada.

出版信息

Inorg Chem. 2009 Aug 17;48(16):7613-29. doi: 10.1021/ic900840w.

DOI:10.1021/ic900840w

PMID:19624118

Abstract

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-C(6)H(4)C[triple bond]CPtL(2)C[triple bond]CC(6)H(4)- (L = PEt(3))) including mixed metalloporphyrin compounds, were synthesized and characterized. The S(1) and T(1) energy transfers Pd(P)-->Zn(P) occur with rates of approximately 2 x 10(9) s(-1), S(1), and 0.15 x 10(3) (slow component) and 4.3 x 10(3) s(-1) (fast component), T(1). 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-C(6)H(4)C[triple bond]CPtL(2)C[triple bond]CC(6)H(4)- spacer in the 300-360 nm range also leads to T(1) energy transfer (spacer --> M(P); M = Zn, Pd) with rates of 10(4) s(-1).

摘要

合成并表征了一系列间隔基/金属卟啉体系（M' = Zn，M = Zn、Pd，P = 卟啉，间隔基 = trans-C(6)H(4)C≡CPtL(2)C≡CC(6)H(4)-，L = PEt(3)）的线性单体（间隔基-M(P)）、二聚体（M(P)-间隔基-M'(P)）和三聚体（M(P)-间隔基-M'(P)-间隔基-M(P)），包括混合金属卟啉化合物。S(1)和T(1)能量转移Pd(P)→Zn(P)的速率分别约为2×10⁹ s⁻¹（S(1)）、0.15×10³（慢组分）和4.3×10³ s⁻¹（快组分）（T(1)）。基于与相关二元体的文献比较，共轭链中的Pt原子减缓了转移。在300 - 360 nm范围内，trans-C(6)H(4)C≡CPtL(2)C≡CC(6)H(4)-间隔基吸收带的激发也导致T(1)能量转移（间隔基→M(P)；M = Zn、Pd），速率为10⁴ s⁻¹。