Nastasi Francesco, Puntoriero Fausto, Natali Mirco, Mba Miriam, Maggini Michele, Mussini Patrizia, Panigati Monica, Campagna Sebastiano
Dipartimento di Scienze Chimiche, Università di Messina and Centro Interuniversitario per la Conversione Chimica dell'Energia Solare (SOLAR-CHEM; sezione di Messina), Messina, Italy.
Photochem Photobiol Sci. 2015 May;14(5):909-18. doi: 10.1039/c4pp00301b.
A novel molecular dyad, 1, made of a dinuclear {[Re2(μ-X)2(CO)6(μ-pyridazine)]} component covalently-linked to a fullerene unit by a carbocyclic molecular bridge has been prepared and its redox, spectroscopic, and photophysical properties - including pump-probe transient absorption spectroscopy in the visible and near-infrared region - have been investigated, along with those of its model species. Photoinduced, intercomponent electron transfer occurs in 1 from the thermally-equilibrated, triplet metal/ligand-to-ligand charge-transfer ((3)MLLCT) state of the dinuclear rhenium(I) subunit to the fullerene acceptor, with a time constant of about 100 ps. The so-formed triplet charge-separated state recombines in a few nanoseconds by a spin-selective process yielding, rather than the ground state, the locally-excited, triplet fullerene state, which finally decays to the ground state by intersystem crossing in about 290 ns.
一种新型分子二元体1已被制备出来，它由一个双核{[Re2(μ-X)2(CO)6(μ-哒嗪)]}组分通过碳环分子桥与一个富勒烯单元共价连接而成，并且研究了其氧化还原、光谱和光物理性质——包括可见光和近红外区域的泵浦-探测瞬态吸收光谱——以及其模型物种的相关性质。在1中，光诱导的组分间电子转移发生在从双核铼(I)亚基的热平衡三重态金属/配体-配体电荷转移((3)MLLCT)态到富勒烯受体的过程中，时间常数约为100皮秒。如此形成的三重态电荷分离态在几纳秒内通过自旋选择性过程复合，产生的不是基态，而是局域激发的三重态富勒烯态，该态最终在约290纳秒内通过系间窜越衰减到基态。
