期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 129, 期 37, 页码 11491-11504出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja072672w
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资金
- Engineering and Physical Sciences Research Council [GR/S97446/01] Funding Source: researchfish
The tritopic bridging ligand hexaazatriphenylene (HAT) has been used to prepare the mono-, di-, and trinuclear cyanoruthenate complexes [Ru(CN)(4)(HAT)](2-) ([1](2-)), [{Ru(CN)(4)}(2)(mu(2)-HAT)](4-) ([2](4-)), and [{Ru(CN)(4)}(3)(mu(3)-HAT)](6-) ([3](6-)). These complexes are of interest both for their photophysical properties and ability to act as sensitizers, associated with strong MLCT absorptions; and their structural properties, with up to 12 externally directed cyanide ligands at a single node for preparation of coordination networks. The complexes are strongly solvatochromic, with broad and intense MLCT absorption manifolds arising from the presence of low-lying pi(*) orbitals on the HAT ligand, as confirmed by DFT calculations; in aprotic solvents [3](6-) is a panchromatic absorber of visible light. Although nonluminescent in fluid solution, the lowest MLCT excited states have lifetimes in D2O of tens of nanoseconds and could be detected by time-resolved iR spectrosocopy. For clinuclear [2](4-) and trinuclear [3](6-) the TRIR spectra are indicative of asymmetric MLCT excited states containing distinct Ru(III) and Ru(II) centers on the IR time scale. The complexes show red 3 MLCT luminescence as solids and in EtOH/MeOH glass at 77 K. Ln(III) salts of [1](2-), [2](4-), and [3](6-) form infinite coordination networks based on Ru-CN-Ln bridges with a range of one-, two-, and three-dimensional polymeric structures. In the Yb(III) and Nd(III) salts of [3](6-) the complex anion forms an 8-connected node. Whereas all of the Gd(III) salts show strong (MLCT)-M-3 luminescence in the solid state, the Ru-based emission in the Nd(III) and Yb(III) analogues is substantially quenched by Ru - Ln photoinduced energy transfer, which results in sensitized near-infrared luminescence from Yb(III) and Nd(III).
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