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首页> 外文期刊>Chemistry: A European journal >Electronic Energy Transfer and Collection in Luminescent Molecular Rods Containing ruthenium(II) and Osmium(II) 2,2':6',2''-Terpyridine Complexes Linked by Thiophene-2,5-diyl Spacers
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Electronic Energy Transfer and Collection in Luminescent Molecular Rods Containing ruthenium(II) and Osmium(II) 2,2':6',2''-Terpyridine Complexes Linked by Thiophene-2,5-diyl Spacers

机译：含噻吩-2,5-二芳基间隔基连接的钌（II）和O（II）2,2'：6'，2''-三联吡啶配合物的发光分子棒中的电子传递和收集

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摘要

The electronic absorption spectra, luminescence spectra and lifetimes (in MeCN at room temperature and in frozen n-C_3H_7CN at 77 K), and electrochemical potentials (in MeCN) of the novel dinuclear [(tpy)Ru(3)Os(tpy)]~(4+) and trinuclear [(tpy)Ru(3)Os(3)Ru(tpy)]~(6+) complexes (3 = 2,5-bis(2,2':6',2''-terpyridin-4-yl)thiophene) have been obtained and are compared with those of model mononuclear complexes and homometallic [(tpy)Ru(3)Ru(tpy)]~(4+), [(tpy)Os(3)Os(tpy)]~(4+) and [(tpy)Ru(3)Ru(3)Ru(tpy)]~(6+) complexes. The bridging ligand 3 is nearly planar in the complexes, as seen from a preliminary X-ray determination of [(tpy)Ru(3)Ru(tpy)][PF_6]_4, and confers a high degree of rigidity upon the polynuclear species. The trinuclear species are rodshaped with a distance of about 3 nm between the terminal metal centers. For the polynuclear complexes, the spectro-scopic and electrochemical data are in accord with a significant intermetal interaction. All of the complexes are luminescent (#PHI) in the range 10~(-4))-10~(-2) and #tau# in the range 6-340 ns, at room temperature), and ruthenium- or osmium-based luminescence properties can be identified. Due to the excited state properties of the various components and to the geometric and electronic properties of the bridge, Ru -> Os directional transfer of excitation energy takes place in the complexes [(tpy)Ru(3)Os(tpy)]~(4+) (end-to-end) and [(tpy)Ru(3)Os(3)Ru(tpy)]~(6) (periphery-to-centre). With respect to the homometallic case, for [(tpy)Ru(3)Os(3)Ru(tpy)]~(6+) excitation trapping at the central position is accompanied by a fivefold enhancement of luminescence intensity.
机译：新型双核[（tpy）Ru（3）Os（tpy）]的电子吸收光谱，发光光谱和寿命（在室温下于MeCN中，在77 K下处于冷冻n-C_3H_7CN中）以及电化学势（在MeCN中） 〜（4+）和三核[[tpy）Ru（3）Os（3）Ru（tpy）]〜（6+）络合物（3 = 2,5-bis（2,2'：6'，2'' -terpyridin-4-yl）thiophene），并与模型单核络合物和同金属的[（tpy）Ru（3）Ru（tpy）]〜（4 +），[（tpy）Os（3）比较Os（tpy）]〜（4+）和[（tpy）Ru（3）Ru（3）Ru（tpy）]〜（6+）络合物。从[（tpy）Ru（3）Ru（tpy）] [PF_6] _4的初步X射线测定中可以看出，桥接配体3在配合物中几乎是平面的，并赋予多核物种高度的刚性。三核物质呈棒状，末端金属中心之间的距离约为3 nm。对于多核配合物，光谱和电化学数据符合重要的金属间相互作用。在室温下，所有络合物均在10〜（-4））-10〜（-2）范围内发光（#PHI），在6-340 ns范围内发光＃tau＃），并且钌或-可以确定基于发光的性质。由于各个组件的激发态特性以及桥的几何和电子特性，在复合物中[[tpy] Ru（3）Os（tpy）]〜（ 4+）（端到端）和[（tpy）Ru（3）Os（3）Ru（tpy）]〜（6）（外围到中心）。对于同金属的情况，对于[（tpy）Ru（3）Os（3）Ru（tpy）]〜（6+），激发陷获在中心位置处伴随着发光强度的五倍增强。

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