Department of Chemistry and Centre for Advanced Materials and Biomaterials, The University of Western Ontario, London, Ontario, Canada N6A 5B7.
J Am Chem Soc. 2012 Sep 19;134(37):15205-8. doi: 10.1021/ja306047u. Epub 2012 Sep 6.
The electrochemistry, near-infrared photoluminescence (NIR-PL) spectroscopy, and electrogenerated chemiluminescence (ECL) of Au(25)(SC(2)H(4)Ph)(18)(+)C(6)F(5)CO(2)(-) (Au(25)(+)) clusters were investigated. For the first time, NIR-ECL emission was observed in both annihilation and coreactant paths. Our newly developed spooling spectroscopy was employed during the ECL evolution and devolution processes along with explicit NIR-PL spectroscopy to elucidate light generation mechanisms. It was discovered that the electronic relaxation of the Au(25)(-) excited state to the ground state plays a key role in giving off ECL at 893 nm, while intermediate, strong, and weak NIR-PL emissions at 719/820, 857, and 1080 nm can be attributed to the excited states higher than the HOMO-LUMO gap, across the HOMO-LUMO gap, and of semi-rings, respectively.
研究了 Au(25)(SC(2)H(4)Ph)(18)(+)C(6)F(5)CO(2)(-)（Au(25)(+)）簇的电化学、近红外光致发光（NIR-PL）光谱和电致化学发光（ECL）。首次在湮灭和反应物路径中观察到近红外 ECL 发射。在 ECL 演化和退演化过程中，我们新开发的卷绕光谱学与明确的 NIR-PL 光谱学一起使用，以阐明发光机制。结果发现，Au(25)(-)激发态到基态的电子弛豫在发射 893nm ECL 中起着关键作用，而在 719/820、857 和 1080nm 的中间、强和弱 NIR-PL 发射分别归因于高于 HOMO-LUMO 能隙、穿过 HOMO-LUMO 能隙和半环的激发态。
