Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
Ligand accommodation causes the anti-centrosymmetric structure of Au13Cu4 clusters with near-infrared emission.
Nanoscale ( IF 5.8 ) Pub Date : 2020-07-01 , DOI: 10.1039/d0nr02448a Rajini Anumula 1 , Arthur C Reber , Pan An , Chaonan Cui , Mengdi Guo , Haiming Wu , Zhixun Luo , Shiv N Khanna
Nanoscale ( IF 5.8 ) Pub Date : 2020-07-01 , DOI: 10.1039/d0nr02448a Rajini Anumula 1 , Arthur C Reber , Pan An , Chaonan Cui , Mengdi Guo , Haiming Wu , Zhixun Luo , Shiv N Khanna
Affiliation
|
We synthesized an [Au13Cu4(PPh3)4(SPy)8]+ nanocluster co-capped by phosphine and thiolate ligands. Interestingly, this Au13Cu4 cluster corresponds to an anti-centrosymmetric structure with the four copper atoms coordinated to the mixed ligands on the same side of the Au13 icosahedron, which is in sharp contrast to the [Au13Cu4(PPh2Py)4(SPhtBu)8]+ and [Au13Cu2(PPh3)6(SPy)6]+ clusters which possess highly symmetric structures with well-separated Cu adatoms. Both [Au13Cu4(PPh3)4(SPy)8]+ and [Au13Cu2(PPh3)6(SPy)6]+ clusters correspond to 8 valence electron superatoms with large HOMO–LUMO gaps, respectively. The difference in structure is rooted in the nature of the mixed ligands, with the bidentate SPy binding strongly to Cu on both binding sites (–N–Cu and Au-SR-Cu) leading to the co-linking of adjacent Cu atoms, while the bidentate PPh2Py binds Cu on one site and Au on the other giving rise to a separation of the Cu atoms even in the presence of relatively higher monomer concentration. Both [Au13Cu4(PPh3)4(SPy)8]+ and [Au13Cu2(PPh3)6(SPy)6]+ display emissions in the near-IR regions. TD-DFT calculations reproduce the spectroscopic results with specified excited states, shedding light on the geometric and electronic behaviors of the ligand-protected Au13Mx clusters.
中文翻译：
配体调节导致具有近红外发射的Au13Cu4团簇的反中心对称结构。
我们合成了[Au 13 Cu 4（PPh 3）4（SPy）8 ] +由膦和硫醇盐配体共同封端的纳米簇。有趣的是，该Au 13 Cu 4团簇对应于一个反中心对称结构，其中四个铜原子与Au 13二十面体同一侧的混合配体配位，这与[Au 13 Cu 4（PPh 2 Py）4（SPh t Bu）8 ] +和[Au 13 Cu 2（PPh 3）6（SPy）6 ] +团簇，具有高度对称的结构，且Cu原子原子分离得很好。[Au 13 Cu 4（PPh 3）4（SPy）8 ] +和[Au 13 Cu 2（PPh 3）6（SPy）6 ] +团簇分别对应于具有大HOMO-LUMO间隙的8个价电子超原子。结构上的差异源于混合配体的性质，双齿SPy在两个结合位点（–N–Cu和Au-SR-Cu）上均与Cu牢固结合，从而导致相邻Cu原子的共连接，而即使在相对较高的单体浓度下，双齿PPh 2 Py也会在一个位置结合Cu，在另一个位置结合Au，从而导致Cu原子的分离。[Au 13 Cu 4（PPh 3）4（SPy）8 ] +和[Au 13 Cu 2（PPh 3）6（SPy）6] +显示近红外区域的发射。TD-DFT计算重现了指定激发态下的光谱结果，从而揭示了配体保护的Au 13 M x团簇的几何和电子行为。
更新日期：2020-07-16
中文翻译：
配体调节导致具有近红外发射的Au13Cu4团簇的反中心对称结构。
我们合成了[Au 13 Cu 4（PPh 3）4（SPy）8 ] +由膦和硫醇盐配体共同封端的纳米簇。有趣的是，该Au 13 Cu 4团簇对应于一个反中心对称结构，其中四个铜原子与Au 13二十面体同一侧的混合配体配位，这与[Au 13 Cu 4（PPh 2 Py）4（SPh t Bu）8 ] +和[Au 13 Cu 2（PPh 3）6（SPy）6 ] +团簇，具有高度对称的结构，且Cu原子原子分离得很好。[Au 13 Cu 4（PPh 3）4（SPy）8 ] +和[Au 13 Cu 2（PPh 3）6（SPy）6 ] +团簇分别对应于具有大HOMO-LUMO间隙的8个价电子超原子。结构上的差异源于混合配体的性质，双齿SPy在两个结合位点（–N–Cu和Au-SR-Cu）上均与Cu牢固结合，从而导致相邻Cu原子的共连接，而即使在相对较高的单体浓度下，双齿PPh 2 Py也会在一个位置结合Cu，在另一个位置结合Au，从而导致Cu原子的分离。[Au 13 Cu 4（PPh 3）4（SPy）8 ] +和[Au 13 Cu 2（PPh 3）6（SPy）6] +显示近红外区域的发射。TD-DFT计算重现了指定激发态下的光谱结果，从而揭示了配体保护的Au 13 M x团簇的几何和电子行为。
京公网安备 11010802027423号