The availability of a range of excited states has endowed low dimensional quantum nanostructures with interesting luminescence properties. However, the origin of photoluminescence emission is still not fully understood, which has limited its practical application. Here we judiciously manipulate the delicate surface ligand interactions at the nanoscale interface of a single metal nanocluster, the superlattice, and mesoporous materials. The resulting interplay of various noncovalent interactions leads to a precise modulation of emission colors and quantum yield. A new p-band state, resulting from the strong overlapping of p orbitals of the heteroatoms (O, N, and S) bearing on the targeting ligands though space interactions, is identified as a dark state to activate the triplet state of the surface aggregated chromophores. The UV-Visible spectra calculated by time-dependent density functional theory (TD-DFT) are in quantitative agreement with the experimental adsorption spectra. The energy level of the p-band center is very sensitive to the local proximity ligand chromophores at heterogeneous interfaces.

一系列激发态的可用性赋予了低维量子纳米结构以令人感兴趣的发光特性。然而，光致发光发射的起源仍未被完全理解，这限制了其实际应用。在这里，我们明智地处理了单个金属纳米团簇，超晶格和介孔材料在纳米级界面上的精细表面配体相互作用。各种非共价相互作用的最终相互作用导致了发射色和量子产率的精确调节。通过空间相互作用，由于载于靶向配体上的杂原子（O，N和S）的p轨道的强烈重叠而产生的新的p带态被识别为暗态，以激活聚集表面的三重态发色团。通过时变密度泛函理论（TD-DFT）计算得到的紫外可见光谱与实验吸附光谱在数量上一致。p带中心的能级对异质界面处的局部邻近配体生色团非常敏感。