The lack of structurally distinct nanoclusters (NCs) of identical size and composition prevented the mechanistic understanding of their structural effects on ion pairing and concomitant optical properties. To produce such highly sought NCs, we designed a new monothiolate-for-dithiolate exchange strategy that enabled the selective transformation of the structure of a NC without affecting its metal atomicity or composition. Through this method, a bimetallic [PtAg₂₈(BDT)₁₂(PPh₃)₄]^4– NC (1) was successfully synthesized from [PtAg₂₈(S-Adm)₁₈(PPh₃)₄]²⁺ NC (2) (S-Adm, 1-adamantanethiolate; BDT, 1,3-benzenedithiolate; PPh₃, triphenylphosphine). The determined X-ray crystal structure of 1 showed a PtAg₁₂ icosahedron core and a partially exposed surface, which are distinct from a face-centered cubic PtAg₁₂ core and a fully covered surface of 2. We reveal through mass spectrometry (MS) that 1 forms ion pairs with counterions attracted by the core charge of the cluster, which is in line with density functional simulations. The MS data for 1, 2, and other NCs suggested that such attraction is facilitated by the exposed surface of 1. The formation of ion pairs increases the photoluminescence (PL) quantum yield of 1 up to 17.6% depending on the bulkiness of the counterion. Unlike small counterions, larger ones are calculated to occupy ≤90% of the volume near the exposed cluster surface and to make the ligand shell of 1 more rigid, which is observed to increase the PL. Thus, the developed synthesis strategy for structurally different NCs of the same size and composition allows us to probe the structure–property relationship for ion pairing and concomitant PL enhancement.

中文翻译：

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通过离子配对定制纳米团簇的晶体结构，揭示高光致发光

缺乏相同大小和组成的结构不同的纳米团簇（NCs），无法从机械上理解它们对离子对和随之而来的光学性质的结构影响。为了生产备受追捧的NC，我们设计了一种新的单硫醇盐为二硫醇盐的交换策略，该策略能够选择性地转换NC结构，而不会影响其金属原子性或组成。通过这种方法，成功地由[PtAg ₂₈（S-Adm）₁₈（PPh ₃）₄ ] ²⁺ NC（₂）合成了双金属[PtAg ₂₈（BDT）₁₂（PPh ₃）₄ ] ⁴ -NC（1）。2）（S-Adm，1-金刚烷硫醇盐； BDT，1，3-苯二硫醇盐； PPh ₃，三苯基膦）。的所确定的X射线晶体结构1显示出PTAG ₁₂二十面体核心和部分暴露的表面，它是由面心立方PTAG不同₁₂芯和一个完全覆盖的表面2。我们通过质谱（MS）揭示1与离子簇形成离子对，离子对被簇的核心电荷吸引，这与密度泛函模拟相符。用于MS数据1，2，和其他的NC提出，这种吸引力是由暴露表面促进1。离子对的形成增加的光致发光（PL）量子产率1度取决于抗衡离子的膨松度高达17.6％。与小抗衡离子不同，较大的抗衡离子被计算为在暴露的簇表面附近占据≤90％的体积，并使1的配体壳更坚硬，这被认为会增加PL。因此，针对相同大小和组成的结构不同的NC开发的合成策略使我们能够探索离子配对和伴随PL增强的结构-性质关系。