Donor-acceptor (D-A) hybrid heterostructures, an emerging class of crystalline hybrid complexes composed of semiconducting organic and inorganic components, have attracted much attention as photochromic materials. Among them, photochromic polyoxometalate/naphthalenediimide D-A hybrid heterostructures represent the most investigated ones, whose photochromic properties are strongly dependent on the structures of polyoxometalates and naphthalenediimides. Herein, we reported their photochromic properties are controlled by their moculelar packings, which were achieved by their diffusion methods. Eight polyoxometalate/naphthalenediimide D-A hybrid heterostructures have been synthesized by the combinations of metal salts (ZnSiF₆·6H₂O or Zn(ClO₄)₂·6H₂O), heteropoly acid (H₃PMo₁₂O₄₀ or H₃PW₁₂O₄₀) and N,N-di(4-pyridyl)-1,4,5,8-naphthalene diimide (DPNDI) via two diffusion methods (A and B). Interestingly, single-crystal X-ray diffraction analyses reveal that they belong to three categories of isostructures with layered, sandwich and interpenetrating packing patterns. Their photochromic properties have been carefully investigated, and the impacts of polyoxometalates as well as packing patterns have also been discussed.

供体-受体（DA）杂化异质结构是一类新兴的由半导体有机和无机成分组成的晶体杂化复合物，已作为光致变色材料引起了广泛关注。其中，光致变色多金属氧酸盐/萘二酰亚胺DA杂化结构代表了研究最多的结构，其光致变色特性强烈依赖于多金属氧酸盐和萘二酰亚胺的结构。在本文中，我们报道了它们的光致变色特性受其分子堆积的控制，这是通过其扩散方法实现的。通过金属盐（ZnSiF ₆ ·6H ₂ O或Zn（ClO ₄）₂）的组合合成了八种多金属氧酸盐/萘二酰亚胺DA杂化结构·6H ₂ O），杂多酸（H ₃ PMo ₁₂ O ₄₀或H ₃ PW ₁₂ O ₄₀）和N，N-二（4-吡啶基）-1,4,5,8-萘二酰亚胺（DPNDI）扩散方法（A和B）。有趣的是，单晶X射线衍射分析表明它们属于具有分层，夹心和互穿堆积模式的三类同质结构。仔细研究了它们的光致变色特性，并讨论了多金属氧酸盐的影响以及堆积方式。