The investigation of metal phosphates/phosphites (MPOs) has received continuous interest of researchers because of their diverse structural characteristics and interesting chemo-physical properties. Compared with inorganic phosphate/phosphite, organic phosphonate not only inherits the structural characteristics of inorganic phosphate/phosphite, but also shows tunable constituents, which provides extra freedom to yield novel hybrid materials with expanding application and broaden the research scope of traditional MPOs. Recent studies have demonstrated that the intermarriage of polydentate N/O-ligands and metal phosphites/phosphates/phosphonates (MPOs) gives birth to a new category of hybrid materials. The topic of this review is to propose strategies towards anchoring polydentate N/O-ligands in MPO-based supramolecular building blocks (SBBs) to generate functionalized MPO-based hybrid materials, reveal relationships between the microscopic functional struct-units and macroscopic physical functionality of resultant hybrid MPOs, extend the available functionality in the field of MPO-studies. Such a topic aims at enriching the research scope of MPOs from conventional MPOs (organically templated phosphates and phosphites with inorganic host structs) to unconventional MPOs (phosphates, phosphites and phosphonates decorated by polydentate N/O-ligands with hybrid host structs) in structural constituents, from traditional applications (adsorbent, ion-exchanger and catalyst) to emerging applications (room temperature phosphorescence (RTP), photochromism, photomagnetism, etc) in properties expansion. This review would offer valuable guidance for researchers engaged in MPO-based materials, and eventually facilitate the new studies of hybrid MPOs materials with desirable properties.

金属磷酸盐/亚磷酸盐 (MPO) 的研究因其多样化的结构特征和有趣的化学物理特性而受到研究人员的持续关注。与无机磷酸盐/亚磷酸盐相比，有机膦酸盐不仅继承了无机磷酸盐/亚磷酸盐的结构特征，而且表现出可调节的成分，为制备新型杂化材料提供了额外的自由度，应用范围不断扩大，也拓宽了传统MPOs的研究范围。最近的研究表明，多齿 N/O-配体和金属亚磷酸盐/磷酸盐/膦酸盐 (MPO) 的杂交产生了一类新的杂化材料。本综述的主题是提出在基于 MPO 的超分子构件 (SBB) 中锚定多齿 N/O-配体以生成功能化的基于 MPO 的杂化材料的策略，揭示微观功能结构单元与宏观物理功能之间的关系。由此产生的混合 MPO，扩展了 MPO 研究领域的可用功能。该课题旨在丰富 MPOs 的研究范围，从传统的 MPOs（具有无机主体结构的有机模板化磷酸盐和亚磷酸盐）到结构成分上的非常规 MPOs（由具有杂化主体结构的多齿 N/O 配体修饰的磷酸盐、亚磷酸盐和膦酸盐） ，从传统应用（吸附剂、离子交换剂和催化剂）到新兴应用（室温磷光 (RTP)，光致变色、光磁等）在性能扩展方面。该综述将为从事基于 MPO 的材料的研究人员提供有价值的指导，并最终促进对具有理想性能的混合 MPO 材料的新研究。