HIGHLIGHTS • A novel coordination polymerization-driven hierarchical assembly approach for spatially controlled fabrication of phytic acid-based bio-derivatives was developed. • The resultant ferric phytate bio-derived polymer featured hollow nanosphere architecture, ordered meso-channels, high surface area, and large pore volume, as anode material, delivering a remarkable electrochemical performance.

The precise regulation of nucleation growth and assembly of polymers is still an intriguing goal but an enormous challenge. In this study, we proposed a pre‐polymerization strategy to regulate the assembly and growth of polymers by facilely controlling the concentration of polymerization initiator, and thus obtained two kinds of different nanosheet‐based porphyrin polymer materials using tetrakis‐5,10,15,20‐(4‐aminophenyl) porphyrin (TAPP) as the precursor. Notably, due to the π–π stacking and doping of TAPP during the preparation process, the obtained PTAPP‐nanocube material exhibits a high intrinsic bulk conductivity reaching 1.49×10−4 S m−1. Profiting from the large π‐conjugated structure of porphyrin units, closely stacked layer structure and excellent conductivity, the resultant porphyrin polymers, as electrode materials for lithium ion batteries, deliver high specific capacity (≈650 mAh g−1 at the current density of 100 mA g−1), excellent rate performance and long‐cycle stability, which are among the best reports of porphyrin polymer‐based electrode materials for lithium‐ion batteries, to the best of our knowledge. Therefore, such a pre‐polymerization approach would provide a new insight for the controllable synthesis of polymers towards custom‐made architecture and function.

Nanomeshes with highly regular, permeable pores in plane, combining the exceptional porous architectures with intrinsic properties of 2D materials, have attracted increasing attention in recent years. Herein, a series of 2D ultrathin metal–organic nanomeshes with ordered mesopores is obtained by a self‐assembly method, including metal phosphate and metal phosphonate. The resultant mesoporous ferric phytate nanomeshes feature unique 2D ultrathin monolayer morphologies (≈9 nm thickness), hexagonally ordered, permeable mesopores of ≈16 nm, as well as improved surface area and pore volume. Notably, the obtained ferric phytate nanomeshes can directly in situ convert into mesoporous sulfur‐doped metal phosphonate nanomeshes by serving as an unprecedented reactive self‐template. Furthermore, as advanced anode materials for Li‐ion batteries, they deliver excellent capacity, good rate capability, and cycling performance, greatly exceeding the similar metal phosphate‐based materials reported previously, resulting from their unique 2D ultrathin mesoporous structure. Therefore, the work will pave an avenue for constructing the other 2D ordered mesoporous materials, and thus offer new opportunities for them in diverse areas.

Conjugated polyimines constructed from aromatic amines and aromatic aldehydes have attracted enormous attention because of their excellent and fascinating properties. However, the structure of these materials constructed by building blocks or linkers is usually confined to a scope of microporosity and small mesopores (less than 5 nm), which largely impedes their applications in many fields. Here, a facile self‐assembly strategy is developed to controllably fabricate conjugated polyimines nanospheres with multichambered mesoporous architecture by using polystyrene‐b‐poly(acrylic acid) diblock copolymer as a soft template. Given the wide availability of amines and aldehydes, it is expected to open new avenues for designing diverse polyimine‐based materials with controlled mesostructure toward applications.

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