Advanced Macromolecular Architectures via Inorganic Polymers

ABSTRACT Advanced macromolecular architectures, extending beyond mere chemical composition, are key to unlocking new functionalities in inorganic polymers. This review highlights recent advances in the design and synthesis of inorganic polymers with complex architectures, ranging from hyperbranched and graft polymers to dendrimers, such as hyperbranched polyphosphoester, star‐branched polyphosphazenes and polydimethylsiloxane bottlebrushes, thus extending well beyond traditional linear chains. These structural motifs enable unique and tunable properties, such as degradation profiles and mechanical performance, expanding the range of applications in biomedical and technical fields. Particular emphasis is placed on synthetic strategies that enable precise architectural control. While such structural diversity is well established in organic systems, this review focuses on inorganic polymers featuring main‐group elements in the polymer backbone and as key structural elements. Phosphorus‐ and silicon‐based polymers, especially polyphosphazenes, polyphosphoesters, and polysiloxanes, constitute the majority of studied systems and are covered in depth, alongside emerging classes incorporating sulfur, tin, selenium, and metallocenes.