Organic-inorganic covalent-ionic molecules for elastic ceramic plastic

Although organic-inorganic hybrid materials have played indispensable roles as mechanical^1-4, optical^5,6, electronic^7,8 and biomedical materials^9-11, isolated organic-inorganic hybrid molecules (at present limited to covalent compounds^12,13) are seldom used to prepare hybrid materials, owing to the distinct behaviours of organic covalent bonds¹⁴ and inorganic ionic bonds¹⁵ in molecular construction. Here we integrate typical covalent and ionic bonds within one molecule to create an organic-inorganic hybrid molecule, which can be used for bottom-up syntheses of hybrid materials. A combination of the organic covalent thioctic acid (TA) and the inorganic ionic calcium carbonate oligomer (CCO) through an acid-base reaction provides a TA-CCO hybrid molecule with the representative molecular formula TA₂Ca(CaCO₃)₂. Its dual reactivity involving copolymerization of the organic TA segment and inorganic CCO segment generates the respective covalent and ionic networks. The two networks are interconnected through TA-CCO complexes to form a covalent-ionic bicontinuous structure within the resulting hybrid material, poly(TA-CCO), which unifies paradoxical mechanical properties. The reversible binding of Ca²⁺-CO₃^2- bonds in the ionic network and S-S bonds in the covalent network ensures material reprocessability with plastic-like mouldability while preserving thermal stability. The coexistence of ceramic-like, rubber-like and plastic-like behaviours within poly(TA-CCO) goes beyond current classifications of materials to generate an 'elastic ceramic plastic'. The bottom-up creation of organic-inorganic hybrid molecules provides a feasible pathway for the molecular engineering of hybrid materials, thereby supplementing the classical methodology used for the manufacture of organic-inorganic hybrid materials.