This paper demonstrates that novel composites of porous silica with carbon-like black materials are different from conventional carbon black. The obtained black composites maintained high porosity of the base silica and exhibited extremely high molecular shape selectivity, especially for geometrical isomers.Keywords: π-Conjugated structure | Porous material | Amorphous carbonTo address the growing demand for enhanced separation selectivity in column technology, a variety of functional molecules have been designed and immobilized on porous carriers to meet this demand, as exemplified by successful applications of macrocycle-grafted silica, 15 where high selectivity is achieved by macrocyclic ordering of heteroatoms as interaction points. On the other hand, non-macrocyclic compounds can also achieve selectivity enhancement if weak interaction points are integrated and oriented. Typical examples include integrated carbonyl group systems like side-chain ordered polymers containing ester bonds, 68 alternating phthalimide-based copolymers, 9 and polypeptide-10 and molecular-gel-based ordered organic phases, 1113 which provide higher selectivity than conventional hydrophobized silica, especially for separating geometrical isomers. These successful applications are directly related to the promotion of multiple carbonyl-π interactions 14 with guest molecules. π-Electron-rich organic phases are also attractive for selectivity enhancement. Although ππ interactions are considerably weaker than carbonylπ interactions, 14,15 integration of aromatic π-moieties enables selectivity enhancement, as exemplified by polymers with aromatic side chains, 16,17 Herein, we introduce a new class of π-electron-rich organic phases (Figure 1) for ultra-selective adsorption, which are based on carbon-like black materials different from conventional carbon black and graphite. The designed materials exhibit the following advantages. (1) The pre-black organic thin layer can be created on porous silica microspheres by direct copolymerization of 1,5-dihydroxynaphthalene (DHN) and 1,3,3, 27 in a simple solvent system. The amount of immobilized material is easy to adjust while preserving the large surface area of porous silica, since polymerization occurs on the silica surface in a semi-quantitative fashion. Additionally, polymer growth does not require silica to be surface-treated. (2) Copolymerization is accompanied by crosslinking; therefore, no elution is observed after washing with solvents. (3) The adhered polymer can be converted into carbonlike black materials by heat treatment at a suitable temperature, allowing the adsorptivity and selectivity of the column system to be flexibly tuned.Copolymerization was carried out at a fixed molar ratio (1:1) of DHN and TMTA. The original milky white mixture of these monomers with YMC silica as porous carrier in ethanol turned green after 1 h stirring at reflux temperature (78°C). Optical microscopy imaging indicated that the above change was due to the coloration of silica and not that of the solvent....