SAINT

4/24(목) 전문가초청특강은 University of Valencia의 Joaquin Calbo 교수님(추천교수-박지상 교수님)을 모시고 진행합니다.

관심있는 분들의 많은 참석 부탁드립니다.

ㅁ주제: Accelerating the discovery of porous conductors through computational chemistry

ㅁ장소: 제2종합연구동 83188호

ㅁ약력:

ㅁ초록:

Despite being traditionally considered as insulators, (metal)-organic frameworks are porous crystalline structures that have proved to be efficient for the transport of electrical charge upon suitable chemical design for next-generation applications. Among the most promising strategies to infuse charge conductivity in porous crystals, we emphasize the π-π stacking of electroactive ligands, the incorporation of guest molecules within the pores, or the exploitation of mixed valency in chemically available metal redox pairs. These porous conductors are meant to unlock new avenues in the design of novel materials for efficient energy conversion and storage.

Herein, we showcase the theoretical modelling of advanced porous materials that take advantage of each of these chemical strategies to boost charge conductivity. First, the charge transport of a series of purely organic porous frameworks based on H-bonding (HOFs) is described in terms of a through-space hopping of charge carriers between stacked electroactive TTF-based ligands in a zwitterionic form (Figure 1a). Second, one of the first examples of perylene-based MOFs with semiconductivity is presented based on the partial oxidation of the ligand upon inclusion of I₂ dopant, and promoted by a herringbone CH···π perylene-perylene stacking (Figure 1b). Last, the record 3D conducting MOF based on Fe(II)/Fe(III) redox pair and tetrazole ligand Fe₂(BDT)₃ (Figure 1c) is characterized theoretically, and compared with its polymorphs, to unveil the origin of its striking high charge transport.

Figure 1. Crystal structure of a) TTF-based MUV-20a, b) perylene-based Per-MOF, and c) tetrazole-based Fe₂(BDT)₃ frameworks