| Institution: | 1. Department of Chemistry and BK21Plus Research Team, Chungbuk National University, 1 Chungdae-ro, Seowon-gu, Cheongju, 28644 Republic of Korea
These authors contributed equally to this work.;2. Department of Nanochemistry, Gachon University, 1342 Seongnamdae-ro, Sujeong-gu, Seongnam, 13120 Republic of Korea;3. Department of Chemistry and BK21Plus Research Team, Chungbuk National University, 1 Chungdae-ro, Seowon-gu, Cheongju, 28644 Republic of Korea;4. Department of Chemistry Education, Chungbuk National University, 1 Chungdae-ro, Seowon-gu, Cheongju, 28644 Republic of Korea;5. Department of Chemistry, Incheon National University, 119 Academy-ro, Yeonsu-gu, Incheon, 22012 Republic of Korea |
| Abstract: | The effect of metal on the degree of flexibility upon evacuation of metal–organic frameworks (MOFs) has been revealed with positional control of the organic functionalities. Although Co-, Cu-, and Zn-based DMOFs (DMOF = DABCO MOF, DABCO = 1,4-diazabicyclo2.2.2]octane) with ortho-ligands (2,3-NH2Cl) have frameworks that are inflexible upon evacuation, MOFs with para-ligands (2,5-NH2Cl) showed different N2 uptake amounts after evacuation by metal exchange. Considering that the structural analyses were not fully sufficiently different to explain the drastic changes in N2 adsorption after evacuation, quantum chemical simulation was explored. A new index (η) was defined to quantify the regularity around the metal based on differences in the oxygen-metal-oxygen angles. Within 2,5-NH2Cl, the η value becomes larger as the metal are varied from Co to Zn. A large η value means that the structures around the metal center are less ordered. These results can be used to explain flexibility changes upon evacuation by altering the metal cation in this regioisomeric system. |
