YRCHEM-2022

Transcript

1. Conductivity enhancement in a perylene-based MOF via iodine doping: A theoretical insight. María Esteve Rochina
2. Introduction Metal Organic Frameworks (MOFs) are crystalline porous materials built from the combination of organic linkers and metal ions (nodes).
3. Introduction Applications Catalysis Gas storage/separation Drug delivery MOF
4. Introduction Applications Catalysis Gas storage/separation Drug delivery Energy storage Optoelectronics MOF
5. Electrically conductive MOFs
6. Electrically conductive MOFs Through-bond approach Charge transport via favourable spatial and energetic overlap of M and L orbitals in covalent bonding
7. Electrically conductive MOFs Through-bond approach Charge transport via favourable spatial and energetic overlap of M and L orbitals in covalent bonding TCNQ@HKUST-1 M. D. Allendorf et al. Science 2014, 343, 66
8. Electrically conductive MOFs Through-bond approach Charge transport via favourable spatial and energetic overlap of M and L orbitals in covalent bonding TCNQ@HKUST-1 M. D. Allendorf et al. Science 2014, 343, 66 Through-space approach Charge transport via non-covalent interactions (S- stacking) between electroactive fragments
9. Electrically conductive MOFs Through-bond approach Charge transport via favourable spatial and energetic overlap of M and L orbitals in covalent bonding TCNQ@HKUST-1 M. D. Allendorf et al. Science 2014, 343, 66 Through-space approach Charge transport via non-covalent interactions (S- stacking) between electroactive fragments TTF-based MOFs M. Dincâ et al. J. Am. Chem. Soc. 2012, 134, 1293
10. Electrically conductive MOFs Through-bond approach Charge transport via favourable spatial and energetic overlap of M and L orbitals in covalent bonding TCNQ@HKUST-1 M. D. Allendorf et al. Science 2014, 343, 66 Through-space approach Charge transport via non-covalent interactions (S- stacking) between electroactive fragments TTF-based MOFs M. Dincâ et al. J. Am. Chem. Soc. 2012, 134, 1293
11. Electrically conductive MOFs J. Calbo, M. J. Golomb. A. Walsh J. Mat. Chem. A 2019, 7, 16571 • Electron-rich linkers • Electron-deficient linkers • d1-d9 metal ions • Covalent linkage • Non-covalent interactions Electroactive organic linkers Metal ion with open- shell configuration Redox-active guest
12. Semiconducting molecular materials One of the first molecular conductors ї Perylene-bromine complex Perylene Conductivity S-S interactions between the planar molecules. Partial oxidation of the perylene units Perylene-based CT complexes with iodine conductivity = 10-2 S/cm
13. Perylene-based MOFs ۶૝ ۾܂۱ ࡷା MOF PTC-K
14. Perylene-based MOFs Experimentally obtained by ۶૝ ۾܂۱ Dr. Manuel Souto Gonçalo Valente ࡷା MOF PTC-K
15. Perylene-based MOFs Experimentally obtained by ۶૝ ۾܂۱ Dr. Manuel Souto Gonçalo Valente Herringbone packing ࡷା MOF PTC-K
16. Results Per-MOF HSE06/tier-1 (light) &ůĂƚďĂŶĚƐїhopping mechanism 2.11 eV
17. Results Per-MOF HSE06/tier-1 (light) PDOS 2.11 eV &ůĂƚďĂŶĚƐїhopping mechanism
18. Results Per-MOF HSE06/tier-1 (light) HOCO LUCO PDOS 2.11 eV &ůĂƚďĂŶĚƐїhopping mechanism
19. Results Per-MOF + I2 2.08 eV HSE06/tier-1 (light) &ůĂƚďĂŶĚƐїhopping mechanism
20. Results Per-MOF + I2 2.08 eV Relative PDOS HSE06/tier-1 (light) &ůĂƚďĂŶĚƐїhopping mechanism
21. Results Per-MOF + I2 2.08 eV Relative PDOS HSE06/tier-1 (light) I2 HOCO &ůĂƚďĂŶĚƐїhopping mechanism
22. Results Per-MOF + I3 2.06 eV 0.09 eV &ůĂƚďĂŶĚƐїhopping mechanism HSE06/tier-1 (light)
23. Results Per-MOF + I3 spin-D (ј) spin-E (љ) 2.06 eV 0.09 eV PDOS HSE06/tier-1 (light) 2.06 eV 0.09 eV &ůĂƚďĂŶĚƐїhopping mechanism
24. Results Per-MOF + I3 spin-D (ј) spin-E (љ) 2.06 eV 0.09 eV PDOS HSE06/tier-1 (light) Unpaired electron on PTC reduces the bandgap 2.06 eV 0.09 eV &ůĂƚďĂŶĚƐїhopping mechanism
25. Results Per-MOF + I3 spin-D (ј) spin-E (љ) 2.06 eV 0.09 eV PDOS HSE06/tier-1 (light) Unpaired electron on PTC reduces the bandgap 2.06 eV 0.09 eV Spin density &ůĂƚďĂŶĚƐїhopping mechanism
26. Results Per-MOF + I3 spin-D (ј) spin-E (љ) 2.06 eV 0.09 eV PDOS HSE06/tier-1 (light) Unpaired electron on PTC reduces the bandgap 2.06 eV 0.09 eV Spin density ȴq (PTC) = +0.90e q (I3 -) = -0.70e &ůĂƚďĂŶĚƐїhopping mechanism
27. Results MOF ࡶ(meV) ҧ ࡶ (meV) Per-MOF 12.16 11.78 11.37 11.82 Per-MOF + I2 7.70 11.16 4.57 21.20 Per-MOF + I3 8.51 8.56 8.61 8.58 J 3 J 1 J 2 FO-DFT PBE Tier-1
28. Results MOF ࡶ(meV) ҧ ࡶ (meV) Per-MOF 12.16 11.78 11.37 11.82 Per-MOF + I2 7.70 11.16 4.57 21.20 Per-MOF + I3 8.51 8.56 8.61 8.58 J 3 J 1 J 2 FO-DFT PBE Tier-1 • Small ҧ ܬ values due to the ineficient herringbone arrangement. • ҧ ܬ values suggest a negligible structural effect of the iodine inclusion on the electronic communication between PTC units.
29. Results MOF ࡶ(meV) ҧ ࡶ (meV) HOCO-half splitting (eV) Per-MOF 12.16 11.78 2.80 11.37 11.82 Per-MOF + I2 7.70 11.16 35.43 4.57 21.20 Per-MOF + I3 8.51 8.56 38.13 (D) 47.16 (E) 8.61 8.58 J 3 J 1 J 2 FO-DFT PBE Tier-1 • Small ҧ ܬ values due to the ineficient herringbone arrangement. • ҧ ܬ values suggest a negligible structural effect of the iodine inclusion on the electronic communication between PTC units. • HOCO-half splitting values indicate that I2 /I3 - species increase the electronic communication between PTC moieties.
30. Results MOF ࡶ(meV) ҧ ࡶ (meV) HOCO-half splitting (eV) Conductivity (S·cm-1) Per-MOF 12.16 11.78 2.80 10-8 11.37 11.82 Per-MOF + I2 7.70 11.16 35.43 10-7-10-5 4.57 21.20 Per-MOF + I3 8.51 8.56 38.13 (D) 47.16 (E) 8.61 8.58 • Small ҧ ܬ values due to the ineficient herringbone arrangement. • ҧ ܬ values suggest a negligible structural effect of the iodine inclusion on the electronic communication between PTC units. • HOCO-half splitting values indicate that I2 /I3 - species increase the electronic communication between PTC moieties. J 3 J 1 J 2 FO-DFT PBE Tier-1
31. Conclusions • We reported the first evidence of the conductivity enhancement of a perylene-based MOF upon iodine-doping. • This conductivity is due to the partial oxidation of the perylene units. The electronic communication between the PTC units in the I2 -doped Per-MOF is boosted by the participation of I2 /I3 - species. • The charge transport in this MOF can be rationalized in terms of a through-space hopping mechanism along the herringbone PTC packing. • The conductivity of the I2 -doped Per-MOF is expected to be increased when the electroactive ligands are packed in a parallel fashion
32. Acknowledgments • Supervisors: Dr. Joaquín Calbo and Prof. Enrique Ortí • All members of MolMatTC group • Collaborators: Dr. Manuel Souto and Gonçalo Valente PID2020-119748GA-I00 funded by MCIN/ AEI/10.13039/501100011033