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VII Colloquium on Computational Simulations in ...

Joaquin
November 24, 2024

VII Colloquium on Computational Simulations in Sciences

Joaquin

November 24, 2024
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  1. Strategies to boost electrical conductivity in porous materials: a computational

    perspective computational-experimental VII Colloquium on Computational Simulation in Sciences
  2. Zn(II) ⇒ d0 benzene MOF-5 Physical and chemical processes: Gas

    adsorption & separation, catalysis Electro-inactive porous materials
  3. Computational materials design in a nutshell Methodologies Density Functional Theory

    High-correlated methods Semiempirical methods Molecular Mechanics Big-data Science Properties Geometry Electronic structure REDOX and magnetism Excited states Charge and energy transport
  4. Tetrathiafulvalene (TTF) Electron donor molecule Facile oxidation π−π interactions Charge

    Transport Model Molecular Electronics Supramolecular Chemistry 166º
  5. Hydrogen-bonded Organic Frameworks H4 TTFTB MUV-20a MUV-20b MUV-21 σ =

    6.07 × 10–7 S cm–1 σ = 1.35 × 10–6 S cm–1 σ = 6.23 × 10–9 S cm–1 Guillermo Mínguez (UV) María Vicent (UV)
  6. Hydrogen-bonded Organic Frameworks H4 TTFTB MUV-20a MUV-20b MUV-21 σ =

    6.07 × 10–7 S cm–1 σ = 1.35 × 10–6 S cm–1 σ = 6.23 × 10–9 S cm–1 PBEsol // HSE06 | FO-DFT
  7. Hydrogen-bonded Organic Frameworks EPR MUV-20a MUV-21 MUV-20b The TTF has

    an unpaired e― HOFs are charge neutral There is no countercation non-radical
  8. Hydrogen-bonded Organic Frameworks EPR MUV-20a MUV-21 MUV-20b The TTF has

    an unpaired e― HOFs are charge neutral There is no countercation non-radical + ‒
  9. Hydrogen-bonded Organic Frameworks vacuum dielectric continuum SPIN DENSITY EPR MUV-20a

    MUV-21 MUV-20b The TTF has an unpaired e― HOFs are charge neutral There is no countercation non-radical + ‒
  10. Hydrogen-bonded Organic Frameworks vacuum dielectric continuum SPIN DENSITY EPR MUV-20a

    MUV-21 MUV-20b The TTF has an unpaired e― HOFs are charge neutral There is no countercation SPIN DENSITY accumulated charge non-radical + ‒
  11. Hydrogen-bonded Organic Frameworks vacuum dielectric continuum SPIN DENSITY EPR MUV-20a

    MUV-21 MUV-20b The TTF has an unpaired e― HOFs are charge neutral There is no countercation SPIN DENSITY accumulated charge non-radical + ‒
  12. Perylene-based MOFs Manel Souto (UA) Gonçalo Valente (UA) Perylene K+

    PTC 8.6 Å Per-MOF Mol. Syst. Des. Eng., 2022,7, 1065-1072 σ = 10‒8 S·cm‒1
  13. Perylene-based MOFs Manel Souto (UA) Gonçalo Valente (UA) σ =

    10‒8 S·cm‒1 Iodine doping Perylene K+ PTC 8.6 Å Per-MOF Mol. Syst. Des. Eng., 2022,7, 1065-1072 Distances in Å I2 "I3 "
  14. Per-MOF: ̅ 𝑱𝑱 = 11.78 meV [Per-MOF@I2 ]: ̅ 𝑱𝑱

    = 11.16 meV [Per-MOF@I3 ]: ̅ 𝑱𝑱 = 8.56 meV Perylene-based MOFs
  15. Per-MOF: ̅ 𝑱𝑱 = 11.78 meV [Per-MOF@I2 ]: ̅ 𝑱𝑱

    = 11.16 meV [Per-MOF@I3 ]: ̅ 𝑱𝑱 = 8.56 meV Perylene-based MOFs
  16. Per-MOF: ̅ 𝑱𝑱 = 11.78 meV [Per-MOF@I2 ]: ̅ 𝑱𝑱

    = 11.16 meV [Per-MOF@I3 ]: ̅ 𝑱𝑱 = 8.56 meV I3 Spin density Perylene-based MOFs TD-HSE06/def2-SVP ─
  17. Per-MOF: ̅ 𝑱𝑱 = 11.78 meV [Per-MOF@I2 ]: ̅ 𝑱𝑱

    = 11.16 meV [Per-MOF@I3 ]: ̅ 𝑱𝑱 = 8.56 meV Spin density Perylene-based MOFs Per-MOF: σ = 10‒8 S·cm‒1 I2 -doped Per-MOF: σ = 10‒5 S·cm‒1 TD-HSE06/def2-SVP I3 ─
  18. Perylene-based MOFs σRT ~10-10 S/cm (pressed pellets) PerMOF: σRT ~10-8

    S/cm (two-contact single-crystal) < 1m0 No relevant porosity
  19. Perylene-based MOFs ‒30 meV +70 meV +60 meV 559 nm

    673 nm 663 nm excitonic coupling TD-DFT/PBE0/6-31G(d,p) Lowest-lying singlet excited state
  20. Iron-based MOFs Chem. Sci., 2017, 8, 4450–4457 Mixed-valency Fe(II)/Fe(III) Fe2

    (BDT)3 J. Am. Chem. Soc. 2018, 140, 7411–7414 Fe(II) σ = 10–4 – 1.8 S/cm
  21. N N N NH N N N HN H2 BDT

    Iron-based MOFs BDT2– Fe(II) Fe2 (H0.67 BDT)3 (II) (2–) P2 P3 P1
  22. Fe2 (BDT)3 Protonated 1.45 80.31 Γ to Z direction VBM

    T to Z direction CBM hole transport electron transport Deprotonated (Cmmm) P1
  23. Fe2 (BDT)3 Protonated 1.45 80.31 Γ to Z direction VBM

    T to Z direction CBM hole transport electron transport Deprotonated Charge transport pathways (Cmmm) P1
  24. Fe2 (BDT)3 1.45 80.31 Γ to Z direction VBM CBM

    hole transport electron transport Deprotonated (Fddd) P2 Partially protonated directions
  25. Fe2 (BDT)3 1.45 80.31 Γ to Z direction VBM CBM

    hole transport electron transport Deprotonated Partially protonated directions Charge transport pathways (Fddd) P2
  26. Fe2 (BDT)3 1.45 80.31 VBM CBM hole transport electron transport

    Random distribution of protonated ligands (R-3m) P3
  27. Fe2 (BDT)3 1.45 80.31 VBM CBM hole transport electron transport

    Charge transport pathways Random distribution of protonated ligands h+ (R-3m) P3
  28.  Cooperation between experiments and theoretical modelling allows boosting the

    development of electrically conducting porous materials.  TTF and perylene are interesting and versatile organic moieties as well as Fe(II)/Fe(III) pair for designing electroactive materials.  Strategies to enhance conductivity in porous frameworks: o Zwitterion species in a π-stacked assembly o Electroactive guests (charge transfer and carrier formation) o Mixed-valence and appropriate protonation pattern Conclusions
  29.  Cooperation between experiments and theoretical modelling allows boosting the

    development of electrically conducting porous materials.  TTF and perylene are interesting and versatile organic moieties as well as Fe(II)/Fe(III) pair for designing electroactive materials.  Strategies to enhance conductivity in porous frameworks: o Zwitterion species in a π-stacked assembly o Electroactive guests (charge transfer and carrier formation) o Mixed-valence and appropriate protonation pattern Conclusions
  30.  Cooperation between experiments and theoretical modelling allows boosting the

    development of electrically conducting porous materials.  TTF and perylene are interesting and versatile organic moieties as well as Fe(II)/Fe(III) pair for designing electroactive materials.  Strategies to enhance conductivity in porous frameworks: o Zwitterion species in a π-stacked assembly o Electroactive guests (charge transfer and carrier formation) o Mixed-valence and appropriate protonation pattern Conclusions