Future directions for metal-organic framework research

Transcript

1. Boosting the discovery of next-generation porous materials through computation Joaquín Calbo – University of Valencia (SPAIN) UoB-UL-ICMol Mini-symposium on MOFs
2. Who and where we are Molecular Materials Theoretical Chemistry Group Valencia - SPAIN Angelo Giussani Juan Aragó Enrique Ortí
4. tiger nut pastry
5. 1. Covalent D-A architectures 2. Supramolecular D-A complexes 3. Supramolecular polymers Complexity S S R R CN CN NC CN Where do I come from (scientifically)
6. Where do I come from (scientifically) Electroactive porous frameworks Perovskite-like materials for OE Prof. Aron Walsh
7. Guillermo Mínguez (UV) Mónica Giménez (UV) Aron Walsh (ICL) Loredana Protesescu (UG) Manel Souto (USC) Science is cooperation
8. Computational materials design in a nutshell Methodologies Density Functional Theory High-correlated methods Semiempirical methods Molecular Mechanics Big-data Science Properties Crystal structure: geometry & stability Electronic structure: REDOX, magnetism, excited states, charge & energy transport
9. Tetrathiafulvalene (TTF) Electron donor molecule Facile oxidation π−π interactions Charge Transport Model Molecular Electronics Supramolecular Chemistry 166º
10. TTF-based MUV-2 a b TTFTB SBU a b c 33 Å 12 Å Fe(III) Micro/meso-porosity 2 H2 O and 1 OH– OH–
11. ∆E = 5 kcal mol–1 → 0º – 80º Eox (MOF, exp) = 5.7 (PYR) – 6.8 (ACN) V J. Am. Chem. Soc., 2018, 140, 10562–10569. Energy penalty for bending
12. Encapsulation of C60 in MUV-2
13. (Stability) Conformational Analysis NCI interactions −20.01 kcal/mol −23.74 kcal/mol
14. Density of States & Crystal Orbitals Density of states Frontier crystal orbital topologies
15. Theoretical absorption spectra CT excitation Time-dependent DFT
16. 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
17. 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 + ‒ J. Am. Chem. Soc. 2022, 144, 9074−9082
18. Perylene-based MOFs σ = 10‒8 S·cm‒1 Iodine doping Perylene K+ PTC 8.6 Å Per-MOF Distances in Å I2 "I3 "
19. Per-MOF: ̅ 𝑱𝑱 = 11.78 meV [Per-MOF@I2 ]: ̅ 𝑱𝑱 = 11.16 meV [Per-MOF@I3 ]: ̅ 𝑱𝑱 = 8.56 meV Perylene-based MOFs I2 -doped Per-MOF: σ = 10‒5 S·cm‒1 TD-HSE06/def2-SVP Per-MOF: σ = 10‒8 S·cm‒1 Mol. Syst. Des. Eng., 2022, 7, 1065-1072 Electronic coupling between dimers Spin density CT
20. Perylene-based MOFs σRT ~10-10 S/cm (pressed pellets) < 1m0 No relevant porosity Poor experimental conductivity
21. Perylene-based MOFs Absorption and emission properties No relevant porosity
22. 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 Inorg. Chem., 2023, 62, 7834-7842
23. 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
24. 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
25. 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 Band structure
26. 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 Band structure
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 Band structure
28. Fe2 (BDT)3 half-protonated protonated Random protonation P3 P2 P1 deprotonated deprotonated
29. MIL-101 (Cr d3) Nanoparticle (perovskite) Tune absorption/emission Interfacial structure & electronic properties Phase stability & transition in ZIFs ZIF-8 (Zn, Co, Fe) + eim / mbim Chem. Sci., 2021, 12, 6129-6135 Chem. Sci., 2022, 13, 842-847
30. MIL-100(Fe) with carvacrol ΔE = −11.23 kcal/mol (carvacrol by water) Spin density (radical formation) Carvacrol-MOF interaction ACS Appl. Mater. & Interfaces, 2022, 14, 10758-10768 Carvacrol liberation Antimicrobial activity MIL-100 (FeIII) NPs Carvacrol encapsulation Without H With H
31. We carry out theoretical studies by performing calculations at the appropriate level of theory for:  Crystal elucidation and structural stability  Understanding electronic structure and redox properties  Excited state phenomena  Strategies to enhance conductivity in porous frameworks: mixed- valence, electroactive guests and/or redox-active ligands Overview
32. Acknowledgements UoB-UL-ICMol Symposium Collaborators: The team: PID2020-119748GA-I00 funded by MCIN/AEI/10.13039/501100011033