# Isoreticular expansion, interpenetration, MTV MOFs

> Isoreticular design on one page: the IRMOF series from MOF-5 to IRMOF-16, IRMOF-74-I to -XI with apertures up to 98 Å, HKUST-1 and MOF-399 on the tbo net, interpenetrated IRMOF-9 against IRMOF-10, ways to prevent or use interpenetration, and multivariate MOF-5 with several functional groups on one backbone. Every statement and number is quoted from the cited papers.

- Page: https://www.labcanvas.com/templates/mof-guides/isoreticular-expansion-interpenetration-mtv-mofs
- Open in the LabCanvas editor (LabCanvas account): https://www.labcanvas.com/editor.html?template=mof-isoreticular-interpenetration-mtv
- Updated: 2026-10-14
- Category: MOF guides
- Method: Isoreticular design
- Product: Isoreticular series of frameworks, interpenetrated and non-interpenetrated pairs, and multivariate MOFs
- Key result: Frameworks, links and nets drawn by LabCanvas from the cited structures; the IRMOF-74 channels and the tbo linkers are to scale, other sizes are schematic, and no panel is a refined structure
- Figure: 1920 × 1080 px, 45 editable layers (6 generated objects with settings)

## Steps

1. **The IRMOF series**: MOF-5 was functionalized with –Br, –NH₂, –OC₃H₇, –OC₅H₁₁, –C₂H₄ and –C₄H₄ and expanded with biphenyl, tetrahydropyrene, pyrene and terphenyl struts: an isoreticular series, one with the same framework topology, of 16 highly crystalline materials with pores from 3.8 to 28.8 Å and open space up to 91.1% of the crystal volume (Eddaoudi 2002). IRMOF-1 is MOF-5 (Boyd 2017); IRMOF-8 is Zn₄O(ndc)₃ (Feldblyum 2012); IRMOF-10 is the non-interpenetrated Zn₄O(BPDC)₃ (Wang 2014); IRMOF-16, Zn₄O(TPDC)₃, has pores up to 28.8 Å (Kalmutzki 2018)
2. **IRMOF-74-I to -XI**: Expanding the link of MOF-74 from one phenylene ring (I) to two to seven, nine and eleven (II to XI) gave IRMOF-74-I to -XI, with pore apertures from 14 to 98 Å; all are noninterpenetrated and stable up to 300 °C, and the apertures of oligoethylene glycol-functionalized IRMOF-74-VII and -IX are large enough for natural proteins to enter the pores (Deng 2012). IRMOF-74-XI has 85 × 98 Å pores, the largest 1D pores in MOFs reported by 2018 (Kalmutzki 2018)
3. **HKUST-1 to MOF-399**: MOF-399, Cu₃(BBC)₂ on the tbo net, has a unit cell volume 17 times that of the first reported material isoreticular to it, 94% porosity and a density of 0.126 g cm⁻³ (Furukawa 2011); BBC is 4,4′,4″-[benzene-1,3,5-triyl-tris(benzene-4,1-diyl)]tribenzoate (Furukawa 2010). ZJU-35 and ZJU-36 have the same tbo topology as HKUST-1, with pores of 14.4 and 16.5 Å against 10.8 Å in HKUST-1 (Kong 2013); HKUST-1 joins [Cu₂(O₂CR)₄] units by benzene-1,3,5-tricarboxylate (Chui 1999)
4. **IRMOF-9 or IRMOF-10**: Zn₄O(BPDC)₃ forms interpenetrated IRMOF-9 or non-interpenetrated IRMOF-10 (Wang 2014). Independent nets interpenetrate in many polymeric, hydrogen-bonded and coordination structures (Batten & Robson 1998); interpenetration greatly reduces the pore size and the available space in a MOF (Shekhah 2009), and catenation diminishes porosity (Farha 2010). IRMOF-8 typically shows only 1000–2000 m² g⁻¹ where more than 4000 m² g⁻¹ is expected, from near-complete interpenetration (Feldblyum 2013). In simulations, catenated MOFs were more selective for CO₂ over CH₄ than their non-catenated counterparts (Babarao 2009)
5. **Preventing or using it**: The steric bulk of a doped linker switched IRMOF-9 to IRMOF-10 (Wang 2014); strut-impervious scaffolds give noncatenated MOFs (Farha 2010). Room-temperature synthesis suppressed interpenetration in IRMOF-8 (Feldblyum 2012); higher temperatures and concentrations favour it (Zhang 2009); liquid-phase epitaxy on an organic template suppressed the second framework (Shekhah 2009). Interpenetration in PCN-6 can lead to higher hydrogen uptake (Zhao 2011); MOF-14, Cu₃(BTB)₂, is a pair of interwoven frameworks that reinforce each other, with pores 16.4 Å across (Chen 2001)
6. **Multivariate MOF-5**: 18 MTV-MOF-5 structures were made from BDC and eight of its derivatives, with up to eight distinct functionalities in one phase; the backbone is ordered but the distribution of the functional groups is disordered, and MTV-MOF-5-EHI is up to 400% more selective for CO₂ over CO than its best same-link counterparts (Deng 2010). Solid-state NMR with simulations told apart random, alternating and cluster apportionments of the groups (Kong 2013). Mixing –H, –NH₂ and –C₄H₄ on BTB helped bring in –NO₂, and multivariate MOF-177 took up 25% more hydrogen (Zhang 2015). With mixed metals, porphyrin MOFs with well-mixed SBUs performed better than the sum of their parts in a photo-oxidation (Liu 2016); MOF-74 took up to ten kinds of divalent metal in one crystal (Wang 2014)

## Strengths

- IRMOF-74-VII and -IX have apertures large enough for natural proteins (Deng 2012)
- MOF-14’s interwoven frameworks reinforce each other (Chen 2001)
- Catenated MOFs were more selective for CO₂ over CH₄ in simulations (Babarao 2009)

## Limitations

- In the Zn₄O-based IRMOF series, accessible porosity is often limited by interpenetration or by pore collapse when guests are removed (Feldblyum 2013)
- Interpenetration greatly reduces the pore size and the available space (Shekhah 2009)
- In MTV-MOF-5 the distribution of the functional groups is disordered (Deng 2010)

## References

1. Eddaoudi et al., “Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage”, Science 2002. https://doi.org/10.1126/science.1067208 (primary)
2. Boyd et al., “Force-field prediction of materials properties in metal-organic frameworks”, J. Phys. Chem. Lett. 2017. https://doi.org/10.1021/acs.jpclett.6b02532 (primary)
3. Feldblyum, Wong-Foy & Matzger, “Non-interpenetrated IRMOF-8: synthesis, activation, and gas sorption”, Chem. Commun. 2012. https://doi.org/10.1039/c2cc34689c (primary)
4. Wang et al., “Functional metal-organic frameworks via ligand doping: influences of ligand charge and steric demand”, Inorg. Chem. 2014. https://doi.org/10.1021/ic402015q (primary)
5. Kalmutzki, Hanikel & Yaghi, “Secondary building units as the turning point in the development of the reticular chemistry of MOFs”, Sci. Adv. 2018. https://doi.org/10.1126/sciadv.aat9180 (primary)
6. Deng et al., “Large-pore apertures in a series of metal-organic frameworks”, Science 2012. https://doi.org/10.1126/science.1220131 (primary)
7. Furukawa et al., “Isoreticular expansion of metal-organic frameworks with triangular and square building units and the lowest calculated density for porous crystals”, Inorg. Chem. 2011. https://doi.org/10.1021/ic201376t (primary)
8. Furukawa et al., “Ultrahigh porosity in metal-organic frameworks”, Science 2010. https://doi.org/10.1126/science.1192160 (primary)
9. Kong et al., “Expanded organic building units for the construction of highly porous metal-organic frameworks”, Chem. Eur. J. 2013. https://doi.org/10.1002/chem.201302515 (primary)
10. Chui et al., “A chemically functionalizable nanoporous material”, Science 1999. https://doi.org/10.1126/science.283.5405.1148 (primary)
11. Batten & Robson, “Interpenetrating nets: ordered, periodic entanglement”, Angew. Chem. Int. Ed. 1998. https://doi.org/10.1002/(SICI)1521-3773(19980619)37:11<1460::AID-ANIE1460>3.0.CO;2-Z (primary)
12. Shekhah et al., “Controlling interpenetration in metal-organic frameworks by liquid-phase epitaxy”, Nat. Mater. 2009. https://doi.org/10.1038/nmat2445 (primary)
13. Farha et al., “Control over catenation in metal-organic frameworks via rational design of the organic building block”, J. Am. Chem. Soc. 2010. https://doi.org/10.1021/ja909519e (primary)
14. Feldblyum et al., “Interpenetration, porosity, and high-pressure gas adsorption in Zn₄O(2,6-naphthalene dicarboxylate)₃”, Langmuir 2013. https://doi.org/10.1021/la401323t (primary)
15. Babarao, Jiang & Sandler, “Molecular simulations for adsorptive separation of CO₂/CH₄ mixture in metal-exposed, catenated, and charged metal-organic frameworks”, Langmuir 2009. https://doi.org/10.1021/la803074g (primary)
16. Zhang et al., “Temperature and concentration control over interpenetration in a metal-organic material”, J. Am. Chem. Soc. 2009. https://doi.org/10.1021/ja906911q (primary)
17. Zhao et al., “Tuning the topology and functionality of metal-organic frameworks by ligand design”, Acc. Chem. Res. 2011. https://doi.org/10.1021/ar100112y (primary)
18. Chen et al., “Interwoven metal-organic framework on a periodic minimal surface with extra-large pores”, Science 2001. https://doi.org/10.1126/science.1056598 (primary)
19. Deng et al., “Multiple functional groups of varying ratios in metal-organic frameworks”, Science 2010. https://doi.org/10.1126/science.1181761 (primary)
20. Kong et al., “Mapping of functional groups in metal-organic frameworks”, Science 2013. https://doi.org/10.1126/science.1238339 (primary)
21. Zhang et al., “Introduction of functionality, selection of topology, and enhancement of gas adsorption in multivariate metal-organic framework-177”, J. Am. Chem. Soc. 2015. https://doi.org/10.1021/ja512311a (primary)
22. Liu, Cong & Deng, “Deciphering the spatial arrangement of metals and correlation to reactivity in multivariate metal-organic frameworks”, J. Am. Chem. Soc. 2016. https://doi.org/10.1021/jacs.6b08724 (primary)
23. Wang et al., “Synthesis and characterization of metal-organic framework-74 containing 2, 4, 6, 8, and 10 different metals”, Inorg. Chem. 2014. https://doi.org/10.1021/ic500434a (primary)

Credit: Drawn by LabCanvas after Eddaoudi et al., Science 2002 (doi:10.1126/science.1067208), Deng et al., Science 2012, Furukawa et al., Inorg. Chem. 2011, Wang et al., Inorg. Chem. 2014 and Feldblyum et al., Langmuir 2013, and the papers in the details.

## Questions

**What does the “Isoreticular expansion, interpenetration, MTV MOFs” template show?** Isoreticular design on one page: the IRMOF series from MOF-5 to IRMOF-16, IRMOF-74-I to -XI with apertures up to 98 Å, HKUST-1 and MOF-399 on the tbo net, interpenetrated IRMOF-9 against IRMOF-10, ways to prevent or use interpenetration, and multivariate MOF-5 with several functional groups on one backbone. Every statement and number is quoted from the cited papers.

**What are the steps shown in “Isoreticular expansion, interpenetration, MTV MOFs”?** 1. The IRMOF series: MOF-5 was functionalized with –Br, –NH₂, –OC₃H₇, –OC₅H₁₁, –C₂H₄ and –C₄H₄ and expanded with biphenyl, tetrahydropyrene, pyrene and terphenyl struts: an isoreticular series, one with the same framework topology, of 16 highly crystalline materials with pores from 3.8 to 28.8 Å and open space up to 91.1% of the crystal volume (Eddaoudi 2002). IRMOF-1 is MOF-5 (Boyd 2017); IRMOF-8 is Zn₄O(ndc)₃ (Feldblyum 2012); IRMOF-10 is the non-interpenetrated Zn₄O(BPDC)₃ (Wang 2014); IRMOF-16, Zn₄O(TPDC)₃, has pores up to 28.8 Å (Kalmutzki 2018). 2. IRMOF-74-I to -XI: Expanding the link of MOF-74 from one phenylene ring (I) to two to seven, nine and eleven (II to XI) gave IRMOF-74-I to -XI, with pore apertures from 14 to 98 Å; all are noninterpenetrated and stable up to 300 °C, and the apertures of oligoethylene glycol-functionalized IRMOF-74-VII and -IX are large enough for natural proteins to enter the pores (Deng 2012). IRMOF-74-XI has 85 × 98 Å pores, the largest 1D pores in MOFs reported by 2018 (Kalmutzki 2018). 3. HKUST-1 to MOF-399: MOF-399, Cu₃(BBC)₂ on the tbo net, has a unit cell volume 17 times that of the first reported material isoreticular to it, 94% porosity and a density of 0.126 g cm⁻³ (Furukawa 2011); BBC is 4,4′,4″-[benzene-1,3,5-triyl-tris(benzene-4,1-diyl)]tribenzoate (Furukawa 2010). ZJU-35 and ZJU-36 have the same tbo topology as HKUST-1, with pores of 14.4 and 16.5 Å against 10.8 Å in HKUST-1 (Kong 2013); HKUST-1 joins [Cu₂(O₂CR)₄] units by benzene-1,3,5-tricarboxylate (Chui 1999). 4. IRMOF-9 or IRMOF-10: Zn₄O(BPDC)₃ forms interpenetrated IRMOF-9 or non-interpenetrated IRMOF-10 (Wang 2014). Independent nets interpenetrate in many polymeric, hydrogen-bonded and coordination structures (Batten & Robson 1998); interpenetration greatly reduces the pore size and the available space in a MOF (Shekhah 2009), and catenation diminishes porosity (Farha 2010). IRMOF-8 typically shows only 1000–2000 m² g⁻¹ where more than 4000 m² g⁻¹ is expected, from near-complete interpenetration (Feldblyum 2013). In simulations, catenated MOFs were more selective for CO₂ over CH₄ than their non-catenated counterparts (Babarao 2009). 5. Preventing or using it: The steric bulk of a doped linker switched IRMOF-9 to IRMOF-10 (Wang 2014); strut-impervious scaffolds give noncatenated MOFs (Farha 2010). Room-temperature synthesis suppressed interpenetration in IRMOF-8 (Feldblyum 2012); higher temperatures and concentrations favour it (Zhang 2009); liquid-phase epitaxy on an organic template suppressed the second framework (Shekhah 2009). Interpenetration in PCN-6 can lead to higher hydrogen uptake (Zhao 2011); MOF-14, Cu₃(BTB)₂, is a pair of interwoven frameworks that reinforce each other, with pores 16.4 Å across (Chen 2001). 6. Multivariate MOF-5: 18 MTV-MOF-5 structures were made from BDC and eight of its derivatives, with up to eight distinct functionalities in one phase; the backbone is ordered but the distribution of the functional groups is disordered, and MTV-MOF-5-EHI is up to 400% more selective for CO₂ over CO than its best same-link counterparts (Deng 2010). Solid-state NMR with simulations told apart random, alternating and cluster apportionments of the groups (Kong 2013). Mixing –H, –NH₂ and –C₄H₄ on BTB helped bring in –NO₂, and multivariate MOF-177 took up 25% more hydrogen (Zhang 2015). With mixed metals, porphyrin MOFs with well-mixed SBUs performed better than the sum of their parts in a photo-oxidation (Liu 2016); MOF-74 took up to ten kinds of divalent metal in one crystal (Wang 2014).

**Which papers is “Isoreticular expansion, interpenetration, MTV MOFs” based on?** Eddaoudi et al., “Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage”, Science 2002 (doi:10.1126/science.1067208); Boyd et al., “Force-field prediction of materials properties in metal-organic frameworks”, J. Phys. Chem. Lett. 2017 (doi:10.1021/acs.jpclett.6b02532); Feldblyum, Wong-Foy & Matzger, “Non-interpenetrated IRMOF-8: synthesis, activation, and gas sorption”, Chem. Commun. 2012 (doi:10.1039/c2cc34689c); Wang et al., “Functional metal-organic frameworks via ligand doping: influences of ligand charge and steric demand”, Inorg. Chem. 2014 (doi:10.1021/ic402015q); Kalmutzki, Hanikel & Yaghi, “Secondary building units as the turning point in the development of the reticular chemistry of MOFs”, Sci. Adv. 2018 (doi:10.1126/sciadv.aat9180); Deng et al., “Large-pore apertures in a series of metal-organic frameworks”, Science 2012 (doi:10.1126/science.1220131); Furukawa et al., “Isoreticular expansion of metal-organic frameworks with triangular and square building units and the lowest calculated density for porous crystals”, Inorg. Chem. 2011 (doi:10.1021/ic201376t); Furukawa et al., “Ultrahigh porosity in metal-organic frameworks”, Science 2010 (doi:10.1126/science.1192160); Kong et al., “Expanded organic building units for the construction of highly porous metal-organic frameworks”, Chem. Eur. J. 2013 (doi:10.1002/chem.201302515); Chui et al., “A chemically functionalizable nanoporous material”, Science 1999 (doi:10.1126/science.283.5405.1148); Batten & Robson, “Interpenetrating nets: ordered, periodic entanglement”, Angew. Chem. Int. Ed. 1998 (doi:10.1002/(SICI)1521-3773(19980619)37:11<1460::AID-ANIE1460>3.0.CO;2-Z); Shekhah et al., “Controlling interpenetration in metal-organic frameworks by liquid-phase epitaxy”, Nat. Mater. 2009 (doi:10.1038/nmat2445); Farha et al., “Control over catenation in metal-organic frameworks via rational design of the organic building block”, J. Am. Chem. Soc. 2010 (doi:10.1021/ja909519e); Feldblyum et al., “Interpenetration, porosity, and high-pressure gas adsorption in Zn₄O(2,6-naphthalene dicarboxylate)₃”, Langmuir 2013 (doi:10.1021/la401323t); Babarao, Jiang & Sandler, “Molecular simulations for adsorptive separation of CO₂/CH₄ mixture in metal-exposed, catenated, and charged metal-organic frameworks”, Langmuir 2009 (doi:10.1021/la803074g); Zhang et al., “Temperature and concentration control over interpenetration in a metal-organic material”, J. Am. Chem. Soc. 2009 (doi:10.1021/ja906911q); Zhao et al., “Tuning the topology and functionality of metal-organic frameworks by ligand design”, Acc. Chem. Res. 2011 (doi:10.1021/ar100112y); Chen et al., “Interwoven metal-organic framework on a periodic minimal surface with extra-large pores”, Science 2001 (doi:10.1126/science.1056598); Deng et al., “Multiple functional groups of varying ratios in metal-organic frameworks”, Science 2010 (doi:10.1126/science.1181761); Kong et al., “Mapping of functional groups in metal-organic frameworks”, Science 2013 (doi:10.1126/science.1238339); Zhang et al., “Introduction of functionality, selection of topology, and enhancement of gas adsorption in multivariate metal-organic framework-177”, J. Am. Chem. Soc. 2015 (doi:10.1021/ja512311a); Liu, Cong & Deng, “Deciphering the spatial arrangement of metals and correlation to reactivity in multivariate metal-organic frameworks”, J. Am. Chem. Soc. 2016 (doi:10.1021/jacs.6b08724); Wang et al., “Synthesis and characterization of metal-organic framework-74 containing 2, 4, 6, 8, and 10 different metals”, Inorg. Chem. 2014 (doi:10.1021/ic500434a).

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