Exploring and Expanding the Fe-Terephthalate Metal-Organic Framework Phase Space by Coordination and Oxidation Modulation

28 July 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


The synthesis of phase pure metal-organic frameworks (MOFs) – network solids of metal clusters connected by organic linkers – is often complicated by the possibility of forming multiple diverse phases from one metal-ligand combination. For example, there are at least six Fe-terephthalate MOFs reported to date, with many examples of erroneous assignment of phase based on diffraction data alone. Herein, we show that modulated self-assembly can be used to influence the kinetics of self-assembly of Fe-terephthalate MOFs. We comprehensively assess the effect of addition of both coordinating modulators and pH modulators to the outcome of syntheses, as well as probing the influence of the oxidation state of the Fe precursor (oxidation modulation) and the role of the counteranion on the phase(s) formed. In doing so, we shed light on the thermodynamic landscape of this phase system, uncover mechanistics of modulation, provide robust routes to phase pure materials, often as single crystals, and introduce two new Fe-terephthalate MOFs to an already complex system. The results highlight the potential of modulated self-assembly to bring precision control and new structural diversity to systems that have already received significant study.


metal-organic frameworks
coordination polymers
coordination modulation

Supplementary materials

Electronic Supporting Information
Synthetic procedures, diffraction data, calculations, etc.


Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.