Orthogonal Postsynthetic Copolymerization of Hydrogen‐Bonded Organic Frameworks into a PolyHOF Membrane

Abstract

Hydrogen‐bonded organic frameworks (HOFs) have shown promise in various fields; however, the construction of HOF/polymer hybrid membranes that can maintain both structural and functional integrity remains challenging. In this study, we here fabricated a new HOF (HOF‐50) with reserved polymerizable allyl group via charge‐assisted H‐bonds between the carboxylate anion and amidinium, and subsequently copolymerized the HOF with monomers to construct a covalently bonded HOF/polymer hybrid (polyHOF) membrane. The resulting polyHOF membrane not only exhibits customizable mechanical properties and extreme stability, but also shows an exceptional ratiometric luminescent temperature‐sensing function with very high sensitivity and visibility even when the lanthanide content is two orders of magnitude lower than that of the reported mixed‐lanthanide metal organic frameworks (MOFs) and lanthanide‐doped covalent organic frameworks (COFs). This orthogonal postsynthesis copolymerization strategy may provide a general approach for preparing covalently connected HOF/polymer hybrid membranes for diverse applications.

Photoresponsive lanthanide luminescent materials

“…55,56 However, co-doping Ln 3+ ions can result in a luminescence increase of one Ln 3+ ion and a decrease of the other Ln 3+ ion, or a luminescence dramatic decrease of one Ln 3+ ion and a slight decrease of the other Ln 3+ ion, which is due to energy transfer between the two Ln 3+ ions. 57 Qian and Chen et al developed a mixed-lanthanide metal–organic framework (LnMOFs) (Eu 0.0069 Tb 0.9931 -DMBDC, DMBDC = 2,5-dimethoxy-1,4-benzenedicarboxylic acid), and constructed a high-sensitivity luminescent thermometer using the temperature-dependent energy transfer between Tb 3+ and Eu 3+ in Eu 0.0069 Tb 0.9931 -DMBDC (Fig. 3).…”

Interconversion and functional composites of metal–organic frameworks and hydrogen-bonded organic frameworks

“…Additionally, oriented growth of crystals on the surface of MOFs can significantly influence their properties; thus achieving oriented growth of HOF crystals on MOF surfaces would further regulate the properties of the obtained composite materials. Although there are no existing examples of core–shell composites with HOF as the core, certain stable HOFs have demonstrated resistance to post-synthesis operations such as photopolymerization or nucleophilic substitution reactions, 61–63 providing opportunities for preparing core–shell complexes featuring HOF cores.…”

Arylsulfonate Ionic Hydrogen-Bonded Organic Frameworks Enable Highly Stable and Superprotonic Conductivity for Enhancing Direct Methanol Fuel Cells

“…The stabilization of PEMs not only ensures the sustained and efficient transfer of protons but also enhances the longevity of battery operation . However, hydrogen bonds, being highly reversible and weak interactions, make HOFs unstable and hinder their further development in PEMs. − We attempt to enhance the stability by introducing π–π stacking, charge-assisted hydrogen bonding, constructing structural interpenetrating networks, etc. ,− Doping HOFs with excellent performance into proton-conducting polymers can greatly improve the continuity of the proton transport channel, leading to the development of PEMs with excellent performance. , Moreover, HOFs have good solution processability and easy healing and regeneration, facilitating the preparation of composite membranes; and they are very compatible with polymers, which avoids the formation of interinterfacial defects to a certain extent. ,,− This will broaden the scope of the fabrication of solid-state proton conductive membranes. Until now, iHOFs with superprotonic conductivity and superior stability have rarely been investigated.…”