A Heteromeric Carboxylic Acid Based Single‐Crystalline Crosslinked Organic Framework

Abstract

The development of large pore single‐crystalline covalently linked organic frameworks is critical in revealing the detailed structure‐property relationship with substrates. One emergent approach is to photo‐crosslink hydrogen‐bonded molecular crystals. Introducing complementary hydrogen‐bonded carboxylic acid building blocks is promising to construct large pore networks, but these molecules often form interpenetrated networks or non‐porous solids. Herein, we introduced heteromeric carboxylic acid dimers to construct a non‐interpenetrated molecular crystal. Crosslinking this crystal precursor with dithiols afforded a large pore single‐crystalline hydrogen‐bonded crosslinked organic framework HCOF‐101. X‐ray diffraction analysis revealed HCOF‐101 as an interlayer connected hexagonal network, which possesses flexible linkages and large porous channels to host a hydrazone photoswitch. Multicycle Z/E‐isomerization of the hydrazone took place reversibly within HCOF‐101, showcasing the potential use of HCOF‐101 for optical information storage.

Hydrogen-bonded cobalt(ii)-organic framework: normal and reverse spin-crossover behaviours

“…Recently, organic/inorganic compounds undergoing self-assembly through H-bonds have been intensively investigated in terms of their porosity, where these materials are referred to as hydrogen-bonded organic/inorganic frameworks (HOFs/HIFs). [17][18][19][20][21][22] However, the strategic molecular construction of these systems depending on intermolecular interactions remains challenging. In particular, H-MOFs require the coexistence of coordination and hydrogen bonds.…”

A Heteromeric Carboxylic Acid Based Single‐Crystalline Crosslinked Organic Framework

“…Top: asymmetric unit, middle: an image of the crystal, bottom: packed structures viewed along the a/b plane and c-axis, hydrogens were omitted for clarity. [24] rotations (Figure 2 c). The pore size of M1-TA crystal is measured to be 16 when accounting for the allylethers, which is smaller than the d = 21 calculated from the 100 diffraction (Figure 2 b,c).…”

“…Z-H1 emits at l em = 560 nm in toluene, but its emission is red-shifted to 620 nm in crystalline form because of its head-to-tail packing. [23] H C OF-101•Z-H1 emits (l em = 575 nm, Figure 5 [24] Angewandte Chemie Zuschriften crystalline form of Z-H1, where no appreciable isomerization was observed even after prolonged photoirradiation. Thus, the inclusion of Z-H1 in H C OF-101 makes H1 behave as it does in solution rather than in its neat crystalline state.…”

“…c) Crystal structures of M1-TA crystal . Top: asymmetric unit, middle: an image of the crystal, bottom: packed structures viewed along the a/b plane and c-axis, hydrogens were omitted for clarity [24].…”

“…c) PXRD profiles of H C OF-101 soaked in various solvents. d) Vapor sorption isotherms of H C OF-101 [24].…”