An Ultra‐Robust and Crystalline Redeemable Hydrogen‐Bonded Organic Framework for Synergistic Chemo‐Photodynamic Therapy

Abstract

The low structural stability of hydrogen-bonded organic frameworks (HOFs) is at horny issue retarding the development of HOFs.Arational design approach is now proposed for construction of astable HOF.The resultant HOF (PFC-1) exhibits high surface area of 2122 m 2 g À1 and excellent chemical stability (intact in concentrated HCl for at least 117 days). An ew method of acid-assisted crystalline redemption is used to readily cure the thermal damage to PFC-1. With periodic integration of photoactive pyrene in the robust framework, PFC-1 can efficiently encapsulate Doxorubicin (Doxo) for synergistic chemo-photodynamic therapy, showing comparable therapeutic efficacy with the commercial Doxoyet considerably lower cytotoxicity.T his work demonstrates the notorious stability issue of HOFs can be properly addressed through rational design, paving away to develop robust HOFs and offering promising application perspectives.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Taming nitroformate through encapsulation with nitrogen-rich hydrogen-bonded organic frameworks

“…3 and 4) [5][6][7][12][13][14][15][16] . Although the density of HOF-NF is lower than most modern energetic compounds [38][39][40] , it has one of the highest densities reported for HOFs so far [19][20][21][22][23][24][25][26][27][28] . This is because (1) the pores, which are filled with NF1 and NF2, occupy about 17% of the volume of the unit cell, which is lower than most of the occupancy of pores among reported HOFs; and (2) the introduction of the highly dense NF.…”

“…Contrary to MOFs and COFs (covalent organic frameworks), HOFs are easily prepared, their structure can be easily elucidated using single-crystal X-ray diffraction, the starting materials are readily found, and their regeneration processes are low energy-consuming 22,23 . In particular, HOFs show excellent thermal stability [24][25][26][27][28] . For example, HOF-19 23 and HOF-TCBP 24 show thermal stabilities as high as 350 and 395°C (Fig.…”

Self-Recognizing π-π Stacking Interactions Designed for the Generation of Ultrastable Mesoporous Hydrogen-Bonded Organic Frameworks

“…Pyrene, a classic fused benzene ring molecule with planar conformation and large π-conjugated system, is chosen as the center of the tectons. Previously, 1,3,6,8-tetrakis (p-benzoic acid) pyrene (H 4 TBAPy), has been used to construct a stable HOF, known as PFC-1 11 (we name it as HOF-101 as this material was made prior to the publication of PFC-1).…”

“…Recently, hydrogen-bonded organic frameworks (HOFs), [1][2][3][4] self-assembled from pre-designed molecular tectons using intermolecular H-bonding interactions, are rapidly expanding into a library of novel functional crystalline porous materials with diverse structures and applications including gas storage and separation, 5,6 chiral separation, 7 chemical sensing, 8 proton conduction, 9 and catalysis. 10,11 However, since the first report of HOF materials with permanent microporosity about a decade ago, 12 the development of HOFs has been hindered due to poor stability as a result of the weak H-bonding nature. Alternatively, various synthetic porous solids such as silicates, 13 carbons, 14 MOFs, 15 and COFs 16 have achieved a wide range of pore sizes from micro-to mesopores.…”

Hydrogen-bonded porous frameworks constructed by rigid π-conjugated molecules with carboxy groups

“…Wu et al reported that biphenyl derivative 9 gave the stable, interpenetrated, 3D-networked framework (HOF-TCBP) with SA (BET) of 2066 m 2 g − 1 [79]. Liu et al constructed the pylene-based HOF (PFC-1) with SA (BET) of 2122 m 2 g − 1 from 10 and demonstrated proof-of-concept for chemo and photodynamic therapy [80]. HOF JLU-SOF-1-R composed of the homochiral 11 had an SA (BET) value of 460 m 2 g − 1 and selective sorption toward CO 2 [81].…”