Robust Biological Hydrogen‐Bonded Organic Framework with Post‐Functionalized Rhenium(I) Sites for Efficient Heterogeneous Visible‐Light‐Driven CO₂ Reduction

Abstract

Ar obust 2,2'-bipyridine (bpy)-derived biological hydrogen-bonded framework (HOF-25) has been realized depending on guanine-quadruplex with the assistance of p-p interaction, which reacts with Re(CO) 5 Cl to give ap ost-functionalizedH OF-25-Re.X-raya bsorption fine structure spectroscopic study on HOF-25-Re confirms the covalent attachment of Re(bpy)(CO) 3 Cl segments to this HOF.R obust and recycled HOF-25-Re bearing photocatalytic Re(bpy)-(CO) 3 Cl centers displays good heterogeneous catalytic activity towards carbon dioxide photoreduction in the presence of [Ru(bpy) 3 ]Cl 2 and triisopropanolamine in CH 3 CN under visible-light irradiation, with both high CO production rate of 1448 mmol g À1 h À1 and high selectivity of 93 %. Under the same conditions,t he experimental turnover number of HOF-25-Re (50) is about 8times as that of the homogeneous control Re(bpy)(CO) 3 Cl. The sustainably regenerated HOF-25-Re via crystallization and post-modification processes shows recovered photocatalytic performance.

Charge‐Assisted Hydrogen‐Bonded Organic Frameworks with Inorganic Ammonium Regulated Switchable Open Polar Sites

“…Thermogravimetric (TG) results showed the activated crystal maintained thermal stability up to 250 °C (Figure S18a, Supporting Information). [17] The observed percent of weight loss was 13.7% at 300 °C, which matched the weight percent of NH 4 and DMF in BTBA•NH 4 •DMF (14%). On the other hand, PTBA•NH 4 •DMF was washed and exchanged in CH 2 Cl 2 for 12 h, followed by the activation at room temperature.…”

Recent Advances in Multifunctional Reticular Framework Nanoparticles: A Paradigm Shift in Materials Science Road to a Structured Future

“…The development of solid-state and materials chemistry hinges on the chemist's aptitude to tailor the molecular architecture of porous materials with exquisite accuracy at the atomic level by incorporating functional moieties. In contrast to other types of nanoparticles, reticular nanoparticles offer a wider range of options for functionalization due to their versatility [203][204][205][206]. Additionally, the unique properties of their internal and external surfaces, along with the variations in the metal-linker composition, create an opportunity for exploiting multiple functionalization techniques within a single framework [207,208].…”

Highly Sensitive Fluorescence Detection of 2,4,6‐Trinitrophenol Based on Hydrogen‐Bonded Organic Framework

“…[10] The flexible hydrogen bonds between molecules in the skeleton improve the self-assembly efficiency, and further improve the stability of the skeleton through other intermolecular interactions (such as π-π interaction, electrostatic interaction, and van der Waals force). [10][11] Due to the advantages of high structural flexibility, large specific surface area, mild synthesis conditions, easy crystallization and recovery, excellent fluorescence performance, good biocompatibility, and low biological toxicity, [12] HOFs materials exhibit broad application prospects in the fields, such as gas adsorption and separation, [13] heterogeneous catalysis, [14] proton conduction, [15] fluorescence sensing, [16] and biomedicine, [17] etc. In recent years, fluorescent sensors based on HOFs materials have received increasing attention due to the following advantages: (1) the π-π conjugation of organic ligands endows HOFs with excellent luminescent properties; [18] (2) high specific surface area and regular pore structure of HOFs materials facilitates the fully contact and interaction with analytes, thereby improving the sensitivity of fluorescence detection; [19] (3) the potential specific recognition sites of HOFs materials makes them highly selective towards specific analytes.…”