Integration of Fluorescent Functionality into Pressure-Amplifying Metal–Organic Frameworks

Abstract

The flexibility of soft porous crystals, i.e., their ability to respond to external stimuli with structural changes, is one of the most fascinating features of metal–organic frameworks (MOFs). In addition to breathing and swelling phenomena of flexible MOFs, negative gas adsorption (NGA) and pressure amplification (PA) are the more recent discoveries in this field initially observed in the cubic DUT-49 framework. In recent years, the structural contraction was monitored by physisorption, X-ray diffraction, nuclear magnetic resonance (NMR), and electron paramagnetic resonance (EPR) techniques, providing only limited information about the electronic structure of the ligand. In this work, we designed a new ligand with a fluorescent core in the linker backbone and synthesized three new MOFs, isoreticular to DUT-49, denoted as DUT-140(M) (M-Cu, Co, Zn), crystallizing in the space group Fm 3̅ m . DUT-140(Cu) can be desolvated and is highly porous with an accessible apparent surface area of 4870 m 2 g –1 and a pore volume of 2.59 cm 3 g –1 . Furthermore, it shows flexibility and NGA upon adsorption of subcritical gases. DUT-140(Zn), synthesized using postsynthetic metal exchange, could only be studied with guests in the pores. In addition to the investigation of the adsorption behavior of DUT-140(Cu), spectroscopic and computational methods were used to study the light absorption properties.

Directionally In Situ Self-Assembled Iridium(III)-Polyimine Complex-Encapsulated Metal–Organic Framework Two-Dimensional Nanosheet Electrode To Boost Electrochemiluminescence Sensing

“…Metal–organic frameworks (MOFs) are one kind of porous nanomaterial with a large surface area and a regulated pore size. , Numerous studies have witnessed that MOFs can load different substrates. , Once being loaded in MOFs, the stability will be improved with enhanced performance because MOFs can maximally encapsulate guest materials in uniform-dispersion state and synergistically interact with each other . Meanwhile, MOFs’ functionality is introduced.…”

A light-operated dual-mode method for neuroblastoma diagnosis based on a Tb-MOF: from biometabolite detection to logic devices

“…As a kind of the crystalline porous materials with structural tunability and functional versatility, luminescent metal-organic frameworks (MOFs) [21][22][23][24][25][26][27][28] have been considered as promising candidates for optical sensors. They not only offer the advantages of high sensitivity, fast response, simple operation and low cost as fluorescent sensors, [29][30][31][32][33][34][35] but can also be designed to perform Boolean logic operations [36][37][38] to transmit and process information, just like the human brain and electronics. Additionally, intelligent, decision-based molecular logic devices show great potential for life science applications.…”

Reticular Synthesis of Flexible Rare‐Earth Metal‐Organic Frameworks: Control of Structural Dynamics and Sorption Properties Through Ligand Functionalization

“…This behavior can be then exploited to generate novel materials with distinctive uses, compared to rigid frameworks, in various fields of high interest. Accordingly, responsive MOFs have been notably utilized for the controlled adsorption, [7] trapping [8] and separation [9][10][11] of gases, the responsive sensing of various molecules, [12][13][14] the synthesis of efficient drug delivery systems [15] and as switchable catalysts with tunable activity. [16][17] The ultimate goal in flexible MOF research is to fully understand the observed dynamic responses and precisely control them towards specific applications, eventually developing adaptive tailor-made materials with advanced properties.…”

“…This behavior can be then exploited to generate novel materials with distinctive uses, compared to rigid frameworks, in various fields of high interest. Accordingly, responsive MOFs have been notably utilized for the controlled adsorption, [7] trapping [8] and separation [9–11] of gases, the responsive sensing of various molecules, [12–14] the synthesis of efficient drug delivery systems [15] and as switchable catalysts with tunable activity [16–17] …”