Cooperative Assembly of 2D-MOF Nanoplatelets into Hierarchical Carpets and Tubular Superstructures for Advanced Air Filtration.

Clean air is an indispensable prerequisite for human health. The capture of small toxic molecules requires the development of advanced materials for air filtration. Two-dimensional nanomaterials offer highly accessible surface areas but for real-world applications their assembly into well-defined hierarchical mesostructures is essential. DUT-134(Cu) ([Cu2 (dttc)2 ]n , dttc=dithieno[3,2-b : 2',3'-d]thiophene-2,6-dicarboxylate]) is a metal-organic framework forming platelet-shaped particles, that can be organized into complex structures, such as millimeter large free-standing layers (carpets) and tubes. The structured material demonstrates enhanced accessibility of open metal sites and significantly enhanced H2 S adsorption capacity in gas filtering tests compared with traditional bulk analogues.

Unraveling the Guest-Induced Switchability in the Metal-Organic Framework DUT-13(Zn)*.

The switching mechanism of the flexible framework Zn4 O(benztb)1.5 (benztb=N,N,N',N'-benzidine tetrabenzoate), also known as DUT-13, was studied by advanced powder X-ray diffraction (PXRD) and gas physisorption techniques. In situ synchrotron PXRD experiments upon physisorption of nitrogen (77 K) and n-butane (273 K) shed light on the hitherto unnoticed guest-induced breathing in the MOF. The mechanism of contraction is based on the conformationally labile benztb ligand and accompanied by a reduction in specific pore volume from 2.03 cm3 g-1 in the open-pore phase to 0.91 cm3 g-1 in the contracted-pore phase. The high temperature limit for adsorption-induced contraction of 170 K, determined by systematic temperature variation of methane adsorption isotherms, indicates that the DUT-13 framework is softer than other mesoporous MOFs like DUT-49 and does not support the formation of overloaded metastable states required for negative gas-adsorption transitions.

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

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 Fm3̅m. DUT-140(Cu) can be desolvated and is highly porous with an accessible apparent surface area of 4870 m2 g-1 and a pore volume of 2.59 cm3 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.

2D framework materials for energy applications.

In recent years a massive increase in publications on conventional 2D materials (graphene, h-BN, MoS2) is documented, accompanied by the transfer of the 2D concept to porous (crystalline) materials, such as ordered 2D layered polymers, covalent-organic frameworks, and metal-organic frameworks. Over the years, the 3D frameworks have gained a lot of attention for use in applications, ranging from electronic devices to catalysis, and from information to separation technologies, mostly due to the modular construction concept and exceptionally high porosity. A key challenge lies in the implementation of these materials into devices arising from the deliberate manipulation of properties upon delamination of their layered counterparts, including an increase in surface area, higher diffusivity, better access to surface sites and a change in the band structure. Within this minireview, we would like to highlight recent achievements in the synthesis of 2D framework materials and their advantages for certain applications, and give some future perspectives.

Tunable Flexibility and Porosity of the Metal-Organic Framework DUT-49 through Postsynthetic Metal Exchange.

As a prominent and representative example of flexible metal-organic frameworks (MOFs), DUT-49(Cu) has gained attention due to the unique phenomenon of negative gas adsorption (NGA), originating from an unprecedented structural contraction during the gas adsorption. Herein, postsynthetic metal exchange is demonstrated to afford DUT-49 frameworks with a wide variety of metal cations, e.g., Mn2+, Fe2+, Ni2+, Zn2+, Cu2+, and Cd2+. The single-crystal-to-single-crystal conversion allowed characterization of the new MOFs by single crystal X-ray diffraction, indicating identical structure and topology compared with that of previously explored DUT-49(Cu) framework. This approach is proven successful in achieving Mn-Mn and Cd-Cd dimers, which are rare examples of M-M paddle-wheel SBUs. The relative stability and flexibility of the resulted frameworks are observed to be highly sensitive to the metal ion of the framework, following the trends predicted by the Irving-Williams series. DUT-49(Ni) was recognized as a second material from the DUT-49 series showing adsorption-induced transitions. A sequential increase in framework flexibility from rigid to flexible and from flexible to NGA has been achieved through selective incorporation of metal centers into the structure. Finally, heterometallic structures are formed by selective and controlled exchange of metal ions to finely tune the flexibility and NGA phenomenon of the framework.

A semiconducting layered metal-organic framework magnet.

The realization of ferromagnetism in semiconductors is an attractive avenue for the development of spintronic applications. Here, we report a semiconducting layered metal-organic framework (MOF), namely K3Fe2[(2,3,9,10,16,17,23,24-octahydroxy phthalocyaninato)Fe] (K3Fe2[PcFe-O8]) with spontaneous magnetization. This layered MOF features in-plane full π-d conjugation and exhibits semiconducting behavior with a room temperature carrier mobility of 15 ± 2 cm2 V-1 s-1 as determined by time-resolved Terahertz spectroscopy. Magnetization experiments and 57Fe Mössbauer spectroscopy demonstrate the presence of long-range magnetic correlations in K3Fe2[PcFe-O8] arising from the magnetic coupling between iron centers via delocalized π electrons. The sample exhibits superparamagnetic features due to a distribution of crystal size and possesses magnetic hysteresis up to 350 K. Our work sets the stage for the development of spintronic materials exploiting magnetic MOF semiconductors.