Christina Lollar

Stable Metal-Organic Frameworks: Design, Synthesis, and Applications

Metal-organic frameworks (MOFs) are an emerging class of porous materials with potential applications in gas storage, separations, catalysis, and chemical sensing. Despite numerous advantages, applications of many MOFs are ultimately limited by their stability under harsh conditions. Herein, the recent advances in the field of stable MOFs, covering the fundamental mechanisms of MOF stability, design, and synthesis of stable MOF architectures, and their latest applications are reviewed. First, key factors that affect MOF stability under certain chemical environments are introduced to guide the design of robust structures. This is followed by a short review of synthetic strategies of stable MOFs including modulated synthesis and postsynthetic modifications. Based on the fundamentals of MOF stability, stable MOFs are classified into two categories: high-valency metal-carboxylate frameworks and low-valency metal-azolate frameworks. Along this line, some representative stable MOFs are introduced, their structures are described, and their properties are briefly discussed. The expanded applications of stable MOFs in Lewis/Brønsted acid catalysis, redox catalysis, photocatalysis, electrocatalysis, gas storage, and sensing are highlighted. Overall, this review is expected to guide the design of stable MOFs by providing insights into existing structures, which could lead to the discovery and development of more advanced functional materials.

Retrosynthesis of multi-component metal−organic frameworks

Crystal engineering of metal−organic frameworks (MOFs) has allowed the construction of complex structures at atomic precision, but has yet to reach the same level of sophistication as organic synthesis. The synthesis of complex MOFs with multiple organic and/or inorganic components is ultimately limited by the lack of control over framework assembly in one-pot reactions. Herein, we demonstrate that multi-component MOFs with unprecedented complexity can be constructed in a predictable and stepwise manner under simple kinetic guidance, which conceptually mimics the retrosynthetic approach utilized to construct complicated organic molecules. Four multi-component MOFs were synthesized by the subsequent incorporation of organic linkers and inorganic clusters into the cavity of a mesoporous MOF, each composed of up to three different metals and two different linkers. Furthermore, we demonstrated the utility of such a retrosynthetic design through the construction of a cooperative bimetallic catalytic system with two collaborative metal sites for three-component Strecker reactions.The crystal engineering of metal–organic frameworks has led to the construction of complex structures, but has yet to reach the same level of sophistication as organic synthesis. Here, Zhou and colleagues use retrosynthetic chemistry to design and produce complex multi-component frameworks.

Controllable Fluorescence Switching of a Coordination Chain Based on the Photoinduced Single-Crystal-to-Single-Crystal Reversible Transformation of a syn-[2.2]Metacyclophane

The observation of a reversible chemical transformation corresponding to an external stimulus in the solid state is intriguing in the exploration of smart materials, which can potentially be applied in molecular machines, molecular switches, sensors, and data storage devices. The solid-state photodimerization reaction of 1,3-bis[2-(4-pyridyl)ethenyl]benzene (1,3-bpeb) in a one-dimensional coordination polymer {[Cd2(1,3-bpeb)2(4-FBA)4]·H2O}n (4-FBA = 4-fluorobenzoate) with 365 nm UV light afforded syn-tetrakis(4-pyridyl)-1,2,9,10-diethano[2.2]metacyclophane (syn-tpmcp) in quantitative yield via a single-crystal-to-single-crystal (SCSC) transformation. Upon irradiation with 254 nm UV light, an SCSC conversion from syn-tpmcp to 1,3-bpeb was also achieved in quantitative yield within the syn-tpmcp-supported coordination polymer {[Cd2(syn-tpmcp)(4-FBA)4]·H2O}n. In particular, accompanied by the reversible transformation between 1,3-bpeb and syn-tpmcp, the coordination chain exhibits photocontrollable fluorescence-switching behavior, which makes this intelligent material an appealing candidate for practical applications.

[Ti8Zr2O12(COO)16] Cluster: An Ideal Inorganic Building Unit for Photoactive Metal–Organic Frameworks

Metal–organic frameworks (MOFs) based on Ti-oxo clusters (Ti-MOFs) represent a naturally self-assembled superlattice of TiO2 nanoparticles separated by designable organic linkers as antenna chromophores, epitomizing a promising platform for solar energy conversion. However, despite the vast, diverse, and well-developed Ti-cluster chemistry, only a scarce number of Ti-MOFs have been documented. The synthetic conditions of most Ti-based clusters are incompatible with those required for MOF crystallization, which has severely limited the development of Ti-MOFs. This challenge has been met herein by the discovery of the [Ti8Zr2O12(COO)16] cluster as a nearly ideal building unit for photoactive MOFs. A family of isoreticular photoactive MOFs were assembled, and their orbital alignments were fine-tuned by rational functionalization of organic linkers under computational guidance. These MOFs demonstrate high porosity, excellent chemical stability, tunable photoresponse, and good activity toward photocatalytic hydrogen evolution reactions. The discovery of the [Ti8Zr2O12(COO)16] cluster and the facile construction of photoactive MOFs from this cluster shall pave the way for the development of future Ti-MOF-based photocatalysts.

Pore‐Environment Engineering with Multiple Metal Sites in Rare‐Earth Porphyrinic Metal–Organic Frameworks

Multi-component metal-organic frameworks (MOFs) with precisely controlled pore environments are highly desired owing to their potential applications in gas adsorption, separation, cooperative catalysis, and biomimetics. A series of multi-component MOFs, namely PCN-900(RE), were constructed from a combination of tetratopic porphyrinic linkers, linear linkers, and rare-earth hexanuclear clusters (RE6 ) under the guidance of thermodynamics. These MOFs exhibit high surface areas (up to 2523 cm2  g-1 ) and unlimited tunability by modification of metal nodes and/or linker components. Post-synthetic exchange of linear linkers and metalation of two organic linkers were realized, allowing the incorporation of a wide range of functional moieties. Two different metal sites were sequentially placed on the linear linker and the tetratopic porphyrinic linker, respectively, giving rise to an ideal platform for heterogeneous catalysis.

Control the Structure of Zr-Tetracarboxylate Frameworks through Steric Tuning

Ligands with flexible conformations add to the structural diversity of metal-organic frameworks but, at the same time, pose a challenge to structural design and prediction. Representative examples include Zr-tetracarboxylate-based MOFs, which afford assorted structures for a wide range of applications, but also complicate the structural control. Herein, we systematically studied the formation mechanism of a series of (4,8)-connected Zr-tetracarboxylate-based MOFs by altering the substituents on different positions of the organic linkers. Different ligand rotamers give rise to three types of structures with flu, scu, and csq topologies. A combination of experiment and molecular simulation indicate that the steric hindrance of the substituents at different positions dictates the resulting MOF structures. Additionally, the controllable formation of different structures was successfully implemented by a combination of linkers with different steric effects at specific positions.

Flexible Zirconium MOFs as Bromine-Nanocontainers for Bromination Reactions under Ambient Conditions

A series of flexible MOFs (PCN-605, PCN-606, and PCN-700) are synthesized and applied to reversible bromine encapsulation and release. The chemical stability of these Zr-MOFs ensures the frameworks integrity during the bromine adsorption, while the frameworks flexibility allows for structural adaptation upon bromine uptake to afford stronger host-guest interactions and therefore higher bromine adsorption capacities. The flexible MOFs act as bromine-nanocontainers which elongate the storage time of volatile halides under ambient conditions. Furthermore, the bromine pre-adsorbed flexible MOFs can be used as generic bromine sources for bromination reactions giving improved yields and selectivities under ambient conditions when compared with liquid bromine.

Stable Metal–Organic Frameworks with Group 4 Metals: Current Status and Trends

Group 4 metal-based metal–organic frameworks (MIV-MOFs), including Ti-, Zr-, and Hf-based MOFs, are one of the most attractive classes of MOF materials owing to their superior chemical stability and structural tunability. Despite being a relatively new field, MIV-MOFs have attracted significant research attention in the past few years, leading to exciting advances in syntheses and applications. In this outlook, we start with a brief overview of the history and current status of MIV-MOFs, emphasizing the challenges encountered in their syntheses. The unique properties of MIV-MOFs are discussed, including their high chemical stability and strong tolerance toward defects. Particular emphasis is placed on defect engineering in Zr-MOFs which offers additional routes to tailor their functions. Photocatalysis of MIV-MOF is introduced as a representative example of their emerging applications. Finally, we conclude with the perspective of new opportunities in synthesis and defect engineering.

Interior Decoration of Stable Metal–Organic Frameworks

Metal-organic frameworks (MOFs) are a diverse class of hybrid organic/inorganic crystalline materials composed of metal-containing nodes held in place by organic linkers. Through a discerning selection of these components, many properties such as the internal surface area, cavity size and shape, catalytic properties, thermal properties, and mechanical properties may be manipulated. Because of this high level of tunability, MOFs have been heralded as ideal platforms for various applications including gas storage, separation, catalysis, and chemical sensing. (1-8) Regrettably, these theoretical possibilities are limited by the reality of constraining conditions for solvothermal synthesis, which typically include high temperatures (usually over 100 °C), the use of specific solvents, and necessary exposure to acidic or basic conditions. In order to incorporate more delicate functionalities, postsynthesis decoration methods were developed. This feature article focuses on developed interior decoration methods for stable MOFs and the dynamic relationship between such methods and MOF stability. In particular, methods to transform organic, inorganic, and organometallic MOF parts as well as combination techniques, the generation of defects, and the inclusion of enzymes are addressed.

A flexible thioether-based MOF as a crystalline sponge for structural characterization of liquid organic molecules

Herein, we present a flexible MOF (PCN-41) composed of a thioether-based linker and a stair-like {Cu4I4} cluster. Upon the inclusion of liquid organic molecules, PCN-41 undergoes a single crystal to single crystal transformation to allow for ordered arrangement of the guest molecules. By virtue of the low symmetry, structural flexibility, and the electron-rich cavity environment, PCN-41 exhibits crystalline sponge behavior toward a series of electron-deficient liquid molecules including DMF, MeCN, NMP, DMSO and benzaldehyde.