Molecular Spring‐like Triple‐Helix Coordination Polymers as Dual‐Stress and Thermally Responsive Crystalline Metal–Organic Materials

2020 ◽  
Vol 59 (37) ◽  
pp. 16061-16068 ◽  
Author(s):  
Lei Mei ◽  
Shu‐wen An ◽  
Kong‐qiu Hu ◽  
Lin Wang ◽  
Ji‐pan Yu ◽  
...  
Keyword(s):  
Coordination Polymers ◽  
Triple Helix ◽  
Organic Materials ◽  
Thermally Responsive ◽  
Metal Organic ◽  
Crystalline Metal

Molecular Spring‐like Triple‐Helix Coordination Polymers as Dual‐Stress and Thermally Responsive Crystalline Metal–Organic Materials

2020 ◽  
Vol 132 (37) ◽  
pp. 16195-16202
Author(s):  
Lei Mei ◽  
Shu‐wen An ◽  
Kong‐qiu Hu ◽  
Lin Wang ◽  
Ji‐pan Yu ◽  
...  
Keyword(s):  
Coordination Polymers ◽  
Triple Helix ◽  
Organic Materials ◽  
Thermally Responsive ◽  
Metal Organic ◽  
Crystalline Metal

scholarly journals Synthesis of Atomically Precise Single-Crystalline Ru2-Based Coordination Polymers

2020 ◽  
Author(s):  
Wen-Yang Gao ◽  
Gerard Van Trieste ◽  
David Powers
Keyword(s):  
Heterogeneous Catalyst ◽  
Coordination Sphere ◽  
Coordination Polymers ◽  
Network Topology ◽  
Metal Organic Frameworks ◽  
Systematic Variation ◽  
Single Crystalline ◽  
Metal Organic ◽  
Crystalline Metal

Methods to incorporate kinetically inert metal nodes and highly basic ligands into single-crystalline metal-organic frameworks (MOFs) are scarce, which prevents synthesis and systematic variation of many potential heterogeneous catalyst materials. Here we demonstrate that metallopolymerization of kinetically inert Ru<sub>2</sub> metallomonomers via labile Ag–N bonds provides access to a family of atomically precise single-crystalline Ru<sub>2</sub>-based coordination polymers with varied network topology and primary coordination sphere.

scholarly journals Synthesis of Atomically Precise Single-Crystalline Ru2-Based Coordination Polymers

2020 ◽  
Author(s):  
Wen-Yang Gao ◽  
Gerard Van Trieste ◽  
David Powers
Keyword(s):  
Heterogeneous Catalyst ◽  
Coordination Sphere ◽  
Coordination Polymers ◽  
Network Topology ◽  
Metal Organic Frameworks ◽  
Systematic Variation ◽  
Single Crystalline ◽  
Metal Organic ◽  
Crystalline Metal

Methods to incorporate kinetically inert metal nodes and highly basic ligands into single-crystalline metal-organic frameworks (MOFs) are scarce, which prevents synthesis and systematic variation of many potential heterogeneous catalyst materials. Here we demonstrate that metallopolymerization of kinetically inert Ru<sub>2</sub> metallomonomers via labile Ag–N bonds provides access to a family of atomically precise single-crystalline Ru<sub>2</sub>-based coordination polymers with varied network topology and primary coordination sphere.

Metal-organic Nanopharmaceuticals

2020 ◽  
Vol 8 (3) ◽  
pp. 163-190
Author(s):  
Benjamin Steinborn ◽  
Ulrich Lächelt
Keyword(s):  
Metal Ions ◽  
Coordination Polymers ◽  
Active Agent ◽  
Lewis Base ◽  
High Loading ◽  
Active Components ◽  
Base Functions ◽  
Metal Organic ◽  
Theranostic Applications ◽  
Pharmacologically Active

: Coordinative interactions between multivalent metal ions and drug derivatives with Lewis base functions give rise to nanoscale coordination polymers (NCPs) as delivery systems. As the pharmacologically active agent constitutes a main building block of the nanomaterial, the resulting drug loadings are typically very high. By additionally selecting metal ions with favorable pharmacological or physicochemical properties, the obtained NCPs are predominantly composed of active components which serve individual purposes, such as pharmacotherapy, photosensitization, multimodal imaging, chemodynamic therapy or radiosensitization. By this approach, the assembly of drug molecules into NCPs modulates pharmacokinetics, combines pharmacological drug action with specific characteristics of metal components and provides a strategy to generate tailorable multifunctional nanoparticles. This article reviews different applications and recent examples of such highly functional nanopharmaceuticals with a high ‘material economy’. : Lay Summary: Nanoparticles, that are small enough to circulate in the bloodstream and can carry cargo molecules, such as drugs, imaging or contrast agents, are attractive materials for pharmaceutical applications. A high loading capacity is a generally aspired parameter of nanopharmaceuticals to minimize patient exposure to unnecessary nanomaterial. Pharmaceutical agents containing Lewis base functions in their molecular structure can directly be assembled into metal-organic nanopharmaceuticals by coordinative interaction with metal ions. Such coordination polymers generally feature extraordinarily high loading capacities and the flexibility to encapsulate different agents for a simultaneous delivery in combination therapy or ‘theranostic’ applications.

scholarly journals Exciton Coupling and Conformational Changes Impacting the Excited State Properties of Metal Organic Frameworks

Molecules ◽  
2020 ◽  
Vol 25 (18) ◽  
pp. 4230
Author(s):  
Andreas Windischbacher ◽  
Luca Steiner ◽  
Ritesh Haldar ◽  
Christof Wöll ◽  
Egbert Zojer ◽  
...  
Keyword(s):  
Conformational Changes ◽  
Photophysical Properties ◽  
Metal Organic Framework ◽  
Metal Organic Frameworks ◽  
Red Shift ◽  
Light Emitting ◽  
Light Emitting Devices ◽  
Exciton Coupling ◽  
Metal Organic ◽  
Crystalline Metal

In recent years, the photophysical properties of crystalline metal-organic frameworks (MOFs) have become increasingly relevant for their potential application in light-emitting devices, photovoltaics, nonlinear optics and sensing. The availability of high-quality experimental data for such systems makes them ideally suited for a validation of quantum mechanical simulations, aiming at an in-depth atomistic understanding of photophysical phenomena. Here we present a computational DFT study of the absorption and emission characteristics of a Zn-based surface-anchored metal-organic framework (Zn-SURMOF-2) containing anthracenedibenzoic acid (ADB) as linker. Combining band-structure and cluster-based simulations on ADB chromophores in various conformations and aggregation states, we are able to provide a detailed explanation of the experimentally observed photophysical properties of Zn-ADB SURMOF-2: The unexpected (weak) red-shift of the absorption maxima upon incorporating ADB chromophores into SURMOF-2 can be explained by a combination of excitonic coupling effects with conformational changes of the chromophores already in their ground state. As far as the unusually large red-shift of the emission of Zn-ADB SURMOF-2 is concerned, based on our simulations, we attribute it to a modification of the exciton coupling compared to conventional H-aggregates, which results from a relative slip of the centers of neighboring chromophores upon incorporation in Zn-ADB SURMOF-2.

Single crystal to single crystal transformation of spin-crossover coordination polymers from 3D frameworks to 2D layers

2021 ◽  
Vol 9 (15) ◽  
pp. 5082-5087
Author(s):  
Yu Gong ◽  
Wang-Kang Han ◽  
Hui-Shu Lu ◽  
Qing-Tao Hu ◽  
Huan Tu ◽  
...  
Keyword(s):  
Magnetic Properties ◽  
Single Crystal ◽  
Coordination Polymers ◽  
Ligand Exchange ◽  
Spin Crossover ◽  
Metal Organic Frameworks ◽  
Crystal Transformation ◽  
Metal Organic

New Hofmann-type metal–organic frameworks display rare and complete ligand exchange induced single crystal to single crystal transformations from 3D frameworks to 2D layers, accompanied by magnetic properties transition from two-step SCO behavior to hysteretic SCO behavior.

scholarly journals Metal(II) Coordination Polymers from Tetracarboxylate Linkers: Synthesis, Structures, and Catalytic Cyanosilylation of Benzaldehydes

Catalysts ◽  
2021 ◽  
Vol 11 (2) ◽  
pp. 204
Author(s):  
Yu Li ◽  
Chumin Liang ◽  
Xunzhong Zou ◽  
Jinzhong Gu ◽  
Marina V. Kirillova ◽  
...  
Keyword(s):  
Coordination Polymers ◽  
Polycarboxylic Acid ◽  
X Ray Diffraction ◽  
X Ray ◽  
Trimethylsilyl Cyanide ◽  
Effect Of Solvent ◽  
Highly Active ◽  
Solvent Type ◽  
Metal Organic ◽  
Chloride Salts

Three 2D coordination polymers, [Cu2(µ4-dpa)(bipy)2(H2O)]n∙6nH2O (1), [Mn2(µ6-dpa)(bipy)2]n (2), and [Zn2(µ4-dpa)(bipy)2(H2O)2]n·2nH2O (3), were prepared by a hydrothermal method using metal(II) chloride salts, 3-(2′,4′-dicarboxylphenoxy)phthalic acid (H4dpa) as a linker, as well as 2,2′-bipyridine (bipy) as a crystallization mediator. Compounds 1–3 were obtained as crystalline solids and fully characterized. The structures of 1–3 were established by single-crystal X-ray diffraction, revealing 2D metal-organic networks of sql, 3,6L66, and hcb topological types. Thermal stability and catalytic behavior of 1–3 were also studied. In particular, zinc(II) coordination polymer 3 functions as a highly active and recoverable heterogeneous catalyst in the mild cyanosilylation of benzaldehydes with trimethylsilyl cyanide to give cyanohydrin derivatives. The influence of various parameters was investigated, including a time of reaction, a loading of catalyst and its recycling, an effect of solvent type, and a substrate scope. As a result, up to 93% product yields were attained in a catalyst recoverable and reusable system when exploring 4-nitrobenzaldehyde as a model substrate. This study contributes to widening the types of multifunctional polycarboxylic acid linkers for the design of novel coordination polymers with notable applications in heterogeneous catalysis.

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