scholarly journals Atomically Precise Crystalline Materials Based on Kinetically Inert Metal Ions via Reticular Mechanopolymerization

2020 ◽  
Author(s):  
Wen-Yang Gao ◽  
Aishanee Sur ◽  
Chen-Hao Wang ◽  
Gregory R. Lorzing ◽  
Alexandra M. Antonio ◽  
...  
Keyword(s):  
Carboxylic Acid ◽  
Metal Ions ◽  
Coordination Polymers ◽  
Solid Solutions ◽  
Mechanochemical Synthesis ◽  
Rational Approach ◽  
Structural Elements ◽  
Coordination Networks ◽  
Crystalline Materials ◽  
Metal Materials

The incorporation of kinetically inert metal ions as structural elements in crystalline coordination polymers is a synthetic challenge. While a small family of materials based on inert ions has been prepared (<i>i.e.</i> Cr(III)-based MIL-100, MIL-101, and [Ru<sub>6</sub>(btc)<sub>4</sub>Cl<sub>3</sub>]), general strategies that enable reticular synthesis have not been reported. Here we describe the mechanochemical synthesis of a reticular family of crystalline Ru<sub>2</sub>[II,III]-based materials by polymerization of molecular Ru<sub>2</sub> complexes, featuring unprotected carboxylic acid substituents, with Cu(OAc)<sub>2</sub>. The resulting crystalline heterobimetallic MOFs are solid-solutions of Ru<sub>2</sub> and Cu<sub>2</sub> sites housed within [M<sub>3</sub>L<sub>2</sub>] phases. The developed mechanochemical strategy is modular and allows for control of the primary coordination sphere of the Ru<sub>2</sub> sites. We anticipate the strategy will provide a rational approach to incorporation of kinetically inert ions in porous crystalline coordination networks, generating a class of atomically precise mixed-metal materials.

scholarly journals Atomically Precise Crystalline Materials Based on Kinetically Inert Metal Ions via Reticular Mechanopolymerization

2020 ◽  
Author(s):  
Wen-Yang Gao ◽  
Aishanee Sur ◽  
Chen-Hao Wang ◽  
Gregory R. Lorzing ◽  
Alexandra M. Antonio ◽  
...  
Keyword(s):  
Carboxylic Acid ◽  
Metal Ions ◽  
Coordination Polymers ◽  
Solid Solutions ◽  
Mechanochemical Synthesis ◽  
Rational Approach ◽  
Structural Elements ◽  
Coordination Networks ◽  
Crystalline Materials ◽  
Metal Materials

The incorporation of kinetically inert metal ions as structural elements in crystalline coordination polymers is a synthetic challenge. While a small family of materials based on inert ions has been prepared (<i>i.e.</i> Cr(III)-based MIL-100, MIL-101, and [Ru<sub>6</sub>(btc)<sub>4</sub>Cl<sub>3</sub>]), general strategies that enable reticular synthesis have not been reported. Here we describe the mechanochemical synthesis of a reticular family of crystalline Ru<sub>2</sub>[II,III]-based materials by polymerization of molecular Ru<sub>2</sub> complexes, featuring unprotected carboxylic acid substituents, with Cu(OAc)<sub>2</sub>. The resulting crystalline heterobimetallic MOFs are solid-solutions of Ru<sub>2</sub> and Cu<sub>2</sub> sites housed within [M<sub>3</sub>L<sub>2</sub>] phases. The developed mechanochemical strategy is modular and allows for control of the primary coordination sphere of the Ru<sub>2</sub> sites. We anticipate the strategy will provide a rational approach to incorporation of kinetically inert ions in porous crystalline coordination networks, generating a class of atomically precise mixed-metal materials.

Crystal structures, topologies and luminescent properties of three Zn(ii)/Cd(ii) coordination networks based on naphthalene-2,6-dicarboxylic acid and different bis(imidazole) linkers

RSC Advances ◽  
2015 ◽  
Vol 5 (21) ◽  
pp. 16190-16198 ◽  
Author(s):  
Zhi-Hao Yan ◽  
Wen Wang ◽  
Liangliang Zhang ◽  
Xiaowei Zhang ◽  
Lei Wang ◽  
...  
Keyword(s):  
Metal Ions ◽  
Dicarboxylic Acid ◽  
Crystal Structures ◽  
Coordination Polymers ◽  
Structural Diversity ◽  
Luminescent Properties ◽  
Coordination Networks ◽  
Bridging Ligands

Three new coordination polymers (CPs) based on H2ndc acid have been synthesized and structurally characterized. Three CPs exhibit structural diversity depending on different bis(imidazole) bridging ligands and center metal ions.

scholarly journals 2D-Coordination polymers based on 1H-indazole-4-carboxylic acid and transition metal ions: magnetic, luminescence and biological properties

CrystEngComm ◽  
2020 ◽  
Vol 22 (30) ◽  
pp. 5086-5095
Author(s):  
Antonio A. García-Valdivia ◽  
Andoni Zabala-Lekuona ◽  
Gloria B. Ramírez-Rodríguez ◽  
José M. Delgado-López ◽  
Belén Fernández ◽  
...  
Keyword(s):  
Carboxylic Acid ◽  
Transition Metal ◽  
Metal Ions ◽  
Coordination Polymers ◽  
Transition Metal Ions ◽  
Biological Properties

Five novel multifunctional coordination polymers (CPs) based on 1H-indazole-4-carboxylic acid are reported. These complexes, the first examples of CPs with this novel ligand, show interesting magnetic, luminescence and biological properties.

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 Dopants Modulate Crystal Growth in Molten Salts Enabled by Surface Energy Tuning

2021 ◽  
Author(s):  
Xiaoqiao Li ◽  
Linming Zhou ◽  
Han Wang ◽  
Dechao Meng ◽  
Guannan Qian ◽  
...  
Keyword(s):  
Crystal Growth ◽  
High Temperature ◽  
Surface Energy ◽  
Molten Salts ◽  
Rational Approach ◽  
Temperature Synthesis ◽  
Crystalline Materials ◽  
Size Dependent ◽  
High Temperature Synthesis ◽  
Energy Tuning

Crystalline materials are routinely produced via high-temperature synthesis and show size-dependent properties; however, a rational approach to regulating their crystal growth has not been established. Here we show that dopants...

scholarly journals Spiers Memorial Lecture: Coordination Networks that Switch between Nonporous and Porous Structures: An Emerging Class of Soft Porous Crystals

2021 ◽  
Author(s):  
Michael Zaworotko ◽  
Shi-Qiang Wang ◽  
Soumya Mukherjee
Keyword(s):  
Metal Ions ◽  
Memorial Lecture ◽  
Crystalline Solids ◽  
Porous Structures ◽  
Coordination Networks

Coordination networks (CNs) are a class of (usually) crystalline solids typically comprised of metal ions or cluster nodes linked into 2 or 3 dimensions by organic and/or inorganic linker ligands....

scholarly journals Photoluminescent Coordination Polymers Based on Group 12 Metals and 1H-Indazole-6-Carboxylic Acid

Inorganics ◽  
2021 ◽  
Vol 9 (3) ◽  
pp. 20
Author(s):  
Antonio A. García-Valdivia ◽  
Estitxu Echenique-Errandonea ◽  
Gloria B. Ramírez-Rodríguez ◽  
José M. Delgado-López ◽  
Belén Fernández ◽  
...  
Keyword(s):  
Carboxylic Acid ◽  
Coordination Polymers ◽  
Density Functional ◽  
Free Ligand ◽  
Emission Spectra ◽  
Point Of View ◽  
Theoretical Point ◽  
Fourier Transformed Infrared Spectroscopy ◽  
3D Network ◽  
The Stability

Two new coordination polymers (CPs) based on Zn(II) and Cd(II) and 1H-indazole-6-carboxylic acid (H2L) of general formulae [Zn(L)(H2O)]n (1) and [Cd2(HL)4]n (2) have been synthesized and fully characterized by elemental analyses, Fourier transformed infrared spectroscopy and single crystal X-ray diffraction. The results indicate that compound 1 possesses double chains in its structure whereas 2 exhibits a 3D network. The intermolecular interactions, including hydrogen bonds, C–H···π and π···π stacking interactions, stabilize both crystal structures. Photoluminescence (PL) properties have shown that compounds 1 and 2 present similar emission spectra compared to the free-ligand. The emission spectra are also studied from the theoretical point of view by means of time-dependent density-functional theory (TD-DFT) calculations to confirm that ligand-centred π-π* electronic transitions govern emission of compound 1 and 2. Finally, the PL properties are also studied in aqueous solution to explore the stability and emission capacity of the compounds.

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