2D-metal–organic coordination polymers of lanthanides (La(iii), Pr(iii) and Nd(iii)) with redox-active dioxolene bridging ligands

CrystEngComm ◽  
2020 ◽  
Vol 22 (28) ◽  
pp. 4675-4679 ◽  
Author(s):  
Alexandr D. Kharitonov ◽  
Olesya Y. Trofimova ◽  
Irina N. Meshcheryakova ◽  
Georgy K. Fukin ◽  
Mikhail N. Khrizanforov ◽  
...  
Keyword(s):  
Coordination Polymers ◽  
Active Networks ◽  
Lanthanide Ions ◽  
Bridging Ligands ◽  
Redox Active ◽  
Metal Organic

2D-coordination redox-active networks bearing t-Bu-substituted anilic bridged ligands and lanthanide ions were synthesized and characterized.

scholarly journals Steric and Electronic Effects of Ligand Substitution on Redox-Active Fe4S4-Based Coordination Polymers

2021 ◽  
Author(s):  
Omar Salinas ◽  
Jiaze Xie ◽  
Robert J. Papoular ◽  
Noah E. Horwitz ◽  
Erik Elkaim ◽  
...  
Keyword(s):  
Coordination Polymers ◽  
Photoelectron Spectroscopy ◽  
Electronic Effects ◽  
Iron Sulfur Clusters ◽  
Iron Sulfur ◽  
Redox Active ◽  
Metal Organic ◽  
Uv Visible ◽  
And Function ◽  
Fine Tune

<div>One of the notable advantages of molecular materials is the ability to precisely tune structure, properties, and function via molecular substitutions. While many studies have demonstrated this principle with classic carboxylate‐based coordination polymers, there are comparatively fewer examples where systematic changes to sulfur‐based coordination polymers have been investigated. Here we present such a study on 1D coordination chains of redox‐active</div><div>iron-sulfur clusters linked by methylated 1,4‐benzene‐dithiolates. A series of new iron-sulfur based coordination polymers were synthesized with either 2,5‐dimethyl‐1,4‐benzenedithiol (DMBDT) or 2,3,5,6‐tetramethyl‐1,4‐benzenedithiol. The structures of these compounds have been characterized based on synchrotron Xray</div><div>powder diffraction while their chemical and physical properties have been characterized by techniques including X‐ray photoelectron spectroscopy, cyclic voltammetry and UV–visible spectroscopy. Methylation results in the general trend of increasing electron‐richness in the series, but the tetramethyl version exhibits unexpected properties arising from steric constraints. All these results highlight how substitutions on organic linkers can modulate electronic factors to fine‐tune the electronic structures of metal‐organic materials.</div>

Syntheses, crystal structures and UV-visible absorption properties of five metal–organic frameworks constructed from terphenyl-2,5,2′,5′-tetracarboxylic acid and bis(imidazole) bridging ligands

2014 ◽  
Vol 43 (18) ◽  
pp. 6701-6710 ◽  
Author(s):  
Liming Fan ◽  
Xiutang Zhang ◽  
Wei Zhang ◽  
Yuanshuai Ding ◽  
Weiliu Fan ◽  
...  
Keyword(s):  
Crystal Structures ◽  
Coordination Polymers ◽  
Metal Organic Frameworks ◽  
Tetracarboxylic Acid ◽  
Absorption Properties ◽  
Visible Absorption ◽  
Bridging Ligands ◽  
Metal Organic ◽  
Uv Visible

Five novel coordination polymers based on terphenyl-2,5,2′,5′-tetracarboxylic acid and bis(imidazole) bridging ligands.

scholarly journals Synthesis, Structures, and Water Adsorption of Two Coordination Polymers Constructed by M(II) (M = Ni (1) and Zn (2)) with 1,3-Bis(4-Pyridyl)Propane (bpp) and 1,2,4,5-Benzenetetracarboxylate (BT4−) Ligands

Polymers ◽  
2020 ◽  
Vol 12 (10) ◽  
pp. 2222
Author(s):  
Chih-Chieh Wang ◽  
Wei-Cheng Yi ◽  
Zi-Ling Huang ◽  
Tsai-Wen Chang ◽  
Wen-Chi Chien ◽  
...  
Keyword(s):  
Coordination Polymers ◽  
Metal Organic Framework ◽  
X Ray Diffraction ◽  
Bridging Ligands ◽  
Coordination Modes ◽  
Distorted Octahedral ◽  
Metal Organic ◽  
Nitrogen Donors ◽  
Oxygen Donors ◽  
Monodentate Coordination

Two coordination polymers (CPs), with chemical formulas {[Ni2(bpp)2(BT)(H2O)6] 1.5(EtOH) 1.5H2O}n (1) and [Zn(bpp)(BT)0.5]·5H2O (2) (bpp = 1,3-bis(4-pyridyl)propane, and BT4− = tetraanion of 1,2,4,5-Benzenetetracarboxylic acid), have been synthesized and structurally characterized by single-crystal X-ray diffraction methods. In compound 1, the coordination environments of two crystallographically independent Ni(II) ions are both distorted octahedral bonded to two nitrogen donors from two bpp ligands and four oxygen donors from one BT4- ligand and three water molecules. Both bpp and BT4− act as bridging ligands with bis-monodentate and 1,4-bis-monodentate coordination modes, respectively, connecting the Ni(II) ions to form a 2D layered metal-organic framework (MOF). Adjacent 2D layers are then arranged orderly in an ABAB manner to complete their 3D supramolecular architecture. In 2, the coordination environment of Zn(II) ion is distorted tetrahedral bonded to two nitrogen donors from two bpp ligands and two oxygen donors from two BT4− ligands. Both bpp and BT4- act as bridging ligands with bis-monodentate and 1,2,4,5-tetrakis-monodentate coordination modes, respectively, connecting the Zn(II) ions to form a 3D MOF. The reversible water de-/adsorption behavior of 1 between dehydrated and rehydrated forms has been verified by cyclic Thermogravimetric (TG) analyses through de-/rehydration processes. Compound 1 also exhibits significant water vapor hysteresis isotherms.

scholarly journals Dual Emission in a Ligand and Metal Co-Doped Lanthanide-Organic Framework: Color Tuning and Temperature Dependent Luminescence

Molecules ◽  
2020 ◽  
Vol 25 (3) ◽  
pp. 523 ◽  
Author(s):  
Despoina Andriotou ◽  
Stavros A. Diamantis ◽  
Anna Zacharia ◽  
Grigorios Itskos ◽  
Nikos Panagiotou ◽  
...  
Keyword(s):  
Photophysical Properties ◽  
Metal Organic Framework ◽  
Lanthanide Ions ◽  
Temperature Dependent ◽  
Dual Emission ◽  
Bridging Ligands ◽  
Color Tuning ◽  
Metal Organic ◽  
Lanthanide Metal ◽  
Organic Framework

In this study, we report the luminescence color tuning in the lanthanide metal-organic framework (LnMOF) ([La(bpdc)Cl(DMF)] (1); bpdc2− = [1,1′-biphenyl]-4,4′-dicarboxylate, DMF = N,N-dimethylformamide) by introducing dual emission properties in a La3+ MOF scaffold through doping with the blue fluorescent 2,2′-diamino-[1,1′-biphenyl]-4,4′-dicarboxylate (dabpdc2−) and the red emissive Eu3+. With a careful adjustment of the relative doping levels of the lanthanide ions and bridging ligands, the color of the luminescence was modulated, while at the same time the photophysical characteristics of the two chromophores were retained. In addition, the photophysical properties of the parent MOF (1) and its doped counterparts with various dabpdc2−/bpdc2− and Eu3+/La3+ ratios and the photoinduced energy transfer pathways that are possible within these materials are discussed. Finally, the temperature dependence study on the emission profile of a doped analogue containing 10% dabpdc2− and 2.5% Eu3+ (7) is presented, highlighting the potential of this family of materials to behave as temperature sensors.

scholarly journals Steric and Electronic Effects of Ligand Substitution on Redox-Active Fe4S4-Based Coordination Polymers

2021 ◽  
Author(s):  
Omar Salinas ◽  
Jiaze Xie ◽  
Robert J. Papoular ◽  
Noah E. Horwitz ◽  
Erik Elkaim ◽  
...  
Keyword(s):  
Coordination Polymers ◽  
Photoelectron Spectroscopy ◽  
Electronic Effects ◽  
Iron Sulfur Clusters ◽  
Iron Sulfur ◽  
Redox Active ◽  
Metal Organic ◽  
Uv Visible ◽  
And Function ◽  
Fine Tune

<div>One of the notable advantages of molecular materials is the ability to precisely tune structure, properties, and function via molecular substitutions. While many studies have demonstrated this principle with classic carboxylate‐based coordination polymers, there are comparatively fewer examples where systematic changes to sulfur‐based coordination polymers have been investigated. Here we present such a study on 1D coordination chains of redox‐active</div><div>iron-sulfur clusters linked by methylated 1,4‐benzene‐dithiolates. A series of new iron-sulfur based coordination polymers were synthesized with either 2,5‐dimethyl‐1,4‐benzenedithiol (DMBDT) or 2,3,5,6‐tetramethyl‐1,4‐benzenedithiol. The structures of these compounds have been characterized based on synchrotron Xray</div><div>powder diffraction while their chemical and physical properties have been characterized by techniques including X‐ray photoelectron spectroscopy, cyclic voltammetry and UV–visible spectroscopy. Methylation results in the general trend of increasing electron‐richness in the series, but the tetramethyl version exhibits unexpected properties arising from steric constraints. All these results highlight how substitutions on organic linkers can modulate electronic factors to fine‐tune the electronic structures of metal‐organic materials.</div>

scholarly journals Magnetic and Luminescent Properties of Isostructural 2D Coordination Polymers Based on 2-Pyrimidinecarboxylate and Lanthanide Ions

Crystals ◽  
2020 ◽  
Vol 10 (7) ◽  
pp. 571
Author(s):  
Amalia García-García ◽  
Andoni Zabala-Lekuona ◽  
Ainhoa Goñi-Cárdenas ◽  
Javier Cepeda ◽  
José M. Seco ◽  
...  
Keyword(s):  
Coordination Polymers ◽  
Single Molecule ◽  
Density Functional ◽  
Magnetic Measurements ◽  
Luminescent Properties ◽  
Rare Earth Ions ◽  
Lanthanide Ions ◽  
Ligand Field ◽  
Bridging Ligands ◽  
Metal Centers

A couple of isostructural coordination polymers with the general formula [Ln4(pymca)4(AcO)8]n have been obtained from reactions between pyrimidine-2-carboxylate (pymca) ligand and rare-earth ions (Ln = Dy (1), Nd (2)). These two-dimensional compounds have been characterized and the crystal structures have been solved by single-crystal X-ray diffraction technique, resulting in layers along the bc plane based on pymca and acetate anions that act as bridging ligands between metal atoms. Given that pymca and acetate anions possess carboxylate and hetero-nitrogen groups, it is possible to build a coordination polymer whose metal centers have a nine coordination. Furthermore, static and dynamic magnetic measurements of compound 1 reveal the lack of single molecule-magnet (SMM) behavior in this system due to the following two effects: (i) the ligand field does not stabilize magnetic ground states well separated from excited states, and (ii) anisotropy axes are not collinear, according to results with Magellan software. On another level, luminescent properties of compounds 1 and 2 are attributed to singlet π-π* transitions centered on pymca ligand as corroborated by time-dependent density functional theory (TD-DFT) calculations.

scholarly journals Coordination Polymers Based on Highly Emissive Ligands: Synthesis and Functional Properties

Materials ◽  
2020 ◽  
Vol 13 (12) ◽  
pp. 2699 ◽  
Author(s):  
Anastasia Kuznetsova ◽  
Vladislava Matveevskaya ◽  
Dmitry Pavlov ◽  
Andrei Yakunenkov ◽  
Andrei Potapov
Keyword(s):  
Coordination Polymers ◽  
Photophysical Properties ◽  
Three Dimensional ◽  
Three Dimensions ◽  
Bridging Ligands ◽  
Electron Transitions ◽  
Metal Organic ◽  
Naphthalene Diimides ◽  
Solid State Structures ◽  
Metal Electron

Coordination polymers are constructed from metal ions and bridging ligands, linking them into solid-state structures extending in one (1D), two (2D) or three dimensions (3D). Two- and three-dimensional coordination polymers with potential voids are often referred to as metal-organic frameworks (MOFs) or porous coordination polymers. Luminescence is an important property of coordination polymers, often playing a key role in their applications. Photophysical properties of the coordination polymers can be associated with intraligand, metal-centered, guest-centered, metal-to-ligand and ligand-to-metal electron transitions. In recent years, a rapid growth of publications devoted to luminescent or fluorescent coordination polymers can be observed. In this review the use of fluorescent ligands, namely, 4,4′-stilbenedicarboxylic acid, 1,3,4-oxadiazole, thiazole, 2,1,3-benzothiadiazole, terpyridine and carbazole derivatives, naphthalene diimides, 4,4′,4′′-nitrilotribenzoic acid, ruthenium(II) and iridium(III) complexes, boron-dipyrromethene (BODIPY) derivatives, porphyrins, for the construction of coordination polymers are surveyed. Applications of such coordination polymers based on their photophysical properties will be discussed. The review covers the literature published before April 2020.

Redox-Active Benzoquinones as Challenging “non-innocent” Linkers to Construct 2D Frameworks and Nanostructures with tunable Physical Properties

2022 ◽  
Author(s):  
Noemi N. Monni ◽  
Marco Sanna Angotzi ◽  
Mariangela M. Oggianu ◽  
Suchithra S. Ashoka Sahadevan ◽  
Maria Laura Mercuri
Keyword(s):  
Physical Properties ◽  
Coordination Polymers ◽  
Molecular Level ◽  
Metal Organic Frameworks ◽  
Redox Activity ◽  
Redox Active ◽  
Metal Organic

Exploiting redox activity in supramolecular frameworks such as coordination polymers, metal-organic frameworks and related nanostructures is of paramount importance both at the molecular level and for their technological applications, since...

Family of Lanthanide Metal-Organic Frameworks Based on Redox-Active Tetrathiafulvalene-Dicarboxylic Ligand Showing Slow Relaxation of Magnetisation and Electronic Conductivity

2021 ◽  
Author(s):  
Jun-Jie Hu ◽  
Yu-Guang Li ◽  
He-Rui Wen ◽  
Sui-Jun Liu ◽  
Yan Peng ◽  
...  
Keyword(s):  
Metal Organic Framework ◽  
Electronic Conductivity ◽  
Metal Organic Frameworks ◽  
Lanthanide Ions ◽  
Framework Materials ◽  
Redox Active ◽  
Important Approach ◽  
Metal Organic ◽  
Lanthanide Metal ◽  
Electro Magnetic

The reaction of redox-active tetrathiafulvalene ligand and lanthanide ions is an important approach to prepare photo-electro-magnetic multifunctional metal-organic framework materials. A series of isostructural lanthanide metal-organic frameworks (Ln-MOFs) based on...

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