Multifunctional coordination polymers based on copper with modified nucleobases, easily modulated in size and conductivity

Vegas, Verónica G.; Maldonado, Noelia; Castillo, Óscar; Gómez‐García, Carlos J.; Amo‐Ochoa, Pilar

doi:10.1016/j.jinorgbio.2019.110805

Cited by 9 publications

(8 citation statements)

References 44 publications

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“…In addition, the electrical conductivity at 300 K of 2D coordination polymer 4 has been measured using the two contact method (Figure S34). The conductivity value (8.3 × 10 –7 S/cm) is in agreement with a possible semiconductor behavior …”

Section: Resultssupporting

confidence: 82%

“…The conductivity value (8.3 × 10 −7 S/cm) is in agreement with a possible semiconductor behavior. 40 Solvent Ratio-Induced Structural Transformation Study. As we have described in the Experimental Section and in the Introduction, the presence of water or ethanol and the supramolecular interactions between molecules will clearly influence the type of axial ligands of the obtained paddlewheel structures, and the transformations observed between the d i ff e r e n t c r y s t a l p h a s e s .…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Experimental and Theoretical Study of Dynamic Structural Transformations between Sensing Copper(II)-Uracil Antiferromagnetic and Metamagnetic Coordination Compounds

Maldonado

Perles

Martínez

et al. 2020

Crystal Growth & Design

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This paper describes the synthesis and characterization of several copper(II)-uracil-1-propionic acid (UPrOH) coordination compounds, including a theoretical and experimental study of their crystalline transformations, from paddlewheel structures ([Cu2(UPrO)4(MeOH)(OH2)]·2H2O (1), [Cu2(UPrO)4(MeOH) 2 ]·2MeOH (2), [Cu2(UPrO)4(OH2)2]·6H2O (3a), [Cu2(UPrO)4(OH2)2]·4H2O·2MeOH (3b)), to two-dimensional coordination polymer ([KCu2(UPrO)5(OH2)2] n (4)), or to dimeric compound ([Cu2(UPrO)4(OH2)4]·4H2O (5)), due to slight modifications in the water–methanol solvent ratio used in their synthetic processes and thanks to the formation of supramolecular structures by hydrogen bonds. The theoretical study analyzes the thermodynamic stability of the phases, finding that, if we do not consider the supramolecular interactions, paddlewheel structures are more stable than the dimeric one, regardless of the medium in which they exist. However, the cohesive energy calculations can explain the final stabilization of the dimeric structure as a result of the subsequent supramolecular interactions. These transformations also involve color changes, rendering these compounds water and methanol sensors. In addition, the magnetic study confirms the paddlewheel environments with the presence of strong antiferromagnetic Cu–Cu coupling and weak antiferromagnetic intradimer Cu–Cu interactions with metamagnetic behavior in the case of dimeric species.

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Section: Resultssupporting

confidence: 82%

Section: ■ Results and Discussionmentioning

confidence: 99%

Experimental and Theoretical Study of Dynamic Structural Transformations between Sensing Copper(II)-Uracil Antiferromagnetic and Metamagnetic Coordination Compounds

Maldonado

Perles

Martínez

et al. 2020

Crystal Growth & Design

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“…recently fabricated a water sensor based on a nonporous copper(II) 1D CP grafted with modified thymine as a terminal ligand and 4,4′‐bipyridine as a bridging ligand between the metal centers (Figure 13 a). [22, 50] The structure also contains one water molecule coordinated to the Cu II metal center and two other solvation water molecules.…”

Section: Three‐dimensional Printed Materials Based On Coordination Bomentioning

confidence: 99%

New Promises and Opportunities in 3D Printable Inks Based on Coordination Compounds for the Creation of Objects with Multiple Applications

Maldonado

Amo‐Ochoa

2020

Chemistry A European J

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This review focuses on the usefulness of coordination bonds to create 3D printable inks and shows how the union of chemistry and 3D technology contributes to new scientific advances, by allowing amorphous or polycrystalline solids to be transformed into objects with the desired shape for successful applications. The review clearly shows how there has been considerable increase in the manufacture of objects based on the combination of organic matrices and coordination compounds. These coordination compounds are usually homogeneously dispersed within the matrix, anchored onto a proper support or coating the printed object, without destroying their unique properties. Advances are so rapid that today it is already possible to 3D print objects made exclusively from coordination compounds without additives. The new printable inks are made mainly with nanoscale nonporous coordination polymers, metal–organic gels, or metal–organic frameworks. The highly dynamic coordination bond allows the creation of objects, which respond to stimuli, that can act as sensors and be used for drug delivery. In addition, the combination of metal–organic frameworks with 3D printing allows the adsorption or selective capacity of the object to be increased, relative to that of the original compound, which is useful in energy storage, gas separation, or water pollutant elimination. Furthermore, the presence of the metal ion can give them new properties, such as luminescence, that are useful for application in sensors or anticounterfeiting. Technological advances, the combination of various printing techniques, and the properties of coordination bonds lead to the creation of surprising, new, printable inks and objects with highly complex shapes that will close the gap between academia and industry for research into coordination compounds.

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“…The large number of coordination modes defined for this anion [2] enables the tailoring of the formed networks. Therefore, oxalato-based coordination polymers were synthesized and studied as materials showing numerous topologies (chains, layers, or 3D networks) [3][4][5][6][7][8][9][10][11][12][13][14] and hence, also different properties, being e.g., single chain magnets [1,15], water soluble magnets [10,16], chiral magnets [17], spin-crossover compounds [18], luminescent materials [19][20][21], NLO materials [22], photocatalysts and catalysts [23,24], materials showing conductivity [11,25,26], sorption materials [27,28], and precursors for nanomaterials possessing pharmacological potential [29].…”

Section: Introductionmentioning

confidence: 99%

Sorption and Magnetic Properties of Oxalato-Based Trimetallic Open Framework Stabilized by Charge-Assisted Hydrogen Bonds

Muzioł

Tereba

Podgajny

et al. 2022

IJMS

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We report a new structure of {[Co(bpy)2(ox)][{Cu2(bpy)2(ox)}Fe(ox)3]}n·8.5nH2O NCU-1 presenting a rare ladder topology among oxalate-based coordination polymers with anionic chains composed of alternately arranged [Cu2(bpy)2(ox)]2+ and [Fe(ox)3]3- moieties. Along the a axis, they are separated by Co(III) units to give porous material with voids of 963.7 Å3 (16.9% of cell volume). The stability of this structure is assured by a network of stacking interactions and charge-assisted C-H…O hydrogen bonds formed between adjacent chains, adjacent cobalt(III) units, and alternately arranged cobalt(III) and chain motifs. The soaking experiment with acetonitrile and bromobenzene showed that water molecules (8.5 water molecules dispersed over 15 positions) are bonded tightly, despite partial occupancy. Water adsorption experiments are described by a D’arcy and Watt model being the sum of Langmuir and Dubinin–Serpinski isotherms. The amount of primary adsorption sites calculated from this model is equal 8.2 mol H2O/mol, being very close to the value obtained from the XRD experiments and indicates that water was adsorbed mainly on the primary sites. The antiferromagnetic properties could be only approximately described with the simple CuII-ox-CuII dimer using H = −J×S1×S2, thus, considering non-trivial topology of the whole Cu-Fe chain, we developed our own general approach, based on the semiclassical model (SC) and molecular field (MF) model, to describe precisely the magnetic superexchange interactions in NCU-1. We established that Cu(II)-Cu(II) coupling dominates over multiple Cu(II)-Fe(III) interactions, with JCuCu = −275(29) and JCuFe = −3.8(1.6) cm−1 and discussed the obtained values against the literature data.

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Multifunctional coordination polymers based on copper with modified nucleobases, easily modulated in size and conductivity

Cited by 9 publications

References 44 publications

Experimental and Theoretical Study of Dynamic Structural Transformations between Sensing Copper(II)-Uracil Antiferromagnetic and Metamagnetic Coordination Compounds

Experimental and Theoretical Study of Dynamic Structural Transformations between Sensing Copper(II)-Uracil Antiferromagnetic and Metamagnetic Coordination Compounds

New Promises and Opportunities in 3D Printable Inks Based on Coordination Compounds for the Creation of Objects with Multiple Applications

Sorption and Magnetic Properties of Oxalato-Based Trimetallic Open Framework Stabilized by Charge-Assisted Hydrogen Bonds

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