Molecular enneanuclear Cu<sup>II</sup> phosphates containing planar hexanuclear and trinuclear sub-units: syntheses, structures, and magnetism

Santra, Biswajit; Kalita, Pankaj; Chandra, Sudeshna; Mandal, Debdeep; Kumar, Vivek; Narayanan, Ramakirushnan Surya; Dey, Atanu; Chrysochos, Nicolas; Hüch, Volker; Biswas, Sourav; Ghoshal, Debajyoti; San̂udo, E. Carolina; Sarkar, Biprajit; Schulzke, Carola; Chandrasekhar, Vadapalli; Jana, Anukul

doi:10.1039/c9dt04584h

Cited by 4 publications

(5 citation statements)

References 68 publications

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“…If L is a di- or tricarboxylate ligand or 4,4′-bipyridine (or its derivatives), then metal–organic frameworks − or coordination polymers − can be obtained. Various discrete higher-nuclearity copper(II) pyrazolate complexes are also known. − …”

Section: Introductionmentioning

confidence: 99%

Capped Nanojars: Synthesis, Solution and Solid-State Characterization, and Atmospheric CO₂ Sequestration by Selective Binding of Carbonate

2021

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Nanojars are a class of supramolecular anion-incarcerating coordination complexes that self-assemble from Cu2+ ions, pyrazole, and a strong base in the presence of highly hydrophilic anions. In this work, we show that if the strong base (e.g., NaOH or Bu4NOH) is replaced by a weak base such as a trialkylamine, capped nanojars of the formula [{Cu3(μ3-OH)(μ-pz)3L3}CO3⊂{Cu(μ-OH)(μ-pz)} n ] (pz = pyrazolate anion; L = neutral donor molecule; n = 27–31) are obtained instead of the conventional nanojars. Yet, to obtain capped nanojars, the conjugate acid side product originating from the weak base must be separated by transferring it to water either by precipitation of the water-insoluble capped nanojars or by liquid–liquid extraction. Full characterization using electrospray ionization mass spectrometry, UV–vis and variable-temperature 1H NMR spectroscopy in solution, and single-crystal X-ray diffraction, elemental analysis, and solubility studies in the solid state reveals similarities as well as drastic differences between capped nanojars and nanojars lacking the [Cu3(μ3-OH)(μ-pz)3L3]2+ cap. Acid–base reactivity studies demonstrate that capped nanojars are intermediates in the pH-controlled assembly–disassembly of nanojars. During the self-assembly of capped nanojars, CO2 is selectively sequestered from air in the presence of other atmospheric gases and converted to carbonate, the binding of which is selective in the presence of NO3 –, ClO4 –, BF4 –, Cl–, and Br– ions.

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Section: Introductionmentioning

confidence: 99%

Capped Nanojars: Synthesis, Solution and Solid-State Characterization, and Atmospheric CO₂ Sequestration by Selective Binding of Carbonate

2021

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“…For 3, the initial weight loss is due to the loss of methoxy and acetate moieties (calc. (found) % 12.96 (13) up to 190 °C), followed by the loss of remaining organic moieties (calc. (found) % 55.…”

Section: Thermal Decomposition Studiesmentioning

confidence: 97%

“…Typically, they bind metal ions in a simple κ 1 fashion through the pyridinic N‐donor, leaving N−H groups available to interact with the H‐bond acceptor [10] . Using these types of systems as ancillary ligands in the synthesis of molecular metal phosphates resulted in the formation of mono‐, [11] di‐, [2d,8d,12] tetra‐, [9g,12a] hexa‐ and enneanuclear complexes [13] . This implies that pyrazole‐based ligand system aids in the formation of various molecular structures.…”

Section: Introductionmentioning

confidence: 99%

“…[10] Using these types of systems as ancillary ligands in the synthesis of molecular metal phosphates resulted in the formation of mono-, [11] di-, [2d,8d,12] tetra-, [9g,12a] hexa-and enneanuclear complexes. [13] This implies that pyrazole-based ligand system aids in the formation of various molecular structures. In order to investigate the role of pyrazole-based ligand in molecular copper phosphate synthesis, we have used 3,5-dimethyl pyrazole (3,5-dmpz) as a co-ligand with sterically encumbered phosphate ligand 2,6-di-tert-butyl phenyl phosphate (dtbppH 2 ) and copper metal precursors, which resulted in mononuclear [Cu(dtbppH) 2 (dmpz)(MeOH) 2 ] (1), dinuclear [Cu(dtbpp)(dmpz) 2 ] 2 (2), and rectangular tetranuclear [Cu 2 (dtbpp)(dmpz) 2 (OAc)(MeO)] 2 (3) copper complexes.…”

Section: Introductionmentioning

confidence: 99%

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Nuclearity Control in Molecular Copper Phosphates Derived from a Bulky Arylphosphate: Synthesis, Structural and Magnetic Studies

Prapakaran

Sathish

et al. 2023

Eur J Inorg Chem

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Dedicated to Professor Dietmar Stalke on the occasion of his 65 th birthdayStarting from sterically encumbered 2,6-di-tert-butylphenyl phosphate (dtbppH 2 ) and co-ligand 3,5-dimethyl pyrazole (dmpz), it is possible to isolate either mono-, di-or tetranuclear copper phosphates by varying the copper source and making attendant changes in the reaction conditions. For example, reaction of copper nitrate with dtbppH 2 and dmpz at 60 °C leads to the isolation of the mononuclear copper phosphate [Cu(dtbppH) 2 (dmpz)(MeOH) 2 ] (1) as the only product. However, the use of copper acetate in place of copper nitrate and conducting the reaction at the room temperature leads to the formation of both dinuclear [Cu(dtbpp)(dmpz) 2 ] 2 (2) and tetranuclear [Cu 2 (dtbpp)(dmpz) 2 (OAc)(MeO)] 2 (3) from the same reaction mixture. Compounds 2 and 3 could be isolated in pure form through fractional crystallization. Copper phosphates 1-3 have been characterized by both analytical and spectroscopic methods including EPR and magnetic measurements. The molecular structures of all three compounds were established through single crystal diffraction studies. Dc magnetic measurements indicate antiferromagnetic interactions between the metal centres in all the compounds.

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“…Among the plethora of available linkers, the employment of nucleic acids and their derivatives in nanotechnology is gaining increasing attention [ 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 , 48 , 49 , 50 ]. The presence of binding sites for metal ions and acceptor and donor functionalities for H-bonds make this class of molecules highly attractive in the field of supramolecular chemistry [ 42 , 49 , 51 , 52 , 53 , 54 , 55 , 56 , 57 ]. Obtained assemblies display controllable morphology and peculiar chemical–physical properties [ 58 , 59 ].…”

Section: Introductionmentioning

confidence: 99%

A Nanoporous Supramolecular Metal–Organic Framework Based on a Nucleotide: Interplay of the π···π Interactions Directing Assembly and Geometric Matching of Aromatic Tails

Bruno¹,

Mastropietro²,

Munno³

et al. 2021

Molecules

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Self-assembly is the most powerful force for creating ordered supramolecular architectures from simple components under mild conditions. π···π stacking interactions have been widely explored in modern supramolecular chemistry as an attractive reversible noncovalent tool for the nondestructive fabrication of materials for different applications. Here, we report on the self-assembly of cytidine 5’-monophosphate (CMP) nucleotide and copper metal ions for the preparation of a rare nanoporous supramolecular metal-organic framework in water. π···π stacking interactions involving the aromatic groups of the ancillary 2,2’-bipyridine (bipy) ligands drive the self-assemblies of hexameric pseudo-amphiphilic [Cu6(bipy)6(CMP)2(µ-O)Br4]2+ units. Owing to the supramolecular geometric matching between the aromatic tails, a nanoporous crystalline phase with hydrophobic and hydrophilic chiral pores of 1.2 and 0.8 nanometers, respectively, was successfully synthesized. The encoded chiral information, contained on the enantiopure building blocks, is transferred to the final supramolecular structure, assembled in the very unusual topology 8T6. These kinds of materials, owing to chiral channels with chiral active sites from ribose moieties, where the enantioselective recognition can occur, are, in principle, good candidates to carry out efficient separation of enantiomers, better than traditional inorganic and organic porous materials.

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Molecular enneanuclear Cu^II phosphates containing planar hexanuclear and trinuclear sub-units: syntheses, structures, and magnetism

Abstract: Highly symmetric enneanuclear copper(ii) phosphates comprising of a hexanuclear and a trinuclear motif are described.

Cited by 4 publications

References 68 publications

Capped Nanojars: Synthesis, Solution and Solid-State Characterization, and Atmospheric CO₂ Sequestration by Selective Binding of Carbonate

Capped Nanojars: Synthesis, Solution and Solid-State Characterization, and Atmospheric CO₂ Sequestration by Selective Binding of Carbonate

Nuclearity Control in Molecular Copper Phosphates Derived from a Bulky Arylphosphate: Synthesis, Structural and Magnetic Studies

A Nanoporous Supramolecular Metal–Organic Framework Based on a Nucleotide: Interplay of the π···π Interactions Directing Assembly and Geometric Matching of Aromatic Tails

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Molecular enneanuclear CuII phosphates containing planar hexanuclear and trinuclear sub-units: syntheses, structures, and magnetism

Abstract: Highly symmetric enneanuclear copper(ii) phosphates comprising of a hexanuclear and a trinuclear motif are described.

Cited by 4 publications

References 68 publications

Capped Nanojars: Synthesis, Solution and Solid-State Characterization, and Atmospheric CO2 Sequestration by Selective Binding of Carbonate

Capped Nanojars: Synthesis, Solution and Solid-State Characterization, and Atmospheric CO2 Sequestration by Selective Binding of Carbonate

Nuclearity Control in Molecular Copper Phosphates Derived from a Bulky Arylphosphate: Synthesis, Structural and Magnetic Studies

A Nanoporous Supramolecular Metal–Organic Framework Based on a Nucleotide: Interplay of the π···π Interactions Directing Assembly and Geometric Matching of Aromatic Tails

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Molecular enneanuclear Cu^II phosphates containing planar hexanuclear and trinuclear sub-units: syntheses, structures, and magnetism

Capped Nanojars: Synthesis, Solution and Solid-State Characterization, and Atmospheric CO₂ Sequestration by Selective Binding of Carbonate

Capped Nanojars: Synthesis, Solution and Solid-State Characterization, and Atmospheric CO₂ Sequestration by Selective Binding of Carbonate