Self-assembly of neutral dinuclear and trinuclear zinc-benzoate complexes

Karmakar, Anirban; Sarma, Rupam; Baruah, Jubaraj B.

doi:10.1016/j.inoche.2006.07.013

Cited by 50 publications

(11 citation statements)

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“…The nuclearity and carboxylate coordination modes in Lewis base coordinated zinc(II) aryl carboxylate complexes were shown to depend upon the method of preparation, nature of carboxylate moiety, Lewis base, the ratio of reactants and other reaction conditions [17,[35][36][37][38][39].…”

Section: Introductionmentioning

confidence: 99%

3,5-Lutidine coordinated zinc(II) aryl carboxylate complexes: Precursors for zinc(II) oxide

Kumar

Thomas

Nagarajan

et al. 2011

Inorganica Chimica Acta

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Section: Introductionmentioning

confidence: 99%

3,5-Lutidine coordinated zinc(II) aryl carboxylate complexes: Precursors for zinc(II) oxide

Kumar

Thomas

Nagarajan

et al. 2011

Inorganica Chimica Acta

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“…These happen as a consequence of variable coordination numbers of cadmium ion deciding the respective self-assembly. There are examples of neutral zinc , molecular complexes where neutral complexes comprise similar ligands; but, in the present case, two independent compositions are held together by weak noncovalent interactions. Such complexes generate interest to study noncovalently linked self-assemblies of closely related dissimilar complexes.…”

Section: Resultsmentioning

confidence: 79%

“…4,5 Wide applications of metallo−organic frameworks as optical materials and sensors make one curious to study discrete units of a framework to understand properties. 52,53 There are also many self-assembled aggregates comprising multiple neutral species of zinc, 54,55 manganese, 56 copper carboxylates. 57,58 Depending on the electronic configuration of the central metal-ion, the inherent magnetic properties of the metal ion directly influence the photoluminescence OFF or ON states.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The 4-formylbenzoate on the species is electron-withdrawing to extend its electronic effect to another fluorescent ligand of the complex through the intervening metal ion. The electronic effects of diamagnetic metal complexes possessing electron-rich and -deficient ligands cause signal transduction through intramolecular charge transfer. , Push–pull electronic effects of zinc complexes of multipolar ligands cause extensive solvato-emissive effects. , Wide applications of metallo–organic frameworks as optical materials and sensors make one curious to study discrete units of a framework to understand properties. , There are also many self-assembled aggregates comprising multiple neutral species of zinc, , manganese, copper carboxylates. , Depending on the electronic configuration of the central metal-ion, the inherent magnetic properties of the metal ion directly influence the photoluminescence OFF or ON states. A diamagnetic 4-formylbenzoate complex with 1,10-phenanthroline-based ligand would assist in intramolecular charge transfer, whereas a paramagnetic metal complex will be in general nonemissive.…”

Section: Introductionmentioning

confidence: 99%

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Copper(II), Zinc(II), and Cadmium(II) Formylbenzoate Complexes: Reactivity and Emission Properties

2019

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Synthesis, characterization, reactivity, and sensing properties of 4-formylbenzoate complexes of copper(II), zinc(II), and cadmium(II) possessing the 1,10-phenanthroline ancillary ligand are studied. The crystal structures of the (1,10-phenanthroline)bis(4-formylbenzoate)(aqua)copper(II) and (1,10-phenanthroline)bis(4-formylbenzo-ate)zinc(II) and a novel molecular complex comprising an assembly of mononuclear and dinuclear species of (1,10-phenanthroline)bis(4-formylbenzoate)cadmium(II) are reported. These zinc and cadmium complexes are fluorescent; they show differentiable sensitivity to detect three positional isomers of nitroaniline. The mechanism of sensing of nitroanilines by 1,10-phenanthroline and the complexes are studied by fluorescence titrations, photoluminescence decay, and dynamic light scattering. A plausible mechanism showing that 1,10-phenanthroline ligand-based emission quenched by electron transfer from the excited state of 1,10-phenanthroline to nitroaniline is supported by density functional theory calculations. In an anticipation to generate a fluorescent d10-copper(I) formylbenzoate complex by a mild reducing agent such as hydroxylamine hydrochloride for similar sensing of nitroaromatics as that of the d10-zinc and cadmium 4-formylbenzoate complexes, reactivity of d9-copper(II) with hydroxylamine hydrochloride in the presence of 4-formylbenzoic acid and 1,10-phenanthroline is studied. It did not provide the expected copper(I) complex but resulted in stoichiometry-dependent reactions of 4-formylbenzoic acid with hydroxylamine hydrochloride in the presence of copper(II) acetate and 1,10-phenanthroline. Depending on the stoichiometry of reactants, an inclusion complex of bis(1,10-phenanthroline)(chloro)copper(II) chloride with in situ-formed 4-((hydroxyimino)methyl)benzoic acid or copper(II) 4-(hydroxycarbamoyl)benzoate complex was formed. The self-assembly of the inclusion complex has the bis(1,10-phenanthroline)(chloro)copper(II) cation encapsulated in hydrogen-bonded chloride-hydrate assembly with 4-((hydroxyimino)methyl)benzoic acid.

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“…These are in the range of conventional zinc−oxygen and zinc−nitrogen complex found in zinc carboxylate complexes. Generally, paddle-wheel structures, μ 2 -bridging mode 54 of carboxylate alone or together with side-on μ 1 -bridging mode, 55 are observed in zinc carboxylate complexes. In the present case, complex 3 has two bridging carboxylates and two monodentate carboxylates.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Self-Assemblies of Zinc Complexes for Aggregation-Induced Emission Luminogen Precursors

Brahma

Baruah

2020

ACS Omega

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Positional isomers of zinc–nitrobenzoate complexes possessing pyridine -3-(or-4-) carboxamide are used for a comparative theoretical and experimental study to understand their utility as model complexes to understand the role of metal-to-ligand charge transfer in aggregation-induced emission (AIE). Among the five different model zinc complexes, four of them are non-ionic, and one is an ionic complex. The frontier molecular energy levels of different combinations of the positional isomeric complexes and the absorption maximum were ascertained by density functional theory calculations. The PolyQ value obtained from solid samples of each complex is different. Shifts in the emissions to higher wavelengths than the expected emission for the S1 to S0 transition were observed due to aggregations. The highest value of PolyQ among the complexes was 13.56% observed for emission at 439 nm (λex = 350) of the non-ionic complex, namely, (di-aqua)bis(pyridine-3-carboxamide)di(2-nitrobenzoato)zinc(II) monohydrate. Close resemblance in emission lifetime decay profiles of the solid samples of those complexes and the respective solutions of those complexes in dimethyl sulfoxide with or without water showed a common trend, suggesting aggregation-induced emission in each case. Aggregation-induced emission caused by adding water in dimethyl sulfoxide solution of each complex showed an initial increase without a shift in the emission wavelength followed by a quenching with a shift of the respective emission peak to a short wavelength. Dynamic light scattering studies showed an increase in the average particle sizes upon an increase in the concentration of water. This indicated initial participation of water molecules to form aggregates with the complexes, favoring an increase in the AIE intensity. Aggregation of each complex changes with the concentration of water, and an increase in the concentration of water beyond a characteristic limit causes lowering of the emission intensity to the short wavelength.

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Self-assembly of neutral dinuclear and trinuclear zinc-benzoate complexes

Cited by 50 publications

References 10 publications

3,5-Lutidine coordinated zinc(II) aryl carboxylate complexes: Precursors for zinc(II) oxide

3,5-Lutidine coordinated zinc(II) aryl carboxylate complexes: Precursors for zinc(II) oxide

Copper(II), Zinc(II), and Cadmium(II) Formylbenzoate Complexes: Reactivity and Emission Properties

Self-Assemblies of Zinc Complexes for Aggregation-Induced Emission Luminogen Precursors

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