Effect of benzoic acid substituents and additional functional groups of ancillary ligands in modulating the nuclearity and aggregation behavior of transition metal carboxylates

Rajakannu, Palanisamy; Kaleeswaran, Dhananjayan; Banerjee, Subarna; Butcher, Ray J.; Murugavel, Ramaswamy

doi:10.1016/j.ica.2018.10.054

Cited by 11 publications

(3 citation statements)

References 66 publications

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“…The unique characteristics of copper(II) carboxylate complexes of general formula [Cu 2 (RCOO À ) 4 (L) 2 ] are based on their easy synthesis, the relative abundance of the starting materials, their stability, and their low toxicity, which enables a vast number of research directions to be performed from such materials. The structural features of these compounds are related to the coordinating aspect of the ligands: the two possible coordination sites through the carboxylate oxygen atoms result in various modes of coordination, such as monodentate, bidentate and bridging, offering a variability of polynuclear metal complexes (Rajakannu et al, 2019;Murugavel et al, 2000;Rao et al, 2004), and a degree of stability for dinuclear and trinuclear complexes. Additionally, the carboxylate group could participate in hydrogen bonds, leading to a supramolecular network (Aakero ¨y et al, 2006).…”

Section: Chemical Contextmentioning

confidence: 99%

“…Copper(II) carboxylate complexes with paddle-like structure have been proposed in solar energy conversion and storage, redox mediators, magnetism, dyes and in catalysis, among other applications (Benesperi et al 2020;Kozlevc ˇar et al, 2004;Rajakannu et al, 2019;Murugavel et al, 2000;Rao et al, 2004;Boulsourani et al, 2017;Baldoma ´et al, 2006;Seo et al, 2000). The unique characteristics of copper(II) carboxylate complexes of general formula [Cu 2 (RCOO À ) 4 (L) 2 ] are based on their easy synthesis, the relative abundance of the starting materials, their stability, and their low toxicity, which enables a vast number of research directions to be performed from such materials.…”

Section: Chemical Contextmentioning

confidence: 99%

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New copper carboxylate pyrene dimers: synthesis, crystal structure, Hirshfeld surface analysis and electrochemical characterization

Nogué-Guzmán,

Burgos-Suazo,

Rivera-Reyes

et al. 2024

Acta Cryst E

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Two new copper dimers, namely, bis(dimethyl sulfoxide)tetrakis(μ-pyrene-1-carboxylato)dicopper(Cu—Cu), [Cu2(C17H9O2)4(C2H6OS)2] or [Cu2(pyr-COO−)4(DMSO)2] (1), and bis(dimethylformamide)tetrakis(μ-pyrene-1-carboxylato)dicopper(Cu—Cu), [Cu2(C17H9O2)4(C3H7NO)2] or [Cu2(pyr-COO−)4(DMF)2] (2) (pyr = pyrene), were synthesized from the reaction of pyrene-1-carboxylic acid, copper(II) nitrate and triethylamine from solvents DMSO and DMF, respectively. While 1 crystallized in the space group P\overline{1}, the crystal structure of 2 is in space group P21/n. The Cu atoms have octahedral geometries, with four oxygen atoms from carboxylate pyrene ligands occupying the equatorial positions, a solvent molecule coordinating at one of the axial positions, and a Cu...Cu contact in the opposite position. The packing in the crystal structures exhibits π–π stacking interactions and short contacts through the solvent molecules. The Hirshfeld surfaces and two-dimensional fingerprint plots were generated for both compounds to better understand the intermolecular interactions and the contribution of heteroatoms from the solvent ligands to the crystal packing. In addition, a Cu2+/Cu1+ quasi-reversible redox process was identified for compound 2 using cyclic voltammetry that accounts for a diffusion-controlled electron-donation process to the Cu dimer.

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Section: Chemical Contextmentioning

confidence: 99%

Section: Chemical Contextmentioning

confidence: 99%

New copper carboxylate pyrene dimers: synthesis, crystal structure, Hirshfeld surface analysis and electrochemical characterization

Nogué-Guzmán,

Burgos-Suazo,

Rivera-Reyes

et al. 2024

Acta Cryst E

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“…Benzoates are a subset of carboxylates, which are particularly interesting because their properties can be tuned based on proper substituent choice. The effect of substituents on the crystal structure of benzoates has been previously established for transition metals [13] and lanthanide complexes [14], and for some main-group elements including Pb [15]. An increased influence is expected for substituents with a strong ability to coordinate the metal (e.g., sulphonate or amine), but is unforeseen when only weak interactions are feasible (e.g., ether-type oxygen, including dioxolanes).…”

Section: Introductionmentioning

confidence: 97%

Solvent Influence in the Synthesis of Lead(II) Complexes Containing Benzoate Derivatives

Ayllón,

Vallcorba,

Domingo

2024

Inorganics

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A series of lead(II) complexes incorporating benzoate derivative ligands was prepared: [Pb(2MeOBz)2]n (1), [Pb(2MeOBz)2(H2O)]n (2), [Pb2(1,4Bzdiox)4(DMSO)]n (3), [Pb(1,4Bzdiox)2(H2O)]n (4), [Pb(Pip)2(H2O)]n (5), and [Pb(Ac)(Pip)2(MeOH)]n (6) (2MeOBz: 2-methoxybenzoate; 1,4Bzdiox: 1,4-benzodioxan-5-carboxylate; DMSO: dimethylsulfoxide; Ac: acetate; Pip: piperonylate; MeOH: methanol). All compounds were characterized via elemental analysis, ATR-FTIR spectroscopy, and powder XRD. In addition, the crystal structures of some compounds were elucidated. Compounds 1 and 2, involving 2-methoxybenzoate, were closely related, only differing in the presence of one extra aqua ligand found for the latter. However, this implies key changes in the studied properties, e.g., 2 shows solid-state luminescence that displays a different color as a function of the crystal orientation, while 1 does not. The crystal structure of 2 revealed a 1D coordination polymer. A similar relationship was found between compounds 3 and 4, incorporating 1,4-benzodioxan-5-carboxylate. In this pair, only 4, with aqua ligands, displayed a greenish-yellow-color solid-state luminescence. Furthermore, two new lead(II) piperonylate complexes, 5 and 6, were obtained from the reaction between lead(II) acetate and piperonylic acid. In water, all acetate ligands in the metal precursor were displaced and [Pb(Pip)2(H2O)]n (5) was isolated, while in methanol, a mixed acetate–piperonylate complex, [Pb(Ac)(Pip)2(MeOH)]n (6), was precipitated. Considering only conventional Pb-O bonds, the crystal structure of 6 was described as a 1D coordination polymer, although, additionally, the chains were associated via tetrel bonds, defining an extended 2D architecture.

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2-Chlorobenzoate Complex of Cu(II): Unexpected Appearance of Halogen···Halogen Contacts in Solid State

et al. 2019

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Effect of benzoic acid substituents and additional functional groups of ancillary ligands in modulating the nuclearity and aggregation behavior of transition metal carboxylates

Cited by 11 publications

References 66 publications

New copper carboxylate pyrene dimers: synthesis, crystal structure, Hirshfeld surface analysis and electrochemical characterization

New copper carboxylate pyrene dimers: synthesis, crystal structure, Hirshfeld surface analysis and electrochemical characterization

Solvent Influence in the Synthesis of Lead(II) Complexes Containing Benzoate Derivatives

2-Chlorobenzoate Complex of Cu(II): Unexpected Appearance of Halogen···Halogen Contacts in Solid State

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