Coordinating and supramolecular prospects of unsymmetrically substituted carbohydrazides

Topić, Edi; Landripet, Ivana; Pisk, Jana; Đilović, Ivica; Vrdoljak, Višnja; Rubčić, Mirta

doi:10.1039/d0nj03106b

Cited by 5 publications

(3 citation statements)

References 109 publications

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“…Complexes 1-3 showed strong stretching frequencies in the 1561-1556 cm −1 and 1443-1331 cm −1 regions due to the attribution to the ν asym (OCO) and ν sym (OCO) vibrations, respectively [54,55]. The presence of [Mo 4 O 10 (OCH 3 ) 6 ] 2− in 10 was identified by the stretching frequencies characteristic for the cis-MoO 2 2+ structural unit (found at 912 cm −1 and 892 cm −1 ) [56,57]. The compound was also identified by the appearance of bands at ~710 cm −1 assigned to δ(O b -Mo = O t ) of the tetramolybdate anion.…”

Section: Spectroscopic Characterisationmentioning

confidence: 99%

Ligand-Modulated Nuclearity and Geometry in Nickel(II) Hydrazone Complexes: From Mononuclear Complexes to Acetato- and/or Phenoxido-Bridged Clusters

Vrdoljak

Hrenar

Rubčić

et al. 2023

IJMS

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The propensity of 4-hydroxybenzhydrazone-related ligands derived from 3-methoxysalicylaldehyde (H2L3OMe), 4-methoxysalicylaldehyde (H2L4OMe), and salicylaldehyde (H2LH) to act as chelating and/or bridging ligands in Ni(II) complexes was investigated. Three clusters of different nuclearities, [Ni3(L3OMe)2(OAc)2(MeOH)2]∙2MeOH∙MeCN (1∙2MeOH∙MeCN), [Ni2(HL4OMe)(L4OMe)(OAc)(MeOH)2]∙4.7MeOH (2∙4.7MeOH), and [Ni4(HLH)2(LH)2(OAc)2]∙4MeOH·0.63H2O·0.5MeCN·HOAc (3∙4MeOH·0.63H2O·0.5MeCN·HOAc), were prepared from Ni(OAc)2∙4H2O and the corresponding ligand in the presence of Et3N. The hydrazones in these acetato- and phenoxido-bridged clusters acted as singly or doubly deprotonated ligands. When pyridine was used, mononuclear complexes with the square-planar geometry seemed to be favoured, as found for complexes [Ni(L3OMe)(py)] (4), [Ni(L4Ome)(py)] (5) and [Ni(LH)(py)] (6). Ligand substituent effects and the stability of square-planar complexes were investigated and quantified by extensive quantum chemical analysis. Obtained results showed that standard Gibbs energies of binding were lower for square-planar than for octahedral complexes. Starting from [MoO2(L)(EtOH)] complexes as precursors and applying the metal-exchange procedure, the mononuclear complexes [Ni(HL3OMe)2]∙MeOH (7∙MeOH) and [Ni(HLH)]∙2MeOH (9∙2MeOH) and hybrid organic–inorganic compound [Ni2(HL4OMe)2(CH3OH)4][Mo4O10(OCH3)6] (10) were achieved. The octahedral complexes [Ni(HL)2] (7–9) can also be obtained by the direct synthesis from Ni(Oac)2∙4H2O and the appropriate ligand under specific reaction conditions. Crystal and molecular structures of 1∙2MeOH∙MeCN, 2∙4.7MeOH, 3∙4MeOH∙0.63H2O∙0.5MeCN∙HOAc, 4, 5, 9∙2MeOH, and 10 were determined by the single-crystal X-ray diffraction method.

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Section: Spectroscopic Characterisationmentioning

confidence: 99%

Ligand-Modulated Nuclearity and Geometry in Nickel(II) Hydrazone Complexes: From Mononuclear Complexes to Acetato- and/or Phenoxido-Bridged Clusters

Vrdoljak

Hrenar

Rubčić

et al. 2023

IJMS

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“…POM anions tend to associate with cationic Mo-complexes via multiple non-covalent interactions and give ionic hybrids (Class I). [44][45][46] However, investigation of their potential was limited by their low stability. Coordination of POM to metal centres offers a way to overcome this issue and allows the discovery of new POM coordination modes.…”

Section: Introductionmentioning

confidence: 99%

Impact of POM's coordination mode and Mo-hybrid constituents on the binding, stability, and catalytic properties of hybrid (pre)catalysts

Pisk,

Vrdoljak,

Mandarić

et al. 2024

RSC Adv.

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“…[13][14][15] In this context, the carbohydrazide type of ligands have remarkable potential since they can, due to their conformational and tautomeric flexibility, accommodate metal cations in multiple coordination modes. [16][17][18][19][20] Vanadium-based metal-organic assemblies, often characterized by interesting electrical and magnetic properties, typically embrace oxovanadium clusters, whereas those containing a single cation as a node remain rare. [21][22][23] This is largely due to vanadium's in situ adaptability, i.e.…”

Section: Introductionmentioning

confidence: 99%

Supramolecular Isomerism of Coordination Compounds Based on the in Situ Formed [V2O3]4+ Core: Discrete and Chain-like Architectures

et al. 2023

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Flexible 1,5-bis(salicilydene)carbohydrazone ligand in combination with an in situ formed divanadium [V2O3] 4+ core afforded one discrete tetranuclear complex and two polymeric chain-like architectures, mutually related as supramolecular isomers. The occurrence of a particular isomer was controlled through the reaction conditions. All isolated products were structurally characterized via X-ray diffraction and infrared spectroscopy, while the relative stability of the architectures was assessed via competitive slurry and thermal experiments. This study highlights the adaptability of oxovanadium species towards the coordination "inventory" of building blocks present in the environment, while at the same time it unveils the richness of assembly modes of the related structural units.

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Coordinating and supramolecular prospects of unsymmetrically substituted carbohydrazides

Abstract: Unsymmetrically substituted carbohydrazides serve as multifunctional ligands, practicing their chelating and supramolecular roles with cis-dioxomolybdenum(vi) cationic core and the Lindqvist anion.

Cited by 5 publications

References 109 publications

Ligand-Modulated Nuclearity and Geometry in Nickel(II) Hydrazone Complexes: From Mononuclear Complexes to Acetato- and/or Phenoxido-Bridged Clusters

Ligand-Modulated Nuclearity and Geometry in Nickel(II) Hydrazone Complexes: From Mononuclear Complexes to Acetato- and/or Phenoxido-Bridged Clusters

Impact of POM's coordination mode and Mo-hybrid constituents on the binding, stability, and catalytic properties of hybrid (pre)catalysts

Supramolecular Isomerism of Coordination Compounds Based on the in Situ Formed [V2O3]4+ Core: Discrete and Chain-like Architectures

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