Aromatic dicarboxylate incorporated new di- and tetranuclear cobalt(II) complexes: Synthetic and structural aspects, and evaluation of properties and catalytic activity

Majumder, Avishek; Dutta, Nityananda; Haldar, Shobhraj; Das, Arpan; Carrella, Luca M.; Bera, Manindranath

doi:10.1016/j.ica.2020.119752

Cited by 4 publications

(5 citation statements)

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“…Although the bidentate μ:η 2 and μ:η 1 :η 1 bridging modes are quite common in metal carboxylate coordination chemistry, the simultaneous existence of both tridentate μ 3 :η 2 :η 1 :η 1 and tetradentate μ 4 :η 1 :η 1 :η 1 :η 1 bridging modes is rare. ,, Hence, 3 is an unprecedented example of a tetranuclear copper(II) complex that exhibits the bidentate μ:η 2 and μ:η 1 :η 1 , tridentate μ 3 :η 2 :η 1 :η 1 , and tetradentate μ 4 :η 1 :η 1 :η 1 :η 1 bridging modes of the carboxylate groups concurrently, linking four copper centers. A careful search of the data in the literature shows that complex 3 is the third example of a structurally characterized μ 4 -phthalate-bridged metal complex.…”

Section: Resultsmentioning

confidence: 99%

“…The focus here is on the symmetrical dinucleating ligand N , N ′-bis[2-carboxybenzomethyl]- N , N ′-bis[2-pyridylmethyl]-1,3-diaminopropan-2-ol (H 3 cpdp), incorporating two pyridine and two benzoate functionalities (Scheme ). Recently, we have shown that the ligand H 3 cpdp coordinates with Co(II), Fe(III), Cu(II), and Zn(II), including Li/Na, forming a variety of higher-nuclearity complexes with smart molecular structures and interesting material/biological properties. ,,,− In those complexes, the ligand H 3 cpdp has either a trianionic (cpdp 3– ) or a dianionic (Hcpdp 2– ) form (Scheme ), exhibiting flexible coordination modes of the carboxylate groups. While further exploring the reactions of H 3 cpdp with copper(II) ions in the presence of different exogenous ancillary ligands such as isophthalate, chloride, and phthalate/chloride/piconol, we isolated new di-, tri-, and tetranuclear copper(II) complexes of the formulas [Cu 2 (cpdp)(μ-Hisophth)] 4 ·2H 2 isophth·21H 2 O ( 1 ), [Cu 3 (Hcpdp)(Cl) 4 ] ( 2 ), and [Cu 4 (cpdp)(μ-Hphth)(μ 4 -phth)(piconol)(Cl) 2 ]·3H 2 O ( 3 ).…”

Section: Introductionmentioning

confidence: 99%

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Ancillary-Ligand-Assisted Variation in Nuclearities Leading to the Formation of Di-, Tri-, and Tetranuclear Copper(II) Complexes with Multifaceted Carboxylate Coordination Chemistry

Majumder

Das

et al. 2022

ACS Omega

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The self-assembly of a carboxylate-based dinucleating ligand, N,N′-bis[2-carboxybenzomethyl]-N,N′-bis[2-pyridylmethyl]-1,3-diaminopropan-2-ol (H3cpdp), and copper(II) ions in the presence of various exogenous ancillary ligands results in the formation of the new dinuclear complex [Cu2(cpdp)(μ-Hisophth)]4·2H2isophth·21H2O (1), trinuclear complex [Cu3(Hcpdp)(Cl)4] (2), and tetranuclear complex [Cu4(cpdp)(μ-Hphth)(μ4-phth)(piconol)(Cl)2]·3H2O (3) (H2phth = phthalic acid; H2isophth = isophthalic acid; piconol = 2-pyridinemethanol; Cl– = chloride). In methanol–water, the reaction of H3cpdp with CuCl2·2H2O at room temperature leads to the formation of 2. On the other hand, 1 and 3 have been obtained by carrying out the reaction of H3cpdp with CuCl2·2H2O/m-C6H4(CO2Na)2 and CuCl2·2H2O/o-C6H4(CO2Na)2/piconol, respectively, in methanol–water in the presence of NaOH at ambient temperature. All three complexes have been characterized by elemental analysis, molar electrical conductivity and magnetic moment measurements, FTIR, UV–vis spectroscopy, and PXRD, including single-crystal X-ray structural analyses. The molecular structure of 1 is based on a μ-alkoxide and μ-isophthalate-bridged dimeric [Cu2] core; the structure of 2 represents a trimeric [Cu3] core in which a μ-alcohol-bridged dinuclear [Cu2] unit is exclusively coupled with a [CuCl2] species by two μ:η1:η1-syn-anti carboxylate groups forming a triangular motif; the structure of 3 embodies a tetrameric [Cu4] core, with two copper(II) ions in a distorted-octahedral coordination environment, one copper(II) ion in a distorted-trigonal-bipyramidal coordination environment, and the other copper(II) ion in a square-planar coordination environment. In fact, 2 and 3 represent rare examples of copper(II)-based multinuclear complexes showing outstanding features of rich coordination chemistry: (i) using a symmetrical dinucleating ligand, trinuclear complex 2 is generated with four- and five-coordination environments around copper(II) ions; (ii) the unsymmetrical tetranuclear complex 3 is obtained by using the same ligand with four-, five- and six-coordination environments around copper(II) ions; (iii) tetracopper(II) complex 3 shows four different bridging modes of carboxylate groups simultaneously such as μ:η2, μ:η1:η1, μ3:η2:η1:η1, and μ4:η1:η1:η1:η1, the μ4:η1:η1:η1:η1 mode of phthalate being unprecedented. The formation of these [Cu2], [Cu3], and [Cu4] complexes can be controlled by changing the exogenous ancillary ligands and pH of the reaction solutions, thus allowing an effective tuning of the self-assembly. The magnetic susceptibility measurements suggest that the copper centers in all three complexes are antiferromagnetically coupled. The thermal properties of 1–3 have been investigated by thermogravimetric and differential thermal analytical (TGA and DTA) techniques, indicating that the decomposition of all three complexes proceeds via multistep processes.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Ancillary-Ligand-Assisted Variation in Nuclearities Leading to the Formation of Di-, Tri-, and Tetranuclear Copper(II) Complexes with Multifaceted Carboxylate Coordination Chemistry

Majumder

Das

et al. 2022

ACS Omega

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“…[34][35][36][37][38] Among the different ligand systems employed in the design and synthesis of transition metal-based model complexes, the carboxylate containing multidentate ligands are an important class showing diverse applications, including broad biological activities. [39][40][41][42][43][44][45] In particular, carboxylate-based ligands are of special interest because of the variety of ways in which they are coordinated to metal ions. The most important coordination modes of the carboxylate groups are monodentate, syn-syn bidentate, syn-anti bidentate and anti-anti bidentate.…”

Section: Introductionmentioning

confidence: 99%

“…Among the different ligand systems employed in the design and synthesis of transition metal‐based model complexes, the carboxylate containing multidentate ligands are an important class showing diverse applications, including broad biological activities [39–45] . In particular, carboxylate‐based ligands are of special interest because of the variety of ways in which they are coordinated to metal ions.…”

Section: Introductionmentioning

confidence: 99%

Cu(II), Mn(II) and Zn(II) Complexes of Anthracene‐Affixed Carboxylate‐Rich Tridentate Ligand: Synthesis, Structure, Spectroscopic Investigation and Their DNA Binding Profile

et al. 2022

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Anthracene-affixed carboxylate-rich tridentate ligand containing three new mononuclear complexes, [Cu(acpa)(H 2 O) 2 ]⋅H 2 O (1), [Mn(acpa)(H 2 O) 2 ] (2) and [Zn(acpa)(H 2 O) 2 ] (3) (H 2 acpa = 3-(anthracene-9-ylmethyl-carboxymethyl-amino)-propionic acid), have been synthesized and characterized by various analytical and spectral methods. In methanol, complexes 1-3 have been prepared by carrying out reaction of the ligand H 2 acpa with stoichiometric amounts of CuSO 4 ⋅ 5H 2 O, MnSO 4 ⋅H 2 O and ZnSO 4 ⋅ 7H 2 O respectively, in the presence of NaOH at ambient temperature. The X-ray crystal structure analysis reveals that complex 1 consists of a distorted square pyramidal copper center, coordinated to one acpa 2À ligand in a tridentate manner (N,O,O) and two exogenous water molecules. On the other hand, the molecular structures of complexes 2 and 3, optimized by DFT method indicate that their core arrangements around the metal centers are similar to that of 1. In solution, the coordination phenomena of Cu((II), Mn(II) and Zn(II) ions with the ligand H 2 acpa and the structural features of the complexes have been authenticated by UV-Vis and fluorescence titration experiments. The composition of the M II /acpa 2À complexes (M = Cu, Mn, Zn) in 1-3 has been observed to be 1 : 1, based on the UV-Vis/fluorescence titration results which are further supported by X-ray crystallography and DFT calculation. Complexes 1-3 are investigated for their binding affinity towards Calf Thymus (CT) DNA in solution at pH ∼ 7.5 by UV-Vis and fluorescence spectroscopic methods. From the electronic absorption spectral studies, it has been found that the DNA binding constants of 1-3 are (5.67 � 0.32) × 10 4 M À 1 , (2.35 � 0.26) × 10 4 M À 1 and (2.49 � 0.33) × 10 4 M À 1 , respectively, following the order 1 > 3 > 2. Measurements of viscosity of DNA in the absence and presence of the metal complexes suggest that all three complexes interact with DNA through partial intercalative mode.

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“…In this context, it is worth mentioning that the use of a carboxylate bridge has proved to be a useful tool for accessing multimetallic complexes in a controlled fashion, thus showing their potential coordination properties for generating different macrocyclic ring systems . Furthermore, it should be pointed out that there are several examples of hexanuclear carboxylate-bridged zinc(II) complexes, some of which exhibit attractive biological activities. − Recently, our research group has reported several di- and tetranuclear copper(II), zinc(II), iron(III), and cobalt(II) model complexes of the ligand H 3 cpdp showing interesting biological properties. − Moreover, we have also reported copper(II)-based hexanuclear and nickel(II)-based tetranuclear complexes of similar carboxylate-containing ligands with methodical biological studies. , Therefore, in the present contribution, we report the synthetic, structural, spectroscopic, and thermal aspects of three new [Zn 6 ] complexes, as well as their biological properties such as antidiabetic and anticancer activities.…”

Section: Introductionmentioning

confidence: 99%

A Family of [Zn₆] Complexes from the Carboxylate-Bridge-Supported Assembly of [Zn₂] Building Units: Synthetic, Structural, Spectroscopic, and Systematic Biological Studies

et al. 2021

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The three discrete [Zn 6 ] c omplexes [Na 3 Zn 6 (cpdp) 3 (μ-Bz) 3 (CH 3 OH) 6 ][ZnCl 4 ][ZnCl 3 (H 2 O)]• 3CH 3 OH•1.5H 2 O (1), [Na 3 Zn 6 (cpdp) 3 (μ-p-OBz) 3 (CH 3 OH) 6 ]• 2H 2 O (2), and [Na 3 Zn 6, have been successfully synthesized and fully characterized (Bz = benzoate; p-OBz = dianion of phydroxybenzoic acid; p-NO 2 Bz = p-nitrobenzoate). The complexes have been characterized by elemental analysis, FTIR, UV−vis, NMR spectroscopy, PXRD, and thermal analysis, including singlecrystal X-ray crystallography of 1 and 2. The molecular architectures of 1−3 are built from the self-assembly of their corresponding [Zn 2 ] units, which are interconnected to the central [Na 3 (CH 3 OH) 6 ] 3+ core by six endogenous benzoate groups, with each linking one Zn(II) and one Na(I) ion in a μ 2 :η 1 :η 1 -syn-anti bidentate fashion. The composition of the (cpdp 3− ) 3 /(Zn 2+ ) 6 complexes in 1−3 has been observed to be 1:2, on the basis of the UV−vis titration and NMR spectroscopic results, which is further supported by Xray crystallography. Systematic biological studies performed with a mice model suggested possible antidiabetic efficacy as well as anticancer activities of the complexes. When complexes 1−3 were administered intraperitoneally in mice, 1 showed a lowering in the blood glucose level, overall maintenance of the pancreatic tissue mass, restriction of DNA damage in pancreatic cells, and retention of lipid droplet (LD) frequency, whereas 2 and 3 showed hepatic tissue mass consistency by inhibiting the DNA damage in hepatic cells, prior to the exposure to a potent diabetic inducer, alloxan (ALX). Similar trends of results were observed in inhibiting the generation of reactive oxygen species (ROS) in the pancreatic and hepatic cells, as examined by spectrofluorometric methods. Thus, 1 seems to be a better compound for overall diabetic management and control, whereas 2 and 3 seem to be promising compounds for designing chemopreventive drugs against hepatic carcinoma.

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Aromatic dicarboxylate incorporated new di- and tetranuclear cobalt(II) complexes: Synthetic and structural aspects, and evaluation of properties and catalytic activity

Cited by 4 publications

References 73 publications

Ancillary-Ligand-Assisted Variation in Nuclearities Leading to the Formation of Di-, Tri-, and Tetranuclear Copper(II) Complexes with Multifaceted Carboxylate Coordination Chemistry

Ancillary-Ligand-Assisted Variation in Nuclearities Leading to the Formation of Di-, Tri-, and Tetranuclear Copper(II) Complexes with Multifaceted Carboxylate Coordination Chemistry

Cu(II), Mn(II) and Zn(II) Complexes of Anthracene‐Affixed Carboxylate‐Rich Tridentate Ligand: Synthesis, Structure, Spectroscopic Investigation and Their DNA Binding Profile

A Family of [Zn₆] Complexes from the Carboxylate-Bridge-Supported Assembly of [Zn₂] Building Units: Synthetic, Structural, Spectroscopic, and Systematic Biological Studies

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Aromatic dicarboxylate incorporated new di- and tetranuclear cobalt(II) complexes: Synthetic and structural aspects, and evaluation of properties and catalytic activity

Cited by 4 publications

References 73 publications

Ancillary-Ligand-Assisted Variation in Nuclearities Leading to the Formation of Di-, Tri-, and Tetranuclear Copper(II) Complexes with Multifaceted Carboxylate Coordination Chemistry

Ancillary-Ligand-Assisted Variation in Nuclearities Leading to the Formation of Di-, Tri-, and Tetranuclear Copper(II) Complexes with Multifaceted Carboxylate Coordination Chemistry

Cu(II), Mn(II) and Zn(II) Complexes of Anthracene‐Affixed Carboxylate‐Rich Tridentate Ligand: Synthesis, Structure, Spectroscopic Investigation and Their DNA Binding Profile

A Family of [Zn6] Complexes from the Carboxylate-Bridge-Supported Assembly of [Zn2] Building Units: Synthetic, Structural, Spectroscopic, and Systematic Biological Studies

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A Family of [Zn₆] Complexes from the Carboxylate-Bridge-Supported Assembly of [Zn₂] Building Units: Synthetic, Structural, Spectroscopic, and Systematic Biological Studies