Metal–organic frameworks based on pyridyl-tetrazole ligands containing ester or carboxylate pendant arms

Sheridan, Ursula; Gallagher, John F.; Bjerrum, Morten J.; Fleming, Adrienne; Kelleher, Fintan; McGinley, John

doi:10.1016/j.ica.2014.05.028

Cited by 16 publications

(8 citation statements)

References 73 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…for the metal‐organic frameworks of Cu(II) and the 1 H and 2 H derivatives of 2‐5(‐(pyridine)‐2‐yl)‐tetrazol‐1‐yl)acetate [Cu(L) x ] . yH 2 O (x, y = 1 or 2), with a Cu(Py‐tet) 2 (O carbox ) 2 ligand set and for the Cu complexes [Cu(bbtz) 2 (MeOH) 2 ]X 2 and [Cu(bbtz) 3 ]X 2 (bbtz = 1,4‐Di(1,2,3,4‐tetrazol‐2‐yl)butane, X = ClO 4 or BF 4 ) with tetragonally distorted Cu(tet) 4 (O) 2 or Cu(tet) 6 coordination, respectively . For the polymeric [(BTFT) 2 Cu(Py) 2 ] n (BTFTH = 5‐(3,5‐bis(trifluoromethyl)phenyltetrazol) we recently reported a similar EPR spectrum, although with markedly smaller g av (2.013) and Δ g (0.018) values, while for the polymeric [Cu(pydtz)(EtOH)] n we obtained a spectrum of axial ‘inverse’ symmetry with g av = 2.128 and Δ g = 0.095) which is in line with a {dz 2 } 1 configuration and a 2D restraint Jahn‐Teller distortion ,…”

Section: Resultsmentioning

confidence: 99%

Heteroleptic Complexes of the Tridentate Pyridine‐2,6‐di‐tetrazolate Ligand

et al. 2017

View full text Add to dashboard Cite

The synthesis and spectroscopic characterisation of a series of heteroleptic complexes of the tridentate pyridine-2,6-di-(5-tetrazolate) (pydtz(2-)) with Co(II), Ni(II), Cu(II) and Zn(II) and pyridine (Py) and H2O as coligands is reported. Single crystal XRD data reveals the formation of octahedrally configured complexes [Co(pydtz)(H2O)(Py)(2)], [Co(pydtz)(H2O)(2)(Py)]2H(2)O, [Ni(pydtz)(Py)(3)]2Py, and [Zn(pydtz)(H2O)(Py)(2)]Py, and a markedly Jahn-Teller distorted octahedral structure for [Cu(pydtz)(H2O)(2)(Py)]. Magnetic measurements reveal a S = 3/2 high-spin configuration for the Co(II) complex [Co(pydtz)(H2O)(Py)(2)], an S = 1 ground state for the Ni(II) derivative and S = 1/2 Cu(II) ions for [Cu(pydtz)(H2O)(2)(Py)], the latter is supported by electron-paramagnetic-resonance spectroscopy. The crystalline materials are subject to severe corrosion as revealed by powder XRD and DSC-TG experiments. H2O and pyridine co-crystallisates and coligands are easily cleaved. At the same time DSC-TG reveal very high stability of the [M(pydtz)] fragments with exothermic decomposition at T > 300 degrees C. As a consequence, in pyridine solution in all cases the species [M(pydtz)(Py)(3)] are observed. Ultraviolet-visible light absorption spectroscopy reveals a strong ligand field procured by the pydtz(2-) ligand and electrochemical measurements suggest very strong sigma-donation but only weak -accepting abilities of pydtz(2-) compared to the isostructural terpy (2,2';6',2''-terpyridine) ligand

show abstract

Section: Resultsmentioning

confidence: 99%

Heteroleptic Complexes of the Tridentate Pyridine‐2,6‐di‐tetrazolate Ligand

et al. 2017

View full text Add to dashboard Cite

show abstract

“…XTT assay (2,3-Bis-(2-methoxy-4-nitro-5-sulfophenyl)-2 H-tetrazolium-5-carboxanilide) was used to measure the cell proliferation activity at different concentrations of 1-4 complexes (5,10,50 and 100 µM) and tested in triplicate for 48 h [30,31]. These results are expressed in average-standard devi- ation of two experiments obtained and Cis platin was used as a standard control.…”

Section: Cytotoxicity Studiesmentioning

confidence: 99%

“…N-donar ligands are biologically important, have a key role in coordinating copper metal and their application as anticancer agents [3,4]. Tetrazoles are an important class of N-donor ligands that are metabolically stable substituent for -COOH functional groups; assist in coordination chemistry as ligands, lipophilic spacers [5]. Introducing tetrazole ring into the molecule will reduce the toxic properties of a drug, because it exhibits stronger resistance to in vivo metabolization than the carboxylate group, causing the drug to stay longer (bioavailability) in blood [6,7].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization of Mixed Cu(II) Pyridyl Tetrazoles and 1,10-Phenanthroline Complexes - DFT and Biological Activity

Himasekar¹,

Mustafa²,

Babu³

2019

Open Chem. J.

View full text Add to dashboard Cite

Background: Mixed ligand copper complexes with 1,10-phenanthroline show good chemical nuclease activity and anticancer activity. Recently, tetrazole derivatives are also promising candidates for anticancer activity. Hence, it is significant to study the DNA binding and anticancer activity of two active N-donor ligands and their copper complexes. Objectives: The main objective of this study was to investigate the regioisomeric mixed ligand copper complexes response with calf thymus DNA binding and anti-toxic activity against MCF-7 cell line. Methods: The DNA binding interactions of complexes 1-4 with calf thymus DNA (CT-DNA) were monitored by UV/VIS spectroscopy. The absorption spectra of the Cu complexes are compared with and without CT-DNA at 400-450 nm. The cell proliferation was measured by using the standard 2,3-bis(2-methoxy-4-nitro-5-sulfophenyl)-2H-tetrazolium-5-carboxanilide (XTT) assay with four different concentrations of the compounds (5, 10, 50, and 100 mm) and cisplatin (as a positive control) was tested in triplicate for 48 h. The results obtained by the XTTassay are expressed as the average standard deviation of two experiments. The IC 50 values of the complexes exhibited differential and dose-dependent inhibitory activities on the growth of MCF-7 cancer cells. Results: Based on the elemental analysis, molar conductance, magnetic moments, mass, electronic, ESR and IR spectral data, the copper is coordinated by N-atoms of 1,10-phenanthroline and pyridyl tetrazole with octahedral structure. DFT calculations of HOMO and LUMO studies showed that electron density is localized on pyridyl tetrazole ring and phenanthroline ring. The calculated DNA binding constant (K b) values of 1-4 complexes are in the range 4.2-7.6 x10 4 M-1 (Table 4) with similar binding affinity to reported copper tetrazole derivative complexes. The 1-4 complexes with CT DNA interaction are through planar phenanthroline and pyridyl tetrazole ring likely via π-stacking interactions. The IC 50 values of complexes show excellent activity with 24(± 0.5); 18(± 0.5); 20(±0.5); (±0.5) and 38 (±0.8) for 1, 2, 3, 4 and cis platin complexes, respectively. After 72 h of the treatment of 1 on MCF-7 cell, IC 50 values hinder the cell growth upto 24(± 0.5) µg/ml at 5 µM concentration range (Fig. 5). It is apparent from IC 50 values that the order inhibition is 1 > 3 >2 > 4. Conclusion: Experimental results are highly encouraging to explore the mixed ligand regio isomeric copper complexes which have shown the parallel result with Cisplatin. By proper structural modification of pyridyl tetrazole ligand, substituent better anticancer agents can be prepared.

show abstract

“…In our previous work, we successfully designed a series of pyridyl-tetrazole ligands with a flexible tethered carboxylate group and introduced them into CP systems, and obtained novel networks and multinuclear clusters (6). In the present research, we have developed these systems into bis-tetrazole systems, where the linker introduced to join these moieties was a pyrazine moiety, a rigid linker with limited conformational freedom; hence the ligands were synthesised as presented in Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterisation of new copper(II) coordination polymers constructed from pyrazine–tetrazole ligands with the formation of a water cluster

Sheridan

Gallagher

Fadda

et al. 2016

Supramolecular Chemistry

Self Cite

View full text Add to dashboard Cite

Three novel bis-tetrazole ligands (1-3) containing carboxylate functional groups on the tetrazole rings and a rigid pyrazine linker unit, for the construction of coordination polymers when coordinated to copper(II) ions, were synthesised and structurally characterised. The use of pyrazine as a rigid linker between the two tetrazole units was expected to increase the dimensionality of the solid phase polymeric network of the resulting copper(II)-containing compounds. X-ray structures of the ligands revealed the effect of the substitution position on the tetrazole ring of the ester/ carboxylate groups. Higher solid phase dimensionality was successfully achieved as shown by the layered two-dimensional (2-D) coordination structure being formed when the pyrazine bis-tetrazole systems were reacted with copper(II) chloride, although not in the expected manner. There was no interaction between the pyrazine nitrogen atoms and the metal ion. Computational studies showed that this was probably due to the geometry, required by the copper ion, to be involved in the close packing between the layers. The 2-D coordination polymer based on the asymmetric substituted pyrazine bis-tetrazole, [Cu(4)(H 2 O)](H 2 O) 2 , was further connected into a three-dimensional (3-D) coordination network through hydrogen bonding between H 2 O molecules. These H 2 O molecules were connected as a unique 1-D chain throughout the structure.Three novel bis-tetrazole ligands (1-3) containing carboxylate functional groups on the tetrazole rings and a rigid pyrazine linker unit, for the construction of coordination polymers when coordinated to copper(II) ions, were synthesised and structurally characterised.

show abstract

Metal–organic frameworks based on pyridyl-tetrazole ligands containing ester or carboxylate pendant arms

Cited by 16 publications

References 73 publications

Heteroleptic Complexes of the Tridentate Pyridine‐2,6‐di‐tetrazolate Ligand

Heteroleptic Complexes of the Tridentate Pyridine‐2,6‐di‐tetrazolate Ligand

Synthesis, Characterization of Mixed Cu(II) Pyridyl Tetrazoles and 1,10-Phenanthroline Complexes - DFT and Biological Activity

Synthesis and characterisation of new copper(II) coordination polymers constructed from pyrazine–tetrazole ligands with the formation of a water cluster

Contact Info

Product

Resources

About