Syntheses, crystal structures and magnetic studies of new 2D coordination polymers containing dinuclear manganese(II) repetitive units using a ditopic isonicotinhydrazone based N,N,O-donor ligand

doi:10.1016/j.poly.2013.09.025

Polyhedron

Volume 67, 8 January 2014, Pages 396-404

https://doi.org/10.1016/j.poly.2013.09.025 Get rights and content

Abstract

Three new complexes of manganese(II) with pseudohalide anions and (E)-N′-(phenyl(pyridin-2-yl)methylene)isonicotinhydrazide (HL), namely a 2D polymer with azide bridged dinuclear unit [Mn₂(L)₂(μ-N₃)₂]_n (1), a 2D coordination polymer [Mn₂(L)₂(NCS)₂]_n (2a) and a monomeric [Mn(HL)(NCS)₂(OHCH₃)] (2b), were synthesized and characterized by elemental analyses and spectroscopic methods. The structures were established by X-ray diffraction, and further studied by magnetic susceptibility measurements. The isonicotinhydrazide ligand acts as a mononegative tetradentate N₃O-donor ligand and coordinates to the manganese center in the enolic form ( double bond N–NC–O) in 1 and 2a while in complex 2b coordinates as NNO-donor tridentate neutral ligand in keto form (N–NH–CO). Two bridging azide ligands connect the two metal centers in an end-on (EO) fashion in 1. For complex 2a the enolic oxygen of the hydrazone moiety spans two metal centers to form a dinuclear unit containing Mn₂O₂ four-membered planar ring. Magnetic measurements revealed antiferromagnetic coupling inside the dimers for 1 and ferromagnetic coupling for 2a.

Graphical abstract

Syntheses and structures of three new N-arylideneisonicotinhydrazide Mn(II) complexes with pseudohalide ligands are reported. Magnetic properties of two 2D coordination polymers are determined.

Introduction

Design and synthesis of novel coordination polymers and metal–organic frameworks (MOFs) have attracted great attention in the fields of inorganic and coordination chemistry [1]. This is mainly due to the peculiar structure diversity of coordination polymers and their potential application as functional materials in fields such as catalysis, drug delivery, separation, gas storage, ion exchange, sensor technology, energy conversion and magnetic materials [2]. Two most successful strategies for the design of coordination polymers with predetermined molecular architectures are employing (i)-appropriate bridging groups [3] and (ii)-ditopic organic ligands [4] with specific structure and donor pockets which simultaneously can bind to several metal ions. The pseudohalide anions (N₃⁻, SCN⁻, etc.) are known as very appealing bridging groups for the design of polynuclear transition metal complexes [5] and 1D, 2D or 3D coordination networks [6]. These bridging ligands also play an important role in the magnetic exchange pathways between paramagnetic centers and generally, show various magnetic interactions which are attributed to the diversity of coordination modes [7]. Usually, the azide ligand links metal ions in end-to-end (μ-1,3-N₃, EE) [8] and/or end-on (μ-1,1-N₃, EO) [9] modes. The thiocyanate ion is a versatile ambidentate ligand and coordinates to the metal ions through N, S, or both atoms, giving rise to linkage isomers [10], dimers [11] or polymers [12]. Some multidentate ligands showed ditopic bridging capability via simultaneous ligations to several metal ions in different directions [13]. The geometries of organic ligands have a great effect on the structural architecture of coordination polymers [14]; therefore, much effort has been devoted to the design and modification of the organic ligands to control the products. To use the second strategy, hydrazone derivatives are appropriate choice. For example aroylhydrazones (Scheme 1) are one of the most important class of flexible and versatile tridentate ligands which show very high efficiency at chelating transition metal ions [15]. Hydrazone ligands obtained from 4-pyridine carboxylic acid hydrazide {Py-C(O)-NH-NH₂} can act as ditopic ligands via two different donor sites (a tridentate coordination pocket and a N-donor pyridine moiety) and show the potential to form mono- [16] and multinuclear [17] structures (Scheme 1). Some interesting coordination polymers have been reported using this kind of ligands [18].

N-arylideneisonicotinhydrazide ligands obtained from the condensation of 4-pyridine carboxylic acid hydrazide with pyridine based aldehyde/ketones (Scheme 1) can coordinate to metal ions as neutral in keto form [17](a), [19] or mono-negative ligand in the enol form [20]

Applications of manganese complexes as model systems for metalloenzymes [21] and their exciting magnetic properties [22] and considering the coordination ability of ditopic N-arylideneisonicotinhydrazide ligands and pseudohalides towards transition metals, prompted us to use mix ligand strategy [23] and employ ditopic and bridging ligands simultaneously to prepare new manganese coordination polymers with new properties. In the present work we report synthesis, structure, spectroscopic studies and magnetic properties of monomeric and 2D polymeric complexes of Mn(II).

Section snippets

Materials and instrumentations

Manganese(II) chloride tetrahydrate, 4-pyridinecarboxylic acid hydrazide, 2-benzoylpyridine, sodium azide and potassium thiocyanate were purchased from Merck and used as received. Solvents of the highest grade commercially available (Merck) were used without further purification. IR spectra were recorded as KBr disks with a Bruker FT–IR spectrophotometer. UV–Vis spectra of solution were recorded on a thermo spectronic, Helios Alpha spectrometer. ¹H and ¹³C NMR spectra of ligand in DMSO-d₆

Syntheses of complexes and spectroscopy

The reaction of 4-pyridinecarboxylic acid hydrazide with 2-benzoylpyridine in methanol gave the desired Schiff base ligand HL in excellent yield and purity (Scheme 1). Complex [Mn₂(L)₂(μ-N₃)₂]_n (1) was synthesized by the reaction of HL, MnCl₂·4H₂O and NaN₃ with molar ratios 1.0:1.1:2.0 in methanol (Scheme 2). Reaction of HL, MnCl₂·4H₂O and KSCN with molar ratios 1.0:1.1:2.0 resulted in [Mn₂(L)₂(NCS)₂]_n (2a). Complex 2a was a major product of this reaction but 40% of red crystals of complex 2a

Conclusion

Three new complexes of Mn(II) 1, 2a and 2b with pseudohalide anions and (E)-N′-(phenyl(pyridin-2-yl)methylene)isonicotinhydrazide (HL) were synthesized and characterized by elemental analyses and spectroscopic methods. The compounds were characterized by X-ray diffraction and magnetic susceptibility measurement studies. In complex 1 the two bridging azide ligands have connected to two metal centers in an end-on fashion and form a dinuclear complex which converts to a 2D coordination polymer by

Acknowledgments

The authors are grateful to the University of Zanjan and Universidad Complutense de Madrid (group 921508) for financial support of this study.

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Syntheses, crystal structures and magnetic studies of new 2D coordination polymers containing dinuclear manganese(II) repetitive units using a ditopic isonicotinhydrazone based N,N,O-donor ligand

Abstract

Graphical abstract

Introduction

Section snippets

Materials and instrumentations

Syntheses of complexes and spectroscopy

Conclusion

Acknowledgments

Dalton Trans.

Inorg. Chem.

Polyhedron

Polyhedron

Polyhedron

Coord. Chem. Rev.

Polyhedron

CrystEngComm

Inorg. Chim. Acta

Inorg. Chem. Commun.

Inorg. Chem. Commun.

Inorg. Chem.

J. Biol. Inorg. Chem.

J. Inorg. Chem.

Inorg. Chem.

Dalton Trans.

Inorg. Chem. Commun.

J. Inorg. Biochem.

Coord. Chem. Rev.

Coord. Chem. Rev.

Acta Crystallogr., Sect. A

Eur. J. Inorg. Chem.

Dalton Trans.

Eur. J. Inorg. Chem.

Inorg. Chim. Acta

Polyhedron

Dalton Trans.

Inorg. Chem.