Elsevier

Inorganica Chimica Acta

Volume 358, Issue 6, 30 March 2005, Pages 1841-1849
Inorganica Chimica Acta

Temperature effect on the conversions of phthalato and maleato manganese(II) complexes with diamine ligands

https://doi.org/10.1016/j.ica.2004.12.011Get rights and content

Abstract

1,10-Phenanthroline hydrogen phthalato manganese(II) dimer [Mn2(Hphth)2(phen)4] · 2Hphth · 6H2O (1), monomeric phenanthroline phthalato manganese(II) monomer [Mn(phth)(phen)2(H2O)] · 2.5H2O (2), 2,2′-bipyridine phthalato manganese(II) polymer [Mn(phth)(bpy)(H2O)2]n (3) and 1,10-phenanthroline maleato polymer [Mn(male)(phen)(H2O)2]n · 2nH2O (4) (H2phth = o-phthalic acid, male = maleic acid, phen = 1,10-phenanthroline and bpy = 2,2′-bipyridine) have been synthesized and characterized spectroscopically and structurally. Each Mn(II) atom in dimeric 1 is octahedrally coordinated by two oxygen atoms of phthalate anions and by two cis-phenanthroline ligands. The hydrogen phthalato anion bridges the Mn(II) ions through the deprotonated carboxyl groups, while the carboxylic acid group remains free. In the monomeric 2, the Mn(II) ion is octahedrally surrounded by four nitrogen atoms from two cis-phen ligands, one carboxyl oxygen from a monodentate phth ion, and one coordinated water molecule. The dimeric phthalato complex 1 can be cleaved into monomer 2 under heating with deprotonation, and the course of the reaction can be qualitatively traced by IR spectra. The phthalate group in the complex 3 binds to two manganese atoms through the vicinal carboxyl-oxygen atoms in syn–syn bridging mode. The Mn(II) atoms are linked by the phthalate group to yield a one-dimensional chain running along the a-axis. The coordination polymer 3 can be obtained from the reaction of dichloro dibipyridine manganese with phthalate under heating. In polymer 4, the manganese atom is six-coordinated by two nitrogen atoms from phen, two oxygen atoms from the coordinated water molecules and two oxygen atoms from two different maleate dianions. Each maleato unit links two neighboring manganese atoms to yield one-dimensional chain along b-axis in bis-monodentate mode. The single-chain polymer 4 prepared at low temperature can be converted to double-chain coordination polymer [Mn(male)(phen)]n · nH2O (5) with dehydration in warm solution.

Graphical abstract

Under heating, phenanthroline hydrogen phthalato manganese(II) dimer could be cleaved into its related monomer with deprotonation of phthalate ligand. The 1D maleato manganese(II) prepared in an ice bath is converted into double-chain coordination polymer.

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Introduction

Carboxylato manganese complexes are of current interest in the studies of molecular magnetism and in applications to diverse areas of technology, such as magnetic recording and magnetic optics [1], and they can also serve as model compounds for photosynthetic oxygen-evolving complexes (OEC) [2]. Many efforts have been made to design and synthesize carboxylato manganese complexes with fascinating architectures [3]. In particular, some dicarboxylate anions such as phthalate [4] and maleate [5] groups have been proved to be powerful bridging spacers to construct noteworthy frameworks. Owing to their versatile bonding modes with metal ions and the fact that the carboxyl groups are noncoplanar within themselves, phthalate and maleate anions are good candidates for constructing multi-dimensional supramolecular architectures with different metal ions like copper [6], [7], nickel [8], [9], cobalt [10], zinc [11], iron [12] and silver [13]. However, up to now, the control of product architecture has been elusive and still remains a major challenge in this field. This is due to the fact that the self-assembly process is frequently influenced by various factors, such as media [14], templates [15], counter-ions [16], [17], pH values [18] and temperature [19]. By the judicious choice of the reaction conditions, it is possible to elaborate specific structures, and even to create expected properties related to the architectures. Though it is well known that temperature is an important factor to affect the resultant structural frameworks, the influence of temperature in the formation of complexes is less well understood and systematic studies are rare [20].

To better understanding of temperature effects on the formation of resulted complexes, in the course of our study on manganese complexation by dicarboxylate anions, we pay special attention to the influence of temperature on the structural topology. Recently, we have obtained two temperature-dependent product of maleato manganese(II) polymers [Mn(male)(bpy)(H2O)]n · 2nH2O and [Mn(male)(bpy)]n [5f]. Herein, four dicarboxylate manganese(II) complexes formulated as [Mn2(Hphth)2(phen)4] · 2Hphth · 6H2O (1) [21], [Mn(phth)(phen)2(H2O)] · 2.5H2O (2) [22], [Mn(phth)(bpy)(H2O)2]n (3) [21], and [Mn(male)(phen)(H2O)2]n · 2nH2O (4) [23] were temperature-dependently prepared and structurally characterized, and their related transformations were studied.

Section snippets

General remarks

All chemicals were analytically pure and used without further purification. Elemental microanalyses were performed on an EA 1100 elemental analyzer. UV–vis spectra were recorded in TU-1901 spectrophotometer and infrared spectra recorded from KBr pellets on a Nicolet FT-IR 360 spectrophotometer in the range of 4000–400 cm−1.

Preparation of [Mn2(Hphth)2(phen)4] · 2Hphth · 6H2O (1) [21]

In a slightly different procedure [21], phthalic acid (0.17 g, 1 mmol) in 50% ethanol solution (15 ml) was slowly added to a 50% ethanol solution (20 ml) of manganese(II)

Synthesis

Assembly process for the reactions of phthalato and maleato manganese(II) complexes with diamine (1,10-phenanthroline and 2,2′-bipyridine) is summarized in Scheme 1. The anions are shown corresponding to compound numbers, which represent both in this description. The scheme illustrates the sensitivity of reaction toward temperature in aqueous solutions. In an ice-water bath, a solution containing phthalato manganese(II) 6 [27] and phen results in the separation of dimer 1. On raising the

Acknowledgements

Financial supports from the Ministry of Science and Technology (001CB108906) and the National Science Foundation of China (Nos. 20171037, 20021002) are gratefully acknowledged.

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