Facile synthesis of paramagnetic Co(II)-hexaborate(2-) based semiorganic complexes: A combined investigation on X-Ray crystal structure, Hirshfield surfaces analysis, optical and magnetic properties

doi:10.21203/rs.3.rs-2695235/v1

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Facile synthesis of paramagnetic Co(II)-hexaborate(2-) based semiorganic complexes: A combined investigation on X-Ray crystal structure, Hirshfield surfaces analysis, optical and magnetic properties

https://doi.org/10.21203/rs.3.rs-2695235/v1

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published 16 Aug, 2023

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Two new paramagnetic hybrid cobalt(II)-hexaborate(2-) based semiorganic complexes; (2A3MP)₂[Co{κ³O-B₆O₇(OH)₆}₂].2H₂O(1) and (2A4MP)₂[Co{κ³O-B₆O₇(OH)₆}₂].2H₂O (2)(2A3MP = 2-amino-3-methylpyridinium, 2A4MP = 2-amino-4-methylpyridinium)have been obtainedand characterized by X-ray diffraction, FT-IR, TG-DTA, optical and magnetic measurements. X-ray diffraction revealed two isostructural lattices with octahedral coordination of Co(II) complexes of bis(κ³O-donor hexaborate(2-)) ligands, [Co{κ³O-B₆O₇(OH)₆}₂]^2-. The hydrated oxidopolyborate anions are extensively H-bounded to perform 3D-porous supramolecular anionic frameworks. In both 1 and 2 isostructures, 2A3MP and 2A4MP cations are pendant in the created voids of the inorganic frameworks through a set of H-bonds with 8.5 % and 60.5%H…O/O…H inter-contact contributions, respectively for 1 and 2 as confirmed by Hirshfield surfaces analysis. The optical band gap of Co(II) complexes range between 2.72 and 3.13 eV. Both compounds exhibited well-resolved paramagnetic properties with magnetic susceptibility values ranged between 0.9552 and 0.0088 cm³.mol^-1, typical of octahedral Co(II) complexes.

Co(II) complexes

Hydrated O-donor hexaborate(2-) ligands

X-Ray crystal structure

Optical Bond gap

Paramagnetic properties

The oxidopolyborates based compounds, more known as Borates, are so renowned by their diversify structures, their interesting architectures and especially their potent employments in several economic areas, as agriculture, vitreous or fire retardant products for example [1–3]. Additionally, some of mineral borates are used in nonlinear optics, and also as photoluminescent and semi-conductor materials with wide bond gap [4, 5]. Recently, the poly-borate-containing compounds are combined with other non-linear optical materials (NLOs) to find lithium electrode batteries [6]. It attracts the main focus of interest in academic and industrial studies because of their rich structures and specially their great aptitude to be coordinated with other species like d-elements (Cu²⁺, Co ²⁺, Ni²⁺….) and organic cations [7–14]. In fact, this great synergy arouses novel coordination metal complexes with significant optical and magnetic properties specifically owing to the existence of electrons in the d orbital (paired or unpaired).For example, Mohammed A. Altahan et al. have recently reported that several oxidoborates templated by nickel ion with d⁸ configuration, coordinate with both inorganic and organic entities such as [Ni(NH₃)₄(H₂O)₂][B₄O₅(OH)₄].H₂O, [Ni(dmen)(H₂O){B₆O₇(OH)₆}].5H₂O and trans-[Ni(en)(H₂O)₂{B₆O₇(OH)₆}].H₂O which showed paramagnetic behaviors with magnetic susceptibility values ranging from 2500 × 10^− 6 to 3600 × 10^− 6 cm³_·mol^− 1 [8].In fact, the combination of d-metal ions, hydrated oxidopolyborate anions and organic moieties may potentially enhance fascinating properties by building magnetic porous architectures. Notably, the exploration of magnetic open structural networks have been challenging owing to their magnetic sensors [15, 16].

Motivated by developing novel and more efficient sensors for magnetic field applications, herein we report the synthesis, structural and magnetic investigations of two paramagnetic Co(II) bis(µ₃-O-donor hexaborate(2-)) complexes templated with 2-aminopyridinium derivatives.

2.1 Crystal growth

The following reactants were used: boric acid (BH₃O₃, 99.5%, Sigma-Aldrich), 2-amino-3-methyl pyridine (C₆H₈N₂, 95%, Sigma-Aldrich), 2-amino-4-methyl pyridine (C₆H₈N₂, 95%, Sigma-Aldrich), Cobalt Chloride (CoCl₂, 97% Sigma-Aldrich), Ethanol (EtoH, 99.8%, Sigma-Aldrich). The chemical reactants were commercially available, were used without any further purification and manipulated under a fume hood.

In synthesis of (1) and (2), Solution A was prepared by dissolution of boric acid (3 mmol, 185.5 mg) in 30 mL of water. The B(OH)₃ will exhibit the Lewis acid state and will take the –OH^- group of water to turn into B(OH)^4-following the equation below [6].

B(OH)₃ + 2H₂O → [H₃O]⁺ + [B(OH)₄]⁻

Solution B was prepared by dissolution of B(OH)₃ (3 mmol, 185.5 mg) in 10 ml of ethanol. This solution was then added to solution A to form the hexaborate anions [B₆O₇(OH)₆]²⁻. To this solution, 2-amino-3-methylpyridine (2 mmol, 216.30 mg) and 2-amino-4-methylpyridine (2 mmol, 216.30 mg) were added for compound 1 and compound 2, respectively. Then, anhydrous CoCl₂ (2mmol, 259.70 mg) was added and, the mixture was stirred for 2 hours to give a pink basic solution. After this period, the pH was adjusted to 8 by HCl addition. The solution was filtered and the filtrate was allowed to stand for crystallization for 10 days after which prismatic pink crystals appeared and were collected.

2.2 .Structural characterization

Single pink crystal’s with the dimensions 0.2 × 0.2 × 0.1 mm³ (1) and 0.18 × 0.13 × 0.08 mm³ (2) were chosen under an optical microscope and were mounted on Micro Mount patented by MiTeGen, inserted into a goniometer base to perform single-crystal X-ray diffraction experiment. X-ray intensity data were collected on a Bruker DUO-APEX2 diffractometer using Ag-Ka radiation (λ = 0.56086Å) with an optical fiber as collimator. Several sets of narrow data frames (30s per frame for 1 and 30s for 2 were collected at different values of q for two initial values of φ and ω, respectively, using 0.3° increments of φ with ω scans. Data reduction was accomplished using SAINT V8.34a.[17] The substantial redundancy in data allowed a semi-empirical absorption correction (SADABS V2014/5) to be applied, on the basis of multiple measurements of equivalent reflections [18]. The structures were solved by direct methods, developed by successive difference Fourier syntheses, and refined by full-matrix least-squares on all F2 data using SHELX program suites, implemented in the OLEX2 graphical tool [19]. Figures of the molecular structure were drawn using DIAMOND software [20].

Crystallographic data for the structural analyses of 1 and 2 have been deposited in the Cambridge Crystallographic Data Centre with CCDC reference numbers 2153000 and 2153011 respectively. These data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/ (or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; e-mail: [email protected]).

A summary of the crystals data and details of structural refinement of compounds 1 and 2 are given in Table 1.

Table 1

Main crystallographic data of isostructures
Compound	1	2
Formula FW Temperature/K Crystal system Space group a (Å) b (Å) c (Å) α (°) β (°) γ (°) V (Å3) Z ρcalculated (g/cm^-3) Crystal size (mm³) Radiation (Å) Thetamin-max (°) µ/mm^-1 Uniquereflections Nref, Npar R1, wR2 Goodness-of-fit on F² Min and max resd. Dens. (e/ Å^-3)	C₁₂H₃₄B₁₂CoN₄O₂₈ 871.08 296.15 Triclinic P\(\stackrel{-}{1}\) 8.2291 (5) 9.0695 (5) 11.4739 (7) 92.938 (2) 98.582(2) 99.271(2) 833.2 (9) 1 1.736 0.2×0.2×0.1 Ag Kα (λ = 0.56086) 2.5–22 0.34 4117, [R(int) = 0.039] 3, 284 0.030, 0.077 0.97 -0.37, 0.32	C₁₂H₃₄B₁₂CoN₄O₂₆ 871.08 296.15 Triclinic P\(\stackrel{-}{1}\) 8.1097 (7) 9.1705 (8) 11.3301 (10) 95.248 (3) 96.141 (3) 98.326 (3) 824.04 (12) 1 1.755 0.18 × 0.13 × 0.08 AgKα (λ = 0.56086) 2.5–20.5 0.34 3396, [R(int) = 0.045] 7, 284 0.066, 0.198 1.16 -0.45, 2.41

2.2 IR spectroscopy

The infrared spectra were measured on a Perkin-Elmer Spectrum Two spectrometer between 4000 and 400 cm^-1, equipped with a diamond attenuated total reflectance (ATR) accessory. No ATR correction was applied on the registered spectra.

2.3 Magnetic measurements

Magnetization measurements were performed in Field Cooled (FC) and Zero Field Cooled (ZFC) procedures with 0.1 T of external magnetic field in Dyna Cool 9T PPMS from Quantum Design. Isothermal hysteresis magnetization measurements against magnetic field were collected at selected temperatures in the same apparatus.

2.4 Thermal analysis

The thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were performed on a TG-DTA92 SETERAM under an air atmosphere at a heating rate of 1°C.min^-1 from room temperature to 800°C.

2.5 Powder X-ray diffraction

Microcrystalline powder patterns were recorded using a Bruker D8 Advance diffractometer equipped with a LynxEye fast detector and using a Cu kα radiation. Each pattern was recorded in the 2θ range of5° − 50° with a 0.5 s/step scan.

3.1 Structural studies and description

Crystalline phases of compounds 1 and 2 were analyzed by PXRD (Fig S1). The superposition of the experimental diagrams with the theoretical ones, obtained from the single-crystal X-ray diffraction, shows a good correspondence, indicating so the purity of the grown crystals .

It should be noted that both compounds are rather similar and contain two hexaborate rings complexing a single Co(II) cation surrounded by oxygen atoms with a coordination number of six in a distorted octahedral environment. The charge balance is assured by the presence of two organic protonated cations,2-amino-3-methylpyridinium and 2-amino-4-methylpyridinium for compound 1 and 2 respectively (Fig. 1).

In both systems, the asymmetric unit is built up from a Co(II) ion, one hexaborate ligand partnered with an organic protonated cation (C₆H₉N₂)⁺ and one water of crystallisation.The full octahedral molecular system [Co{κ³O-B₆O₇(OH)₆}₂]²⁻can be generated through the inversion center located on the cobalt atom. Considering the charge of the hexameric polyborates, the boron centers should be 3⁺ the cobalt cation should be 2⁺. This is confirmed by BVS calculation for both systems where the calculated values are on average2.1617v.u and 3.050v.u for compound 1 and 2.1605v.uto3.036v.u for compound 2 [21]. Complete composition considering the protonated organic parts and the hydration composition is then (C₆N₂H₉)₂[Co{κ³O-B₆O₇(OH)₆}₂].2H₂O. In these molecules, the hexaborate(2-)anions,[B₆O₇(OH)₆]²⁻, are composed of three six-membered rings in which three trigonal B1 centers (BO₂(OH)group) and the three tetrahedral B₂ centers(BO₄group) are linked by six µ₂-O and one µ₃-Obridging oxygen atoms (Fig. 2). Using the classification of polyborates anions proposed by Hellen, Chris and Clark [22], the fundamental building blocks(FBB) shorthand notation for the hexameric [B₆O₇(OH)₆]²⁻anion present in compounds1 and 2is 6:3Δ + 3T.

The main bond lengths and angles of the two systems are recorded in (Table S1). The Co-O bonds lengths are ranged between 2.0125(11) Å and 2.1776(11) Å in compound 1 and 2.041(3) Å and 2.147(3) Å in compound 2with a good agreement with previously obtained hexaborato-cobaltate complexes in (C₄H₁₂N₂)[Co{B₆O₇(OH)₆}₂].6H₂O [7], (C₅H₁₄N₂)[Co{B₆O₇(OH)₆}₂].2H₂O [23] and (C₅H₁₁N₃)[Co{B₆O₇(OH)₆}₂].4H₂O [24].

In the triangular boron groups, the B-O distances vary from 1.3510(2) Å to 1.373(2) Å [av. = 1.362 Å] in compound1 and from 1.352(7) Å to 1.383(6) Å [av. = 1.3635 Å] in compound 2. In the tetrahedral boron groups, the B-O bands vary from 1.440(2) Å to 1.5146(19) Å [av. = 1.4773 Å] and 1.435(6) Å to 1.5180(6) Å [av. = 1.468 Å] in compound1 and 2, respectively. These values are comparable with distances observed in several hexaborate compounds [25–29].

Furthermore, the structures of 1 and 2 are specifically stabilized by a set of potential H-bond interactions involving both anion-anion and cation-anion contacts leading so to generate three-dimensional porous architectures. In fact, the adjacent [Co{κ³O-B₆O₇(OH)₆}₂]²⁻ complex anions are interconnected via extensive O_hexborate—H⋅⋅⋅O_hexaborate (O…O distance: 2.7051 (18)- 3.365 (3) Å for 1, 2.725 (5)- 3.371 (6) for 2) (Table S2) giving rise to a porous 3D net-like inorganic subnetwork with channels voids along c and a-axis for compounds 1 and 2, respectively, as exposed in Fig. 2.As well, each compound includes tow interstitial H₂O molecules which are H-bonding to the hexaborate (2-) units through O_hexborate—H⋅⋅⋅OW and OW —H⋅⋅⋅O_hexborate. These potential hydrogen bond interactions are also evidenced by the molecular Hirshfeld surfaces (HS) analysis coupled with the 2D-fingerprint [30, 31] which indicate that the contributions ofH…O/ O…H interactions ( 58. % and 60.5% for 1and 2, respectively)are the most important in the building of a stabilized 3D-porous networks to easily hold the organic moieties. In addition ,the amine groups are located in the channel voids running down the crystallographic c and a-axis,in compound 1and 2 respectively, and interacted with the inorganic framework by a set of N—H…O and C—H…O hydrogen bonds. In this case, the HS analysis reveals a relatively moderate contribution of H…H intercontacts (30. %and 27.5% for 1and 2, respectively) with much more less ones for other intercontacts (B⋯H, O⋯O,B⋯O, C⋯O, C⋯H, C⋯C, C⋯N,O⋯N,N⋅⋅H, B⋯C, B⋯B, N⋯O, B⋯N and N⋯N).

With regard to the organic moities, π···πstacking interactions are detected between the centroid (Cg) of the pyridinium cations Cg1–Cg1i (distances of 4.170Å) for compound 1 and Cg2-Cg2i (distances of 3.3573 Å)for compound 2which is confirmed by the appearing of the red triangles on the Hirshfeld surface mapped with shape-index (Fig. 4). Moreover, supplementary interactions between the pyridine and the µ3-O bridge (O4) in the center of the hexameric polyborates are also observed (with distances of 4.0963 Å and 4.16549 Å for compound 1 and 2 respectively), giving so more stability of the crystalline network of both systems.

3.2 Optical Properties

The UV-Vis spectra and the gap energy determination curves are shown in Figs. 5 and 6. An intense bands are observed in the UV region of the spectra, at 235 and 311 nm, respectively for compound 1 and 2which can be referred to the π−π∗ and n−π∗ interactions [24, 37].On the other hand, the characteristic bands of the octahedral coordination sphere of Co(II) metal ion appeared in the visible region at 510 nm and 660 nm for compound 1 and 512 and 661 nm for compound 2, well assigned to ⁴T_1g (F)->⁴T_1g (P) and ⁴T_1g (F) ->⁴A_2g(F) transitions of Co(II) in octahedral coordination.

Using the Tauc equation and by extrapolation of the plot of (αh𝛎)² versus (h𝛎) we found that the Eg value is 2.72 and 3.13 eV for compound 1 and 2, respectively, corresponding so to a semi-conductor band gap energy difference [24, 28].

3.3 Magnetic moment

Data were recorded following standard procedures by cooling from room temperature to 2K at zero fields (ZFC) to align the spins followed by a second cooling analysis (FC) under different fields. Magnetization as a function of the field was measured between − 90000 Oe and + 90000 Oe at different temperatures. The magnetization of the two compounds as a function of the applied field shows linear behaviors for 300K. When the temperature drops to 2K, we see a complete alignment of the spins within the cobalt atoms of the two hexaborate(2^-) complexes with a maximum value of 2.2µB and 2.1 µB for compounds 1 and 2 respectively. The presence of a tray as well as the large distance between the monomeric cobalt centers of compounds 1 and 2 (< 8Å) indicates their paramagnetic characteristics. The magnetic susceptibility in the range 100K − 300K which follows a Curie-Weiss law (Fig. 7) gives the curie constancy and the Curie temperature when extrapolated (Table 2).

Table 2

Curie constancy and Curie temperature of 1 and 2.
Compound	1	2
Curie Constancy C	0.3314	0.3812
Curie Temperature θCW	0.67	6.76

Molar magnetic susceptibility (χ_m) data for compounds 1 and 2, varied between 0.9552-0.01 cm³.mol^-1and 0.9223 − 0.0088 cm³.mol^-1, respectively. These values are typical of paramagnetic polyborate complexes with octahedral metallic ion [14, 36].

The isolated paramagnetic ion cobalt (II) (d⁷) high spin (S = 3/2) gives a spin only value of 3.88 µB. This value deviates from the experimental value (4.91 µB and 4.58 µB for compounds 1 and 2 respectively (Fig. 8) because of the presence of a spin-orbit coupling with this element. By taking this coupling into account, the theoretical value becomes 4.9µB. It is then in good agreement with the experimental value measured considering isolated cobalt (II) paramagnetic center [32, 33]. In other hand the X-ray diffraction results show that the minimum distances between two cobalt atoms (Co-Co) are 8.229 Å for compound 1 and 9.170 Å for compound 2 which explain the absence of interactions between the cobalt magnetic moments and consequently the paramagnetic aspect of our compounds.

To better understand the magnetic behavior of our compounds and confirm the results obtained, a comparative study was carried out with compounds containing transition metals in octahedral geometries, hexaborate anions or organic cations in common with our compounds studied. This study allows us to present the source of the paramagnetic aspect of our compounds by the absence of organic cations in compound C1 ([CoB₁₂O₁₄(OH)₁₀]) and by the absence of hexaborate anion in compound C2 ([Co(2A4MP)₂(Cl)₂]). In addition, it was found that compound C3 ([Ni(en)₃][B₅O₆(OH)₄][CH₃COO]) has a paramagnetic appearance with an octahedral geometry of nickel similar to that of cobalt in our case study. This full comparison can confirms the factors related to the absence of interaction between the cobalt spins in compounds 1 and 2 and hence the dominant paramagnetic feature.

Table 3

Main magnetic characteristics of 1, 2 and related compounds
Compound	1	2	CoB₁₂O₁₄(OH)₁₀ C1 [12]	[Co(2A4MP)2(Cl)2] C2 [33]	[Ni(en)₃][B₅O₆(OH)₄][CH₃COO] C3 [14]
Metalgeometry	Octahedral	Octahedral	Octahedral	Tetrahedral	Octahedral
magnetic moment	4.91 µ_B	4.58 µ_B	3.95µ_B	4.58µ_B	3.16 µ_B
Spins	High-spin(d⁷)	High-spin(d⁷)	High spin (d⁷)	High-spin (d⁷)	High-spin (d⁸)
Magnetic aspect	Para-magnetic	Para-magnetic	Antiferro-magnetic	Paramagnetic	paramagnetic

3.4 Thermal Analysis

To examine the thermal stability of reported compounds, thermogravimetric analysis coupled with differential thermal analysis (TG-ATD) were carried out under air from ambient temperature up to 700°C at a heating rate of 5°C/min (Fig.S3).The thermal behavior of reported compounds pursued three decomposition steps. The first weight loss of 2.6% and 2.9% below 90°C respectively for compound 1 and 2are related to the departure of water of crystallization consistent with the XRD structure determination. The second ones of 13.8% and 13.05% spreading until 220°Crespectively for compound 1 and 2, can be attributed to the departure of six lattice water molecules belonging tothe hydrated hexaborate(2-) anions. The same behavior is entirely consistent with related hydrated oxidopolyborates [37–39]. The third step corresponds to the release of organic cations which ongoing over a wide temperature range. The total dehydration and decomposition processes can be schematized as follows:

(C₆N₂H₉)₂[Co{B₆O₇(OH)₆}₂].2H₂O\(\underrightarrow{-{2H}_{2}O}\)(C₆N₂H₉)₂[Co{B₆O₇(OH)₆}₂]\(\underrightarrow{-6{H}_{2}O}\)(C₆N₂H₉)₂CoB₁₂O₂₀\(\underrightarrow{-2{\text{C}}_{6}{\text{N}}_{2}{\text{H}}_{9}}\)CoB₁₂O₂₀

Two paramagnetic cobalt (II) hexaborate (2-)complexes templated with 2-aminopyridinium derivatives have been successfully synthesized and characterized. XRD determination revealed two isostructural crystals featuring 3D-porous supramolecular networks of [Co{κ³O-B₆O₇(OH)₆}₂]^2-complex anions templated by 2A3MP and 2A4MP cations and water of crystallization which are extensively interconnected by O...H inter-contacts with a contribution of 58. % and 60.5% respectively for 1and 2as determinedby Hirshfield surface analysis. Both Co(II) complexes revealed well-resolved paramagnetic behaviors with magnetic susceptibilitiesof0.9552 and 0.0088 cm³.mol^-1and spin values of 4.91 µB and 4.58 µB for compounds 1 and 2, respectively. Notably, the use of O-donor hexaborate(2-) ligands may be an efficient way for the preparation of magnetic micro porous materials because of the geometrical versatility of boron coordination, their capability to be good super exchange pathways for magnetic coupling and the possibility to arrange transition metal ions within a variety of open framework structures.

Acknowledgments

The authors are extremely thankful to the Department of Chemistry, University of Carthage, Faculty of Sciences of Bizerte for providing necessary facilities.

Declarations

Ethical Approval

This article does not contain any studies with human participants performed by any of the authors.

Competing Interests

The authors have no relevant financial or non-financial interests to disclose.

Authors’ Contributions

All authors contributed to the study conception and design. Material preparation, data collection, and analysis were performed by Brahim Karoui, AhlemMaalaoui, Mohamed Rzaigui, Samah Akriche and Sylvain Duval. The first draft of the manuscript was written by Brahim Karoui and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

Funding

The authors declare that no funds, grants, or other support were received during the preparation of this manuscript.

Availability of data and materials

All relevant data generated or analyzed during this study are included in this published article

CCDC 2153000 and 2153011 contain supplementary crystallographic data for 1 and 2, respectively. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html or the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: [email protected].

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No competing interests reported.

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Facile synthesis of paramagnetic Co(II)-hexaborate(2-) based semiorganic complexes: A combined investigation on X-Ray crystal structure, Hirshfield surfaces analysis, optical and magnetic properties

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Abstract

Figures

1. Introduction

2. Materials And Methods

2.1 Crystal growth

2.2 .Structural characterization

2.2 IR spectroscopy

2.3 Magnetic measurements

2.4 Thermal analysis

2.5 Powder X-ray diffraction

3. Results And Discussions

3.1 Structural studies and description

3.2 Optical Properties

3.3 Magnetic moment

3.4 Thermal Analysis

4. Conclusion

Declarations

References

Additional Declarations

Supplementary Files

Status:

Journal Publication

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