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Syntheses, Crystal Structures and Magnetic Properties of Mixed-valence Linear Trinuclear Cobalt and 2D Nickel Complexes Tian-Fu Liu, Zai-Xin Wang PII: S1387-7003(13)00004-X DOI: doi: 10.1016/j.inoche.2012.12.020 Reference: INOCHE 4922 To appear in: Inorganic Chemistry Communications Received date: 31 July 2012 Accepted date: 21 December 2012 Please cite this article as: Tian-Fu Liu, Zai-Xin Wang, Syntheses, Crystal Structures and Magnetic Properties of Mixed-valence Linear Trinuclear Cobalt and 2D Nickel Com- plexes, Inorganic Chemistry Communications (2013), doi: 10.1016/j.inoche.2012.12.020 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

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Syntheses, Crystal Structures and Magnetic Properties of Mixed-valenceLinear Trinuclear Cobalt and 2D Nickel Complexes

Tian-Fu Liu, Zai-Xin Wang

PII: S1387-7003(13)00004-XDOI: doi: 10.1016/j.inoche.2012.12.020Reference: INOCHE 4922

To appear in: Inorganic Chemistry Communications

Received date: 31 July 2012Accepted date: 21 December 2012

Please cite this article as: Tian-Fu Liu, Zai-Xin Wang, Syntheses, Crystal Structuresand Magnetic Properties of Mixed-valence Linear Trinuclear Cobalt and 2D Nickel Com-plexes, Inorganic Chemistry Communications (2013), doi: 10.1016/j.inoche.2012.12.020

This is a PDF file of an unedited manuscript that has been accepted for publication.As a service to our customers we are providing this early version of the manuscript.The manuscript will undergo copyediting, typesetting, and review of the resulting proofbefore it is published in its final form. Please note that during the production processerrors may be discovered which could affect the content, and all legal disclaimers thatapply to the journal pertain.

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Syntheses, Crystal Structures and Magnetic Properties of

Mixed-valence Linear Trinuclear Cobalt and 2D Nickel Complexes

Tian-Fu Liu* and Zai-Xin Wang

School of Chemistry, Beijing Institute of Technology, Beijing, 100081, P. R. China

Corresponding author: tel.: +86 10 68912667; fax: +86 10 68914780.

E-mail: [email protected]

ABSTRACT: Two new complexes, [CoL2]2[Co(CH3OH)4] (1), and [Ni2L2(CH3OH)2]n

(2) (H2L = 2-(((2-hydroxynaphthalen-1-yl)methylene)amino)acetic acid), have been

synthesized and structurally characterized. Single-crystal X-ray analysis reveals that

complex 1 is linear trinuclear mixed valence cobalt complex, while complex 2 is a 2D

complex by double naphtholate bridged and syn-anti carboxylate bridged. Magnetic

susceptibility measurements indicate that 1 shows mononuclear CoII behavior whereas

2 exhibits an antiferromagnetism behavior.

Keywords: cobalt complex; nickel complex; crystal structure; magnetic property

Over the past two decades, the rational design and synthesis of molecule-based

magnetic materials have attracted considerable interest [1-5]. In order to design

coordination complexes with interesting structure and performance, the match of

metal centers with suitable ligands is one of the most important factors [6]. The

tetradentate Schiff base ligands, derived from the condensation of an amino acid and

salicylaldehyde derivative, have been used extensively to construct various

polynuclear and coordination polymers of CoII and Ni

II that show interesting structural

and magnetic properties [7-11]. The carboxylate anion has shown versatile

coordinating ability to variety of transition metal ions through different coordination

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(syn-anti, syn-syn and anti-anti) modes and efficiently mediates ferromagnetic (FM)

and antiferromagnetic (AFM) coupling between metal centers [12-15]; and the

phenolate anion has also shown efficiently magnetic transmission capacity [16, 17].

We report in this article the synthesis, crystal structures and the magnetic properties of

two complexes [CoL2]2[Co(CH3OH)4] (1) and [Ni2L2(CH3OH)2]n (2) using

2-(((2-hydroxynaphthalen-1-yl)methylene)amino)acetic acid [18] (H2L , Scheme 1) as

building block ligands.

Scheme 1

The reaction of Co(ClO4)26H2O, H2L and NaOH in a 1:1:2 molar ratios in MeOH

gave a red-brown solution from which (1) was subsequently isolated in 40% yields. In

a similar reaction, but employing Ni(ClO4)26H2O with H2L and NaOH in 1:1:2 ratio

in MeOH gave a green solution from which 2 was isolated in 45% yield [19]. The IR

spectra of complexes 1 and 2 are quite similar: the discussion is confined to the most

important vibrations of the 4000-400 cm-1

region in terms of the structure. A broad

peak centered at 3424 cm-1

is most likely due to the νOH group. The νC=N and νC-O

vibration is assigned to the strong-intensity band at 1630, 1600 and 1544 cm-1

.

Fig. 1

The structure of the linear trinuclear cobalt compound 1 [CoL2]2[Co(CH3OH)4] is

provided in Fig. S1 [20]. The deprotonated ligand L acts as a dianionic tetradentate

ligand: one naphtholate oxygen, one carboxyl and one Schiff base nitrogen in one

ligand are bound to the terminal cobalt ions and the other carboxyl is chelated to the

central cobalt ion. All cobalt are octahedral, they are connected by two bridging

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carboxyl, forming a linear trinuclear cobalt structure unit (Fig. 1) with a

Co–O-C–O–Co–O-C–O–Co core and the neighboring Co---Co distance is 5.225(1) Å.

The trinuclear cobalt complex molecule is strictly linear by symmetry, and the central

cobalt atom (Co2) is on a crystallographic symmetry center. The equatorial plane of

the octahedron is perfectly planar and the cobalt ion (Co2) lies in this plane. The plane

coordination sites are occupied by methanol molecules. The terminal cobalt ions have

an octahedral surrounding with another ligand. Co1 is in the +3 oxidation state, and

Co2 is in the +2 oxidation state, as confirmed by combination of bond-length

considerations, BVS calculations, and charge-balance [21]. The terminal Co–O and

Co–N bond lengths for Co–O(naphtholate), Co–O(carbonyl) and Ni–N(-C=N) are

1.887(2), 1.934(1) and 1.881(2) Å, respectively. They are slightly shorter than the

central Co-O bond lengths for Co–O(carbonyl) which are 2.062(2) and 2.072(1) Å

respectively. Adjacent molecules are linked by intermolecular H bonds to form a 2D

infinite layer structure (Fig. S2), and there is no obvious π-π stacking interaction

between naphtholates.

Fig. 2

Crystal structure of 2 [Ni2L2(CH3OH)2]n exhibits a 2D character. The

crystallographically independent Ni(II) atoms, Ni1, is hexa-coordinated in the form of

deformed octahedral cis NiO3O2N; three atoms are from the Schiff base H2L, one

oxygen atom from methanol, with Ni-N distance of 1.979(3) Å, and Ni-O distances in

the range of 2.013(2) to 2.146(3) Å (Fig. S3). The Ni(II) ions are related by inversion

centers and bridged by naphtholate oxygen atoms forming a binuclear unit with the

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Ni-Ni distances being 3.108(1) Å (Fig. 2). Furthermore, each unit is connected by

carboxylate bridging using syn-anti mode, resulting in a 2D layer with Ni---Ni

distance between the dimer units of 5.460(2) Å (Fig. S4). There are intramolecular

hydrogen bonding in the layers and no obvious π-π stacking interaction between

naphtholates.

Fig. 3

The temperature dependence of the χMT vs. T in a field of 1 kOe for 1 is shown in Fig.

3, where χM is the magnetic susceptibility per Co3 unit. The χMT value at 300 K is ca.

3.31 cm3

mol-1

K, which is greater than the spin-only value expected for a high-spin

CoII and corresponds to the presence of the Co

III(l.s., S = 0)–Co

II(h.s., S = 3/2)–Co

III(l.s., S = 0)

trinuclear systems. The decrease of the magnetic moment at low-temperature is most

likely due to zero-filed splitting of CoII. Therefore, in order to estimate the magnitude

of zero-filed splitting, the magnetic susceptibility data were fitted to Co(II) ions (S =

3/2) with the Hamiltonian in the form ZFSH S D S ,

taking into account the TIP of

octahedral Co(III) ions possessing a 1A1g ground state [22]. The best least squares

fitting was obtained with g = 2.43, D = -4.79 cm-1

and TIP = 0.00168 cm3 mol

-1 with R

= 7.7110-5

(R value is defined as 22])[(/)()( obsMcalcMobsM ).

Fig. 4

In the case of 2, the χMT value is 2.61 cm3

mol-1

K at room temperature, greater than

those expected for two spin only NiII with S = 1. Upon cooling, the χMT values

decrease more and more rapidly, indicating an antiferromagnetic behavior (Fig. 4).

The maxima of χM is observed at 20 K, suggesting antiferromagnetic ordering. The

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Neel temperature, TN, determined by the peaks of d(χMT)/dT, is 9.0 K. The

field-dependent magnetizations (insert Fig. 8), even at 1.8 K and 70 kOe, being 0.27

B, far from the saturated values, confirm the significant antiferromagnetic

interactions in material.

Regarding the structure feature, 2 consists of two types of bridges connecting the

Ni(II) sites. While layer consists of double symmetric 2 naphtholate-O bridges that

lead to the formation of the dimer locally. These dimers which are subsequently

interconnected through syn-anti carboxylate bridges give rise to the infinite 2D layer.

It should be noted that complex 2 exhibits four types of magnetic exchange

interactions between two Ni(II) ions: (1) a doubly naphtholate-bridged Ni(II) dimer,

(2) A carboxylate bridged Ni(II) dimer, (3) Ni(II) dimer intralayer, and (4) interlayer

(Fig. 7). Actually, because of the long distance of COO-, the overlap of magnetic

orbitals through the O atoms of COO- is weak. Hence, the double naphtholate-bridged

Ni(II) dimer cage plays an important role in the magnetic properties.

Therefore, the magnetic susceptibility data of 2 were fitted to the modified

Bleaney-Bowers equation for two interacting Ni(II) ions (S = 1) with the Hamiltonian

in the form 1 2H JS S taking into account the interaction between the dimers [23].

The susceptibility equation for such a dimeric system, with an interdimer parameter

zJ’, can be written as follows:

2 2' 2 exp( / ) 5exp(3 / )

1 3exp( / ) 5exp(3 / )M

N g J kT J kT

kT J kT J kT

'

2 21 (2 ' )

MM

MZJ Ng

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where N, g, and k parameters in the equation bear their usual meanings. The best

least squares fitting was obtained with g = 2.23, J = -8.12 cm-1

and J’ = 0.71 cm-1

with

R = 5.8710-6

(R value is defined as 22])[(/)()( obsMcalcMobsM ).

In summary, the tetradentate Schiff base ligand

2-(((2-hydroxynaphthalen-1-yl)methylene)amino)acetic acid produces two new

complexes, linear trinuclear mixed valence cobalt complex [CoL2]2[Co(CH3OH)4]

and 2D nickel complex [Ni2L2(CH3OH)2]n, respectively. Compound 1 shows a

mononuclear CoII whereas 2 exhibits an antiferromagnetism behavior. Magnetic

investigation reveals 2 naphtholate bridge transmitting antiferromagnetic interaction

and syn-anti carboxylate bridge transmitting ferromagnetic coupling in complex 2.

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Supplementary materials

Crystallographic data for the structural analysis have been deposited with the

Cambridge Crystallographic Data Center, CCDC 887618 & 887619, for complexes 1

& 2. These data can be obtained free of charge at

www.ccdc.cam.ac.uk/conts/retrieving.html.

Acknowledgement

We are very grateful to the Natural Science Foundation Council of China (NSFC)

(grant No. 21171021), Beijing National Laboratory for Molecular Sciences (BNLMS)

and Scientific Research Foundation for the Returned Overseas Chinese Scholars,

State Education Ministry for financial support.

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[19] Caution! Perchlorate compounds are potentially explosive, especially in the presence of organic

ligands. Only a small amount of these materials should be prepared and handled with

care.Preparation of complex (1): A solution of Co(ClO4)26H2O (365 mg, 1 mmol) was added to a

solution of 2-(((2-hydroxynaphthalen-1-yl)methylene)amino)acetic acid (229 mg, 1 mmol) and NaOH

(2 mmol) in MeOH (25 ml). The solution was stirred for 5 min and filtered, and the red-brown filtrate

left undisturbed to concentrate slowly by evaporation. Red-brown crystals appeared within a few days

in 40% yield. Elemental analysis for 1: Calculated (%) for C56H52Co3N4O16: C, 55.4; H, 4.3; N, 4.6; Found:

C, 55.3; H, 4.3; N, 4.5. Preparation of complex (2): Ni(ClO4)26H2O (364 mg, 1 mmol),

2-(((2-hydroxynaphthalen-1-yl)methylene)amino)acetic acid (229 mg, 1 mmol) and NaOH (2 mmol) in

MeOH (25 ml) were allowed to stir for 1 h at room temperature. The solution was left undisturbed to

slowly evaporate at room temperature. X-ray quality dark green crystals of 1 were obtained in 45%

yield. Elemental analysis for 2: Calculated (%) for C14H13NNiO4: C, 52.9; H, 4.1; N, 4.4; Found: C, 52.9; H,

4.3; N, 4.2.

[20] Crystal data: for 1, monoclinic system, space group P21/c, a= 15.2696(19), b= 15.327(2),

c=11.8496(15) Å, β= 111.176(2)°, V= 2585.9(6) Ǻ3, Z = 2, Dc =1.559 g/cm

3, μ = 1.029 mm

−1, F(000)

=1250, R1 = 0.0323 and wR =0.0965 for 15339 independent reflections (Rint =0.0288) and 5868

observed reflections (I > 2σ(I)); for 2, monoclinic system, space group P21/c, a= 13.0970(7), b=

7.0797(2), c=14.1771(5) Å, β= 101.260(4)°, V= 1289.24(9) Ǻ3, Z = 4, Dc =1.638 g/cm

3, μ = 1.517 mm

−1,

F(000) =656, R1 = 0.0390 and wR = 0.0835 for 4951 independent reflections (Rint =0.0546) and 2274

observed reflections (I > 2σ(I)).

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[21] N.E. Brese, M. Okeeffe, BOND-VALENCE PARAMETERS FOR SOLIDS, Acta Crystallogr. B, 47 (1991)

192-197.

[22] D. Reinen, M. Atanasov, The Influence of Jahn–Teller Coupling on the High-Spin/Low-Spin

Equilibria of Octahedral MIII

L6 polyhedra (MIII

: Mn−Cu), with NiF63-

as the Model Example, The

Jahn-Teller Effect, in: H. Köppel, D.R. Yarkony, H. Barentzen (Eds.), Springer Berlin Heidelberg, 2009, pp.

451-486.

[23] Y. Pang, D. Tian, X.-F. Zhu, Y.-H. Luo, X. Zheng, H. Zhang, Copper(II) and nickel(II) coordination

polymers assembled from 2,4-dibenzoylisophthalic acid and different N-donor co-ligands: syntheses,

crystal structures, and magnetic properties, CrystEngComm, 13 (2011) 5142-5151.

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Figure Captions

Scheme 1 The structures of H2L ligand (a) and coordination models (b).

Fig. 1 Perspective view of the trinuclear complex 1 (30% thermal probability

ellipsoids, for clarity hydrogen atoms are omitted).

Fig. 2 Partial view of the crystal structure of 2 displaying the bis(chelate)type bridging

ability of the L2-

ligand. (symmetry codes: A -x+1, -y+1, -z+1; B -x+1, y-1/2, -z+1/2;

C -x+1, y+1/2, -z+1/2)

Fig 3 Plot of χMT vs T for 1. The solid line represent the best fit of the experimental

data.

Fig 4 Plot of χMT vs T for 2. The solid line represent the best fit of the experimental

data. Inset: field-dependent magnetization of 2 at 1.8 K.

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(a) (b)

(E)-2-(((2-hydroxynaphthalen-1-yl)methylene)amino)acetic acid

Scheme 1

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Fig. 1

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Fig. 2

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0 50 100 150 200 250 300

1.5

2.0

2.5

3.0

3.5

M

T (

cm

3 K

mo

l-1

)

T (K)

Fig 3

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0 50 100 150 200 250 300

0.01

0.02

0.03

0.04

0.05

0.06

0 10 20 30 40 50 60 700.00

0.05

0.10

0.15

0.20

0.25

0.30

M (

N

H (KOe)

T (K)

M

(c

m3

mo

l-1

)

0.0

0.4

0.8

1.2

1.6

2.0

2.4 M

T (c

m3

K m

ol -1

)

Fig 4

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Graphical abstract

Two new complexes, [CoL2]2[Co(CH3OH)4] (1), and [Ni2L2(CH3OH)2]n (2) (H2L =

2-(((2-hydroxynaphthalen-1-yl)methylene)amino)acetic acid), were successfully

synthesized and magnetic properties studied.

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Highlights

► A linear trunuclear cobalt 1 and a 2D nickel complex 2 have been characterized.

► Magnetic measurements reveal 1 shows mononuclear CoII behavior whereas 2

exhibits an antiferromagnetism behavior.