Dalton Transactions View Article Online

Published on 06 June 2014. Downloaded by University of Chicago on 26/10/2014 04:34:10.

PAPER

Cite this: Dalton Trans., 2014, 43, 11819

View Journal | View Issue

Topological ferrimagnetic behaviours of coordination polymers containing manganese(II) chains with mixed azide and carboxylate bridges and alternating F/AF/AF’/AF’/AF interactions† Yan-Qin Wang,a Hou-Ting Liu,a Yan Qib and En-Qing Gao*b Two Mn(II) complexes with azide and a new zwitterionic tetracarboxylate ligand 1,2,4,5-tetrakis(4-carboxylatopyridinium-1-methylene)benzene (L1), {[Mn5(L1)2(N3)8(OH)2]·12H2O}n (1) and {[Mn5(L1)2(N3)8(H2O)2](ClO4)2·6H2O}n (2), have been synthesized and characterized crystallographically and magnetically. 1 and 2 contain similar alternating chains constructed by azide and carboxylate bridges. The independent sets of bridges alternate in an ABCCB sequence between adjacent Mn(II) ions: (EO-N3)2 double bridges (EO = end-on) (denoted as A), [(EO-N3)(OCO)2] triple bridges (denoted as B) and [(EO-N3)(OCO)] double bridges (denoted as C). The alternating chains are interlinked into 2D coordination networks by the tetrapyridinium spacers. Magnetic studies demonstrate that the magnetic coupling through the double EO azide

Received 19th April 2014, Accepted 3rd June 2014

bridges is ferromagnetic and that through mixed azide/carboxylate bridges is antiferromagnetic. The

DOI: 10.1039/c4dt01151a

unprecedented F/AF/AF’/AF’/AF coupling sequence along the chain dictates an uncompensated ground spin state (S = 5/2 per Mn5 unit) and leads to one-dimensional topological ferrimagnetism, which features

www.rsc.org/dalton

a minimum in the χT versus T plot.

1.

Introduction

Coordination polymers in which paramagnetic metal ions are bridged by short ligands have attracted great attention in recent years, not only aimed at understanding the fundamental relationship between structures and magnetic behaviours, but also for constructing new functional molecular magnetic materials with potential applications.1–7 In this context, the azide ion (N3−) has proved to be very versatile and diverse in both coordination chemistry and magnetism, and a great number of azide-bridged discrete polynuclear and infinite polymeric systems with different dimensionality and magnetic properties have been demonstrated,8–19 including some longrange ordered materials and a few single molecule/-chain magnets (SMMs and SCMs).8–11,16–24 A useful synthetic approach to obtaining new structures with interesting magnetic properties is to construct systems in which the paraa College of Chemistry and Chemical Engineering, Key Laboratory of Nanomagnetic and Functional Materials, Inner Mongolia University, Huhhot, 010021, China. E-mail: [email protected]; Fax: +86-471-4992147; Tel: +86-471-4995414 b Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry, East China Normal University, Shanghai 200062, P.R. China. E-mail: [email protected]; Fax: +86-21-62233404; Tel: +86-21-62233404 † Electronic supplementary information (ESI) available. CCDC 981762 (1) and 981763 (2). For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4dt01151a

This journal is © The Royal Society of Chemistry 2014

magnetic metal ions are bridged simultaneously by azide and carboxylate bridges.25–45 Recently, we demonstrated that the use of zwitterionic ligands as carboxylate sources is a good synthetic approach towards mixed azide- and carboxylate-bridged systems.37–47 Using this approach, different magnetic compounds based on mixed-bridge polynuclear clusters,37–39 infinite chains and layers,40,41 and even 3D frameworks have been obtained,42,43 exhibiting interesting magnetic properties, such as ferromagnetic (F) coupling,40–42 single-chain magnetism,41,46,47 solvent-modulated magnetism45,46 and mixedmetal single-chain magnetism.48,49 Ferrimagnetism is well known for 1D, 2D and 3D heterospin (usually heterometallic) systems in which antiferromagnetic (AF) coupling between spins of different magnitudes leads to uncompensated moment. Ferrimagnetic-like properties have also been identified in some homospin (usually homometallic) structures where the alternation of ferro- and AF coupling leads to some specific spin topology with uncompensated moment.50–57 The term “topological ferrimagnetism” has been coined for the latter case. However, the rational design of topological ferrimagnetic systems is still an intellectual challenge because it is difficult to achieve noncompensation of spin moments in homospin systems. To date the known examples are still rare and serendipitous. Some 1D spin coupling systems that have led to topological ferrimagnetism are given in Scheme 1. The most frequently used bridging

Dalton Trans., 2014, 43, 11819–11825 | 11819

View Article Online

Paper

Dalton Transactions

preparing 1,2,4,5-tetrakis(4-carboxylatopyridinium-1-methylene)benzene tetrahydrobromide ([H4L1]Br4) is similar to that for 1,4-bis(4-carboxylatepyridinium-1-methylene)benzene).58 CAUTION! Although not encountered in our experiments, azido compounds of metal ions are potentially explosive. Only a small amount of the materials should be prepared, and it should be handled with care.

Published on 06 June 2014. Downloaded by University of Chicago on 26/10/2014 04:34:10.

2.2.

Scheme 1

[H4L1]Br4 (0.062 g, 0.10 mmol) and sodium azide (0.13 g, 2.0 mmol) were dissolved in water (3 ml), and then the solution was added to an ethanol solution (1 ml) of Mn(OAc)2·4H2O (0.098 g, 0.40 mmol). The mixture was stirred for a few minutes and filtered. Slow evaporation of the filtrate at room temperature afforded red block crystals of 1 after one day. The crystals were collected by filtration, washed with water and ethanol, and dried in air. Yield: 55.2% based on L1. Excessive NaN3 has been used in the syntheses, which could act as a weak base to deprotonate [H4L1]Br4 besides serving as the ligand to bind metal ions. Elem anal. Calcd (%) for C68H78Mn5N32O30: C, 38.93; H, 3.75; N, 21.36%. Found: C, 38.58; H, 3.50; N, 21.19%. Main IR bands (KBr, cm−1): 2074s [ν(N3)], 2051 [ν(N3)], 1632s [νas(COO)], 1563m, 1456w, 1382s [νs(COO)], 1301w, 872w.

2.3. Scheme 2 1,2,4,5-Tetrakis(4-carboxylatopyridinium-1-methylene) benzene (L 1 ).

ligands to achieve these spin topologies have been carboxylates and especially azides, which can mediate AF or F interactions depending upon the bridging modes. As part of our systematic studies on mixed azide and carboxylate systems, here we report the synthesis, structure and magnetic properties of two coordination polymers with similar structure and magnetic properties obtained from manganese(II), azide and a new zwitterionic tetracarboxylate ligand, 1,2,4,5-tetrakis(4-carboxylatopyridinium-1-methylene)benzene (L1, Scheme 2). Compounds 1 and 2 contain 2D layers based on Mn(II) chains in which three different bridges, (EO-N3)2 (denoted as A), (EO-N3)(OCO)2 (denoted as B) and (EO-N3)(OCO) (denoted as C), alternate in the ABCCB sequence. Owing to the different nature of the magnetic coupling induced by the bridges (F for A, and AF for B and C), the bridging sequence dictates an unprecedented F/AF/AF′/AF′/AF coupling sequence, which leads to 1D topological ferrimagnetic behaviours.

2. Experimental section 2.1.

General procedure

The reagents were obtained from commercial sources and used without further purification. The method used for

11820 | Dalton Trans., 2014, 43, 11819–11825

Synthesis of {[Mn5(L1)2(N3)8(OH)2]·12H2O}n (1)

Synthesis of {[Mn5(L1)2(N3)8(H2O)2](ClO4)2·6H2O}n (2)

The compound was prepared as red block crystals by the procedure described above for 1 except that manganese acetate tetrahydrate was replaced by manganese perchlorate hexahydrate. Yield: 47.6% based on L1. Elem anal. Calcd (%) for C68H68Cl2Mn5N32O32: C, 37.28; H, 3.13; N, 20.46%. Found: C, 37.53; H, 2.98; N, 20.43%. Main IR bands (KBr, cm−1): 2076s [ν(N3)], 2047s [ν(N3)], 1630s [νas(COO)], 1564m, 1449w, 1380s [νs(COO)], 1334w, 1095s [ν(ClO4)], 781W. Note: the number of lattice water molecules in the above formula is calculated according to elemental analysis. The formula according to single-crystal X-ray crystallography is [Mn5(L1)2(N3)8(H2O)2](ClO4)2·9H2O (C68H74Mn5Cl2N32O35, see below). The difference suggests the loss of water in the sample for elemental analysis upon standing. PXRD measurements indicate that the overall structure remains unchanged (Fig. S1 and S2†).

2.4.

Physical measurements

Elemental analyses were determined on an Elementar Vario ELIII analyzer. The FT-IR spectra were recorded in the range 500–4000 cm−1 using KBr pellets on a Nicolet NEXUS 670 spectrophotometer. The phase purity of the bulk or polycrystalline samples was verified by powder X-ray diffraction (PXRD) measurements performed on a Bruker D8-Advance diffractometer equipped with Cu Kα at a scan speed of 1° min−1. Temperature dependent magnetic measurements were performed on a Quantum Design MPMS-XL5 SQUID magnetometer.

This journal is © The Royal Society of Chemistry 2014

View Article Online

Dalton Transactions

Published on 06 June 2014. Downloaded by University of Chicago on 26/10/2014 04:34:10.

Table 1

Paper

Crystal data and structure refinement for 1 and 2

Compound

1

2

Empirical formula Formula weight Crystal system Space group a (Å) b (Å) c (Å) α (°) β (°) γ (°) V (Å3) Z ρcalcd (g cm−3) µ (mm−1) Unique reflections Rint S on F2 R1, wR2 [I > 2σ(I)] R1, wR2 (all data)

C68H78Mn5N32O30 2098.32 Triclinic ˉ P1 11.5037(2) 12.4720(2) 16.3870(3) 77.007(5) 76.790(5) 81.216(5) 2217.5(6) 1 1.571 0.791 8642 0.0281 1.063 0.0480, 0.1466 0.0588, 0.1563

C68H74Mn5Cl2N32O35 2245.19 Triclinic ˉ P1 11.2421(3) 12.7398(4) 16.5024(5) 75.9880(10) 75.3790(10) 81.4150(10) 2209.12(11) 1 1.688 0.862 8590 0.0312 1.048 0.0563, 0.1600 0.0719, 0.1754

2.5.

X-ray crystallographic measurements

Diffraction intensity data were collected at 293 K on a Bruker APEX II diffractometer equipped with a CCD area detector and graphite-monochromated Mo Kα radiation (λ = 0.71073 Å). Empirical absorption corrections were applied using the SADABS program.59 The structures were solved by the direct methods and refined by the full-matrix least-squares method on F2, with all non-hydrogen atoms refined with anisotropic thermal parameters.60 All the hydrogen atoms attached to carbon atoms were placed in calculated positions and refined using the riding model. The hydrogens attached to coordinated hydroxo (1) and water (2) were located from the difference Fourier maps and refined isotropically with restrained O–H and H–O–H parameters. The hydrogens of the lattice water molecules were not located, and most of these waters are disordered and refined with fractional occupancies. Crystallographic data are summarized in Table 1.

Fig. 1 (a) Local coordination environment of the Mn center in compound 1 with the atom labeling scheme. The thermal ellipsoids were drawn at 30% probability. Symmetry codes: (A) −x, −y, 1 − z; (B) x − 1, y − 1, z; (C) −x, 1 − y, −z. (b) 1D alternate chain along the a direction in 1. (c) 2D network formed by the L1 ligands connecting the chains.

3. Results and discussion 3.1.

Crystal structure

Compounds 1 and 2. The structures of compounds 1 and 2 were determined by single crystal X-ray analyses. They are in ˉ space group and exhibit very similar 2D coordithe triclinic P1 nation networks based on the chain motifs with alternating bridges (Fig. 1 and 2). The selected bond distances and angles are listed in Table 2. The coordination environments of the metal ions are shown in Fig. 1a for 1 and Fig. 2a for 2. There are respectively three crystallographically independent Mn(II) ions in 1 and 2. Mn1 shows the [N4O2] coordination environment completed by four azide ions and two carboxylate groups, Mn2 shows the [N2O4] coordination environments completed by two azide ions and four carboxylate groups, while Mn3 shows the [N2O4] coordination environments completed by two azide ions, two carboxylate groups and two

This journal is © The Royal Society of Chemistry 2014

hydroxo (1) or water (2) ligands. For each manganese, the Mn–N distances [2.201(3)–2.297(3) Å] are generally longer than Mn–O [2.140(3)–2.198(3) Å]. While Mn1 and Mn2 are in general sites, Mn3 is located at inversion centers. The geometry around Mn1 is cis-octahedral with two oxygens at adjacent vertices, while that for Mn2 and Mn3 is trans-octahedral with two nitrogens defining a somewhat elongated axis. There are three kinds of bridging moieties between neighboring Mn(II) ions including the (EO-N3)2 double bridges (A) between Mn1A and Mn1, the (EO-N3)(OCO)2 triple bridges (B) between Mn1 and Mn2, and the (EO-N3)(OCO) double bridges (C) between Mn2 and Mn3. The metal ions are linked by the bridges alternating in an A–B–C–C–B sequence to give a 1D chain along the a direction (Fig. 1b and 2b).

Dalton Trans., 2014, 43, 11819–11825 | 11821

View Article Online

Paper

Dalton Transactions

Published on 06 June 2014. Downloaded by University of Chicago on 26/10/2014 04:34:10.

Table 2

Selected bonds [Å] and angles [°] for compounds 1 and 2

Compound 1 Mn1–N1 Mn1–N1–Mn1A Mn1–O1 Mn2–N7 Mn2–O6B Mn2–N10 Mn3–O4 Mn2–N10–Mn3

2.244(3) 100.00(1) 2.174(2) 2.237(3) 2.167(2) 2.217(3) 2.140(3) 119.85(1)

Mn1–N1A Mn1–N7 Mn1–O7B Mn2–O2 Mn1–N7–Mn2 Mn2–O3 Mn3–N10

2.293(3) 2.218(3) 2.174(2) 2.183(2) 115.29(1) 2.165(2) 2.236(3)

Compound 2 Mn1–N1 Mn1–N1–Mn1A Mn1–O1 Mn2–N7 Mn2–O6B Mn2–N10 Mn3–O4 Mn2–N10–Mn3

2.249(3) 100.25(1) 2.180(3) 2.234(3) 2.144(3) 2.201(3) 2.160(3) 121.2(2)

Mn1–N1A Mn1–N7 Mn1–O7B Mn2–O2 Mn1–N7–Mn2 Mn2–O3 Mn3–N10

2.297(3) 2.228(3) 2.169(3) 2.198(3) 115.2(2) 2.165(3) 2.212(3)

Symmetry codes: for 1: (A) −x, −y, −z + 1; (B) x − 1, y − 1, z; for 2, (A) −x + 2, −y + 2, −z + 1; (B) x + 1, y + 1, z.

only coordinated hydroxyl, water, azide and carboxylate groups, but also uncoordinated water molecules and perchlorate ions. 3.2.

Magnetic properties

Fig. 2 (a) Local coordination environment of the Mn center in compound 2 with the atom labeling scheme. The thermal ellipsoids were drawn at 30% probability. Symmetry codes: (A) −x, −y, 1 − z; (B) x − 1, y − 1, z; (C) −x, 1 − y, −z. (b) 1D alternate chain along the a direction in 2. (c) 2D network formed by the L1 ligands connecting the chains with the perchlorate anions enclosed.

Magnetic measurements were carried out on polycrystalline samples of 1 and 2 under 1000 Oe in the range of 2–300 K, and the χT versus T and χ versus 1/T plots are given in Fig. 3 and 4 respectively. The two compounds show similar temperature-dependent behaviours. The χT values per manganese at 300 K are both about 4.02 emu K mol−1 for 1 and 2, lower than the spin-only value (4.38 emu K mol−1) expected for a magnetically isolated high-spin Mn(II) ion. As the sample is cooled from room temperature, the χT values first decrease to a minimum at 10 K for 1 and 9 K for 2 and then show rapid monotonic increases. The data above 35 K for 1 and 50 K for 2 follow the Curie–Weiss law with C = 4.45 emu K mol−1 and θ = −31.1 K for 1, and C = 4.44 emu K mol−1 and

The L1 ligand in the structure is noncentrosymmetric and the four pyridinium rings are nearly perpendicular to the benzene ring, the dihedral angles being 81.6°–99.4° for 1 and 81.6°–101.2° for 2. Each ligand L1 serves as a μ5 bridge between two different chains, with three carboxylate groups in the bidentate bridging mode and the fourth one in the monodentate mode. Thus, a 2D layer is formed extending along the (002) plane (Fig. 1c and 2c). The nearest interchain Mn⋯Mn distances within the layer are 17.05(2) Å for 1 and 17.35(1) Å for 2. With an M2+ : N3− : OH− ratio of 5 : 8 : 2, the 2D network of 1 is neutral. With water in place of OH− in 1, the 2D network of 2 is positively charged. The positive network charge is compensated by perchlorate anions, which are enclosed within the layers. Some lattice water molecules are present in both 1 and 2. There are lots of hydrogen bonds involving not

Fig. 3 Thermal variation of χT and χ−1 of 1. The solid lines represent the best fit to the equation in the text.

11822 | Dalton Trans., 2014, 43, 11819–11825

This journal is © The Royal Society of Chemistry 2014

View Article Online

Dalton Transactions

Paper

χT¼

Ng 2 β2 SðS þ 1Þ D 15k ð1  u1 u2 2 u3 2 Þ

ð2Þ

where ui ¼ coth½ J i SðS þ 1Þ=kT  kT=½ J i SðS þ 1Þ

ð3Þ

D ¼ 5 þ 2u1 þ 4u2 þ 4u3 þ 4u1 u2 þ 4u2 u3 þ 2u3 2 þ 2u1 u2 2 þ 4u2 u3 2 þ 4u1 u2 u3 þ 4u1 u2 u3 2 þ 4u1 u2 2 u3 þ 2u2 2 u3 2 Published on 06 June 2014. Downloaded by University of Chicago on 26/10/2014 04:34:10.

þ 5u1 u2 2 u3 2

Fig. 4 Thermal variation of χT and χ−1 of 2. The solid lines represent the best fit to the equation in the text.

θ = −29.4 K for 2. The high-temperature behaviours suggest that overall AF interactions are operative in 1 and 2. The presence of low-temperature minima in the χT versus T plots is typical of a ferrimagnetic system. Considering the homospin character of the compounds, the ferromagnetism should be of topological origin. Neglecting the interchain magnetic interactions through the bulky organic pathways, 1 and 2 could be magnetically treated as isolated chains of S = 5/2 classical spins with alternating J1–J2–J3–J3–J2 interactions (Scheme 3), where J1, J2 and J3 refer to the interactions transmitted by (EO-N3)2, (EO-N3)(OCO)2 and (EO-N3)(OCO) bridges, respectively. Such a complex alternating coupling topology is very rare, and a known example is the Mn(II)–azide chain in which (EO-N3)2 alternates with two independent (EE-N3)2 (EE = end-to-end) bridging moieties. 1 and 2 are the first examples with mixed azide and carboxylate bridges. On the basis of the spin Hamiltonian given in eqn (1), the expression of magnetic susceptibility per spin site for such systems has been deduced by Cano et al.61 as eqn (2): H¼

 1  X J 1 S5iþ1  S5iþ2 þ J 2 S5iþ2  S5iþ3 þ J 2 S5iþ3  S5iþ4 i¼0

þ J 3 S5iþ4  S5iþ5 þ J 3 S5iþ5  S5iþ6

Scheme 3

This journal is © The Royal Society of Chemistry 2014

ð1Þ

ð4Þ

The least-squares fit of the experimental data in the whole temperature range led to J1 = 0.40 cm−1, J2 = −2.89 cm−1, J3 = −5.38 cm−1, g = 2.01 for 1 and J1 = 0.33 cm−1, J2 = −3.12 cm−1, J3 = −4.84 cm−1, g = 2.01 for 2. The experimental χT versus T behaviours including the low-temperature minimum were well reproduced by these parameters. The results confirm F–AF– AF′–AF′–AF interactions through the (EO-N3)2, (EO-N3)(OCO)2 and (EO-N3)(OCO) bridges along the chain. The F coupling J1 through the (EO-N3)2 double bridges is very common in metal azide compounds and the double (EO-N3)2 usually have Mn– N–Mn = 99–105° and induce F coupling, as demonstrated in compounds 1, 2 and a number of previous compounds.62–67 The (EO-N3)(OCO) double and (EO-N3)(OCO)2 triple bridges have been found in a few Mn(II) compounds reported elsewhere by some of us and others.28,38,42,44,47 We note that all the Mn(II) compounds with simultaneous azide and carboxylate bridges exhibit AF interactions, whether the bridges are double or triple [(EO-N3)(OCO), (EO-N3)(OCO)2 and (EO-N3)2(OCO)].38–42,44,49 The values of J2 and J3 are in the usual range of 1–10 cm−1 for Mn(II) species with simultaneous azide and carboxylate bridges.28,38–42,44,68 With the alternating F–AF–AF′–AF′–AF interactions, the spin coupling topology along the chain in 1 and 2 can be illustrated in Scheme 3a. Consistent with the χT versus T behaviours, the chain can be taken as a ferrimagnetic chain in which effective spins with Seff = 5 (for the ferromagnetic Mn2(EO-N3)2 unit) and Seff = 5/2 (for the Mn(EO-N3)(OCO)2Mn(EO-N3)(OCO)Mn unit with AF interactions) are alternately aligned and antiferromagnetically coupled. Alternatively, it can be taken as a ferromagnetic chain in which effective spins with Seff = 5/2 (for each Mn5 repeating unit) are parallelly aligned in the ground state. The spin topology is consistent with the isothermal magnetization behaviours of 1 and 2 at 2.0 K (Fig. 5). The molar magnetization increases monotonously with increased field, and the values per Mn5 unit are 4.94Nβ for 1 and 5.02Nβ for 2 at 50 kOe, close to the saturation value of 5Nβ for S = 5/2 with g = 2, supporting the ferrimagnetic ground state associated with the F–AF–AF′–AF′–AF interactions. As is mentioned, azide and carboxylate have generated some topological ferrimagnetic systems, benefiting from the versatilities of the ligands in bridging metal ions and mediating magnetic coupling. The bridges usually mediate AF coupling in the μ-1,3 bridging mode while the μ-1,1 bridging mode (μ2-N or μ2-O) can induce F coupling. The most frequently observed 1D ferrimagnetic topology is the F–AF–AF alternating chains (Scheme 1a), as exemplified by a few compounds with

Dalton Trans., 2014, 43, 11819–11825 | 11823

View Article Online

Paper

Dalton Transactions

work demonstrates the potential of using zwitterionic carboxylate ligands to construct novel magnetic systems with mixed carboxylate and azide bridges.

Published on 06 June 2014. Downloaded by University of Chicago on 26/10/2014 04:34:10.

Acknowledgements We are thankful for the financial support from NSFC (21173083 and 21301087), the Inner Mongolia Autonomous Region Natural Science fund project (2013MS0206), and Programs of Higher-level Talents of Inner Mongolia University (SPH-IMU-30105-125135).

Fig. 5 Field-dependent isothermal magnetization curves for compounds 1 and 2 at 2 K (the solid lines are only a guide for the eye).

azide or carboxylate bridges.50,53–56 The F–F–AF–AF topology has been observed in a Cu(II)–azide chain.52 The nonlinear topology shown in Scheme 1c has been found in a Mn(II) species with azide/diazine bridges51 and a Ni(II) compound with carboxylate/hydroxo bridges.57 The coupling topology in 1 and 2 is different, with the more complex sequence F–AF–AF′–AF′–AF and with mixed azide and carboxylate bridges. The F pathway is provided by double EO-azide bridges, while the AF pathways are mixed azide and carboxylate bridges ((EO-N3)(OCO) or (EO-N3)(OCO)2). Evidently, the occurrence of topological ferrimagnetism in a linear chain necessitates an alternating sequence in which a number (n ≥ 1) of F interactions followed by an even number (2m) of AF interactions. Such a system can be taken as a chain with alternate and AF coupled (n + 1)S and S spins, and thus the chain has a ferrimagnetic ground state, ST = nS for each repeating units containing (n + 2m) spin carriers (for 1 and 2, n = 1, 2m = 4, S = 5/2). If the number of AF interactions is odd (2m + 1), the spin moments are completely compensated and the chain has a nonmagnetic ground state (ST = 0). The simplest example is the well-studied alternating chain with F–AF interactions (n = 1, 2m + 1 = 1). A more complex example is a Mn(II) compound with alternating EE– EO–EO′–EO′–EO azide bridges. The resulting AF–F–F′–F′–F interactions (n = 4, 2m + 1 = 1, Scheme 3b) are opposite to F–AF–AF′–AF′–AF in 1 and 2. Obviously, the AF–F–F′–F′–F chain is not ferrimagnetic because of the S = 0 ground state.

4.

Conclusion

With a zwitterionic tetracarboxylate ligand and azide ions, we have successfully synthesized two 2D novel coordination polymers based on Mn(II) chains with the (EO-N3)2 (A), (EO-N3)(OCO)2 (B) and (EO-N3)(OCO) (C) bridges alternating in the ABCCB sequence. Magnetic studies suggest that the (EO-N3)2 double bridges transmit F interactions, while the (EO-N3)(OCO)2 and (EO-N3)(OCO) bridges induce AF interactions between Mn(II) ions. The alternating F–AF–AF′–AF′–AF coupling along the chain leads to topological ferrimagnetism. This

11824 | Dalton Trans., 2014, 43, 11819–11825

Notes and references 1 J. S. Miller, Adv. Mater., 2002, 14, 1105; Magnetism: Molecules to Materials, ed. J. S. Miller and M. Drillon, Willey-VCH, Weinheim, 2002–2005, vol. I–V. 2 O. Kahn, Molecular Magnetism, Wiley-VCH, Weinheim, 1993. 3 E. Coronado, P. Delhaes, D. Gatteschi and J.-S. Miller, Molecular Magnetism: from Molecular Assemblies to Devices, NATO ASI Series 15, Kluwer, Dordrecht, The Netherlands, 1995, vol. 321. 4 D. Gatteschi, O. Kahn, J.-S. Miller and F. Palacio, Magnetic Molecular Materials, Kluwer Academic, Dordrecht, The Netherlands, 1991. 5 J. S. Miller, Adv. Mater., 2002, 14, 1105–1110. 6 D. Gatteschi and R. Sessoli, Angew. Chem., Int. Ed., 2003, 42, 268–297. 7 J.-S. Miller and A.-J. Epstein, Angew. Chem., Int. Ed. Engl., 1994, 33, 385–415. 8 J. Ribas, A. Escuer, M. Monfort, R. Vicente, R. Cortés, L. Lezama and T. Rojo, Coord. Chem. Rev., 1999, 193, 1027–1068. 9 A. Escuer and G. Aromí, Eur. J. Inorg. Chem., 2006, 4721–4736. 10 X.-Y. Wang, Z.-M. Wang and S. Gao, Chem. Commun., 2008, 281–294. 11 Y.-F. Zeng, X. Hu, F.-C. Liu and X.-H. Bu, Chem. Soc. Rev., 2009, 38, 469–480. 12 K. S. Lim, D. W. Ryu, W. R. Lee, E. K. Koh, H. C. Kim and C. S. Hong, Chem. – Eur. J., 2012, 18, 11541–11544. 13 S. Mukherjee and P. S. Mukherhee, Acc. Chem. Res., 2013, 46, 2556–2566. 14 M.-M. Yu, Z.-H. Ni, C.-C. Zhao, A.-L. Cui and H.-Z. Kou, Eur. J. Inorg. Chem., 2007, 5670–5676. 15 E.-Q. Gao, P.-P. Liu, Y.-Q. Wang, Q. Yue and Q.-L. Wang, Chem. – Eur. J., 2009, 15, 1217. 16 Y.-Z. Zhang, W. Wernsdorfer, F. Pan, Z.-M. Wang and S. Gao, Chem. Commun., 2006, 3302–3304. 17 T. C. Stamatatos, K. A. Abboud, W. Wernsdorfer and G. Christou, Angew. Chem., Int. Ed., 2007, 46, 884–888. 18 C. I. Yang, W. Wernsdorfer, G. H. Lee and H. L. Tsai, J. Am. Chem. Soc., 2007, 129, 456–457.

This journal is © The Royal Society of Chemistry 2014

View Article Online

Published on 06 June 2014. Downloaded by University of Chicago on 26/10/2014 04:34:10.

Dalton Transactions

19 T. C. Stamatatos, K. A. Abboud, W. Wernsdorfer and G. Christou, Angew. Chem., Int. Ed., 2008, 47, 6694–6698. 20 H. B. Xu, B. W. Wang, F. Pan, Z. M. Wang and S. Gao, Angew. Chem., Int. Ed., 2007, 46, 788–7392. 21 D.-F. Weng, Z.-M. Wang and S. Gao, Chem. Soc. Rev., 2011, 40, 3157–3181. 22 Z.-X. Li, Y.-F. Zeng, H. Ma and X.-H. Bu, Chem. Commun., 2010, 46, 8540–8542. 23 T.-F. Liu, D. Fu, S. Gao, Y.-Z. Zhang, H.-L. Sun, G. Su and Y.-J. Liu, J. Am. Chem. Soc., 2003, 125, 13976–13977. 24 D. Visinescu, A. M. Madalan, M. Andruh, C. Duhayon, J. P. Sutter, L. Ungur, W. V. Heuvel and L. F. Chibotaru, Chem. – Eur. J., 2009, 15, 11808. 25 L. K. Thompson, S. S. Tandon, F. Lloret, J. Cano and M. Julve, Inorg. Chem., 1997, 36, 3301–3306. 26 X.-T. Wang, X.-H. Wang, Z.-M. Wang and S. Gao, Inorg. Chem., 2009, 48, 1301–1308. 27 T. Liu, Y.-J. Zhang, Z.-M. Wang and S. Gao, Inorg. Chem., 2006, 45, 2782–2784. 28 Z. He, Z.-M. Wang, S. Gao and C.-H. Yan, Inorg. Chem., 2006, 45, 6694–6705. 29 Y. F. Zeng, F. C. Liu, J. P. Zhao, S. Cai, X. H. Bu and J. Ribas, Chem. Commun., 2006, 2227–2229. 30 J. P. Zhao, B. W. Hu, X. F. Zhang, Q. Yang, M. S. E. Fallah, J. Ribas and X. H. Bu, Inorg. Chem., 2010, 49, 11325–11332. 31 C. J. Milios, A. Prescimone, J. Sanchez-Benitez, S. Parsons, M. Murrie and E. K. Brechin, Inorg. Chem., 2006, 45, 7053–7055. 32 K. C. Mondal, O. Sengupta, M. Nethaji and P. S. Mukherjee, Dalton Trans., 2008, 767–775. 33 J. P. Zhao, B. W. Hu, E. C. Sañudo, Q. Yang, Y. F. Zeng and X. H. Bu, Inorg. Chem., 2009, 48, 2482–2489. 34 F.-C. Liu, Y.-F. Zeng, J. Jiao, X.-H. Bu, J. Ribas and S. R. Batten, Inorg. Chem., 2006, 45, 2776–2778. 35 Y.-F. Zeng, J.-P. Zhao, B.-W. Hu, X. Hu, F.-C. Liu, J. Ribas, J. R. Arino and X.-H. Bu, Chem. – Eur. J., 2007, 13, 9924–9930. 36 Q. Yang, J.-P. Zhao, B.-W. Hu, X.-F. Zhang and X.-H. Bu, Inorg. Chem., 2010, 49, 3746–3751. 37 Y. Ma, K. Wang, E.-Q. Gao and Y. Song, Dalton Trans., 2010, 39, 7714–7772. 38 Y.-Q. Wang, Q. Sun, Q. Yue, A.-L. Cheng, Y. Song and E.-Q. Gao, Dalton Trans., 2011, 40, 10966–10974. 39 Y. Q. Wang, A. L. Cheng, X. Wang and E. Q. Gao, RSC Adv., 2012, 2, 10352–10358. 40 Y. Ma, J.-Y. Zhang, A.-L. Cheng, Q. Sun, E.-Q. Gao and C.-M. Liu, Inorg. Chem., 2009, 48, 6142–6151. 41 Q.-X. Jia, H. Tian, J.-Y. Zhang and E.-Q. Gao, Chem. – Eur. J., 2011, 17, 1040–1051. 42 Y.-Q. Wang, X.-M. Zhang, X.-B. Li, B.-W. Wang and E.-Q. Gao, Inorg. Chem., 2011, 50, 6314–6322. 43 Y. Ma, X. B. Li, X. C. Yi, Q. X. Jia, E. Q. Gao and C. M. Liu, Inorg. Chem., 2010, 49, 8092–8097. 44 Y.-Q. Wang, Q.-X. Jia, K. Wang, A.-L. Cheng and E.-Q. Gao, Inorg. Chem., 2010, 49, 1551–1560.

This journal is © The Royal Society of Chemistry 2014

Paper

45 W.-W. Sun, C.-Y. Tian, X.-H. Jing, Y.-Q. Wang and E.-Q. Gao, Chem. Commun., 2009, 4741–4743. 46 Y.-Q. Wang, W.-W. Sun, Z.-D. Wang, Q.-X. Jia, E.-Q. Gao and Y. Song, Chem. Commun., 2011, 6386–6388. 47 X.-M. Zhang, Y.-Q. Wang, K. Wang, E.-Q. Gao and C.-M. Liu, Chem. Commun., 2011, 1815–1817. 48 Y.-Q. Wang, A.-L. Cheng, P.-P. Liu and E.-Q. Gao, Chem. Commun., 2013, 49, 6995–6997. 49 Y.-Q. Wang, Q. Yue, K. Wang, Q. Sun and E.-Q. Gao, Inorg. Chem., 2013, 52, 4259–4268. 50 M. A. M. Abu-Youssef, M. Drillon, A. Escuer, M. A. S. Goher, F. A. Mautner and R. Vicente, Inorg. Chem., 2000, 39, 5022–5027. 51 E. Q. Gao, Y. F. Yue, S. Q. Bai, Z. He and C. H. Yan, J. Am. Chem. Soc., 2004, 126, 1419–1429. 52 A. Escuer, R. Vicente, M. S. EI. Fallah, M. A. S. Goher and F. A. Mautner, Inorg. Chem., 1998, 37, 4466–4469. 53 A. Escuer, F. A. Mautner, B. Sodin, M. A. S. Goher and R. Vicente, Dalton Trans., 2010, 39, 4482–4484. 54 R. H. Wang, E. Q. Gao, M. C. Hong, S. Gao, J. H. Luo, Z. Z. Lin, L. Han and R. Cao, Inorg. Chem., 2003, 42, 5486–5488. 55 A. Escuer, F. A. Mautner, M. A. S. Goher, M. A. M. AbuYoussef and R. Vicente, Chem. Commun., 2005, 605–607. 56 S. Konar, P. S. Mukherjee, E. Zangrando, F. Lloret and N. R. Chaudhuri, Angew. Chem., Int. Ed., 2002, 41, 1561– 1563. 57 N. Guillou, S. Pastre, C. Livage and G. Fèrey, Chem. Commun., 2002, 2358–2359. 58 F.-K. Zheng, A.-Q. Wu, Y. Li, G.-C. Guo and J.-S. Huang, Chin. J. Struct. Chem., 2005, 24, 940–944. 59 G. M. Sheldrick, Program for Empirical Absorption Correction of Area Detector Data, University of Göttingen, Germany, 1996. 60 G. M. Sheldrick, SHELXTL Version 5.1, Bruker Analytical X-ray Instruments Inc., Madison, Wisconsin, USA, 1998. 61 J. Cano, Y. Journaux, M. A. S. Goher, M. A. M. Abu-Youssef, F. A. Mautner, G. J. Reiß, A. Escuer and R. Vicente, New J. Chem., 2005, 29, 306–314. 62 E.-Q. Gao, A.-L. Cheng, Y.-X. Xu, M.-Y. He and C.-H. Yan, Inorg. Chem., 2005, 44, 8822. 63 M.-M. Yu, Z.-H. Ni, C.-C. Zhao, A.-L. Cui and H.-Z. Kou, Eur. J. Inorg. Chem., 2007 (36), 5670. 64 L. K. Thompson, S. S. Tandon, F. Lloret, J. Cano and M. Julve, Inorg. Chem., 1997, 36, 3301. 65 Z.-H. Ni, H.-Z. Kou, L. Zheng, Y.-H. Zhao, L.-F. Zhang, R.-J. Wang, A.-L. Cui and O. Sato, Inorg. Chem., 2005, 44, 4728. 66 S.-Q. Bai, E.-Q. Gao, Z. He, C.-J. Fang, Y.-F. Yue and C.-H. Yan, Eur. J. Inorg. Chem., 2006, 2, 407–415. 67 T. K. Karmakar, B. K. Ghosh, A. Usman, H.-K. Fun, E. Rivière, T. Mallah, G. Aromí and S. K. Chandra, Inorg. Chem., 2005, 44, 2391–2399. 68 C.-Y. Tian, W.-W. Sun, Q.-X. Jia, H. Tian and E.-Q. Gao, Dalton Trans., 2009, 6109.

Dalton Trans., 2014, 43, 11819–11825 | 11825

AF interactions.

Two Mn(ii) complexes with azide and a new zwitterionic tetracarboxylate ligand 1,2,4,5-tetrakis(4-carboxylatopyridinium-1-methylene)benzene (L(1)), {[...
2MB Sizes 1 Downloads 4 Views