English

• 1. INTRODUCTION

  The design and synthesis of metal directed supramolecular frameworks have received much attention in coordination chemistry because of their interesting molecular topologies and tremendous potential applications in host-guest chemistry, catalysis, molecular selection, nonlinear optics, ion exchange and microelectronics^[1]. Manganese plays an important role in the enzymatic catalysis of biochemistry, and the study of manganese complexes has aroused great interest. In addition, in order to synthesize molecular magnets, multi-nuclear magnetic exchange between manganese has also attracted people's attention^[2]. Aromatic carboxylic acid complexes exhibit rich topology structure and high stability, which have captured the extensive interest of researchers due to their potential applications in many fields such as magnetism, catalyst and biology^[3]. 2-Benzoylbenzoic acid is an important benzoic acid, which acts as a crucial role in medicine and dyestuff^[4]. For instance, it is an major principal material of the anthraquinone dyestuff intermediate, which can be used to produce anthraquinone benzanthrone amino anthraquinone, etc^[5]. As a rigid aromatic carboxylic acid ligand, 2-benzoylbenzoic acid can also be used in the design and construction of coordination compounds. However, it is rarely reported^[6]. A new manganese(II) complex [Mn(C₁₄H₉O₃)₂(C₁₂H₈N₂)₂]·4H₂O with o-benzoylbenzoic acid and 1, 10-phenanthroline (phen) as a ligand has been synthesized, and its structure was characterized by X-dif- fractometer. We also investigated its luminescent, magnetic and thermal stability properties. The result shows that 1 has one fluorescent emission band at around 424 nm. In addition, the magnetic behaviors of 1 are antiferromagnetism and it is stable under 383 K.

  2. EXPERIMENTAL

  2.1 Reagents and instruments

  All reagents from commercial sources were of analytical grade and used without further purification. Crystal structure was determined on a Bruker SMART CCD 6000 single-crys- tal diffractometer. IR spectra were recorded on a Bruker Vector22 FT-IR spectrophotometer using KBr discs. Thermogravimetric analyses were performed on a simul- taneous SPRT-2 pyris1 thermal analyzer at a heating rate of 10 K/min. Magnetic measurements in the range of 300~2 K were performed on a MPMS-SQUID magnetometer at a field of 2 kOe on a crystalline sample in the temperature settle mode. The fluorescence for the powdered samples was measured on an RF-5301PC spectrofluorometer with a xenon arc lamp as the light source.

  2.2 Synthesis of the complex

  2 mmol of manganese sulfate (about 0.302 g), 3 mmol of o-benzoylbenzoic acid (about 0.720 g) and 3 mmol of phen (about 0.595 g) were added to 30 mL of acetonitrile-water solvent mixture (volume ratio: 5:3) by stirring at 343~353 K for about 4.0~5.0 h, and then mixed with pH being adjusted to 6.5~7.0 with dilute potassium hydroxide solution under stirring for about 23 h at 353 K. Afterwards, the resultant solution was filtrated, and the filtrate was kept untouched and evaporated slowly at room temperature. Yellow block-shaped single crystals suitable for X-ray diffraction analysis were obtained after one month in 46.5% yield based on phen. m.p.: 609~610 K. Anal. Calcd. (%) for C₅₂H₄₂MnN₄O₁₀: C, 66.60; H, 4.51; N, 5.97. Found (%): C, 66.40; H, 4.53; N, 5.60. Main IR (KBr, cm^–1): IR (v/cm^-1): 3410(w), 3055(w), 1662(vs), 1584(vs), 1560(vs), 1427(vs), 1381(vs), 1313(m), 1273(m), 1146(m), 1101(m), 95(vs), 851(vs), 767(m), 731(vs), 700(m), 671(w), 451(w).

  2.3 Structure determination

  A single crystal with dimensions of 0.24mm × 0.20mm × 0.18mm was put on a Bruker SMART APEX CCD diffractometer equipped with a graphite-monochromatic MoKa radiation (λ = 0.71073 Å) by using a φ-w scan mode at 100.03(18) K. A total of 23959 reflections were collected in the range of 1.5≤θ≤25.01°, of which 7763 were independent (R_int = 0.0433, R_sigma = 0.0436) and 6348 were observed (I > 2σ(I)). All data were corrected by Lp factors and empirical absorption. The structure was solved by direct methods and refined on F² by full-matrix least-squares methods using the SHELX-2014 program package^[7]. The final refinement including hydrogen atoms converged to R = 0.0404 and wR = 0.0956 (w = 1/[σ²(F_o²) + (0.0397P)² + 2.1088P], where P = (F_o² + 2F_c²)/3), (∆/σ)_max = 0.000, S = 1.049, (∆ρ)_max = 0.279 and (∆ρ)_min = –0.364 e·Å^–3.

  3. RESULTS AND DISCUSSION

  3.1 Crystal structure of the complex

  The crystal structure of the title complex is revealed in Fig. 1. Hydrogen bonding between adjacent molecules of the title complex is given in Fig. 2. Selected bond lengths and bond angles are shown in Table 1, and the hydrogen bond lengths and bond angles in Table 2.

  Figure 1

  

  Figure 1.  Molecular structure of the title complex

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  Figure 2

  

  Figure 2.  Hydrogen bonding between adjacent molecules of the title complex

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  Table 1

  

  Table 1.  Selected Bond Lengths (Å) and Bond Angles (°)

  DownLoad: CSV

  Bond	Dist.		Bond	Dist.		Bond	Dist.
  Mn(1)–O(1)	2.143(1)		Mn(1)–O(5)	2.143(1)		Mn(1)–N(1)	2.239(2)
  Mn(1)–N(2)	2.361(2)		Mn(1)–N(3)	2.344(2)		Mn(1)–N(4)	2.244(2)
  O(1)–C(25)	1.270(2)		O(2)–C(25)	1.243(2)		O(4)–C(39)	1.245(2)
  O(5)–C(39)	1.264(2)
  Angle	(°)		Angle	(°)		Angle	(°)
  O(1)–Mn(1)–N(1)	97.07(6)		O(1)–Mn(1)–N(2)	82.18(6)		O(1)–Mn(1)–N(3)	160.81(6)
  O(1)–Mn(1)–N(4)	93.48(6)		O(5)–Mn(1)–O(1)	114.66(6)		O(5)–Mn(1)–N(1)	91.54(6)
  O(5)–Mn(1)–N(2)	158.35(6)		O(5)–Mn(1)–N(3)	81.59(6)		O(5)–Mn(1)–N(4)	102.08(5)
  N(1)–Mn(1)–N(2)	72.14(6)		N(1)–Mn(1)–N(3)	92.38(6)		N(1)–Mn(1)–N(4)	157.45(7)
  N(2)–Mn(1)–(3)	84.91(6)		N(2)–Mn(1)–N(4)	89.73(6)		N(3)–Mn(1)–N(4)	72.27(6)

  Table 2

  

  Table 2.  Hydrogen Bond Lengths (Å) and Bond Angles (°)

  DownLoad: CSV

  D–H⋅⋅⋅A	d(D–H)	d(H⋅⋅⋅A)	d(D⋅⋅⋅A)	∠DHA
  O(8)–(8B)⋅⋅⋅O(2)	0.81	2.07	2.841(2)	159
  O(9)–H(9A)⋅⋅⋅O(3)a	0.85	2.17	3.004(2)	165
  O(7)–H(7A)⋅⋅⋅O(9)	0.85	2.09	2.893(2)	158
  O(7)–H(7B)⋅⋅⋅O(4)	0.85	1.97	2.760(2)	155
  O(10)–H(10A)⋅⋅⋅O(2)	0.73	2.07	2.798(2)	177
  O(10)–H(10B)⋅⋅⋅O(7)b	0.85	2.06	2.892(3)	165
  Symmetry codes: (a): 3/2–x, –1/2+y, 1/2–z; (b): –1/2+x, 1/2–y, –1/2+z

  As shown in Fig. 1, the whole unit consists of one manganese ion, two o-benzoyl-benzoic acids, two phen molecules and four free water molecules. The central manganese ion is coordinated with two oxygen atoms from two o-benzoylbenzoic acid molecules and four nitrogen atoms from two phen molecules, giving an octahedral coordination geometry. In the MnN₄O₂ octahedron, the total bond angles of N(2)–Mn(1)–N(3), N(3)–Mn(1)–O(5), O(5)–Mn(1)–O(1) and O(1)–Mn(1)–N(2) are 84.91(6), 81.59(6), 114.66(6) and 82.18(6)º, respectively, with the total to be 363.34º which is close to 360.0º, indicating that N(2), N(3), O(5), O(1) and Mn(II) are almost coplanar, while N(1) and N(4) occupy the axial positions. The Mn–N bond lengths range from 2.239 to 2.344 Å, averaged by 2.322 Å and close to the similar coordination of Mn(phen)₂(H₂O)[C₈H₁₁O₂(COO)]}·(ClO₄)·H₂O (Mn–N = 2.375 Å), Mn₂(phen)₂(p-CBA)₄(H₂O) (Mn–N = 2.276 Å) and Mn₂(phen)₂·(o-ABA)₂·(H₂O)₂ (Mn–N = 2.261 Å)^[8], which suggests that the complex is stably coordinated with the phen. The Mn–O bond lengths are 2.143 Å. In carboxyl group participating in coordination, the O(1)–C(25) bond in 1.270(2) Å is different from O(2)–C(25) being 1.243(5) Å (Δ = 0.027 Å, smaller than 0.03 Å), but the Mn–O(2) = 3.007 and Mn–O(4) = 2.999 Å are significantly greater than the mean value of 2.55 Å for Mn–O bond^[9], indicating a monodentate coordination mode of o-benzoyl- benzoic acid after dissociating hydroxyl hydrogen atom. Another noticeable characteristic of the title complex lies in a large number of hydrogen bonding interactions, which exist between oxygen atoms in water connected with o-benzoyl- benzoic acid via their coordinated oxygen atoms: O(8)–(8B)⋅⋅⋅O(2) (2.841(2) Å, 159º), O(9)–H(9A)⋅⋅⋅O(3)^a (3.004(2) Å, 165º) (symmetry codes: (a): 3/2–x, –1/2+y, 1/2–z), O(7)–H(7B)⋅⋅⋅O(4) (2.760(2) Å, 155º) and O(10)–H(10A)⋅⋅⋅O(2) (2.798(2) Å, 177º). Also, there are plenty of hydrogen bonds among water molecules: O(7)–H(7A)⋅⋅⋅O(9) (2.893(2) Å, 158º) and O(10)– H(10B)⋅⋅⋅O(7)^b (2.892(3) Å, 164.7º) (symmetry codes: (b): –1/2+x, 1/2–y, –1/2+z). All hydrogen bonds contribute to the stability of the compoud^[10].

  3.2 Spectral analysis of 1

  The wide adsorption peak at about 3410 cm^-1 is the characteristic peak of OH group of H₂O^[11]. Two strong peaks at 1662 and 1381 cm^-1 could be assigned to the v_as(coo-) and v_s(coo-) stretching vibration of o-benzoylbenzoic acid ligand, with Δv_coo- = 281 cm^-1 (Δv_coo- = v_as(coo-) – v_s(coo-)) greater than 200 cm^-1, which indicates that carboxylic radicals in the o-benzoylbenzoic acid ligand coordinated with the manganese ions in a monodentate manner. The characteristic absorption peak of the phen ligand in complex has obvious shift from 1421, 853 and 739 cm^-1 to 1427, 851 and 731 cm^-1, respectively, thus revealing the coordination of nitrogen atoms in phen with the manganese(II). There are Mn–O and Mn–N characteristic absorption peaks at 671 and 451 cm^-1[12]. The above analysis conforms to the crystal test results.

  Fig. 3 shows the emission spectra, recorded in the range of 360~520 nm, of the title complex and free ligands in solid state at ambient temperature. As seen in Fig. 3, phen, o-benzoylbenzoic acid and the title complex display the characteristic emission peaks at 436, 422 and 424 nm, respectively. Compared with the free ligand and o-benzoyl- benzoic acid, the title complex has the same characteristic emission peak and similar figure, but its luminescence is relatively stronger, suggesting that this may be mainly ascribed to electronic transition of the intraligand o-benzoyl- benzoic acid^[13].

  Figure 3

  

  Figure 3.  Luminescence property curves of the title complex and ligands

  a: phen; b: o-benzoylbenzoic acid; c: the title complex

  DownLoad: Full-Size Img PowerPoint

  3.3 Magnetic properties of 1

  The temperature dependence of the magnetic susceptibility of 1 was investigated from 300 to 2 K with an applied magnetic field of 2 kOe. The X_m T vs. T and X_m vs. T curves are in Fig. 4. The maximum experimental value of X_m T is 3.03362 at 300 K, then the X_m T of 1 decreases with reducing the temperature, which indicates antiferromagnetic interaction in the complex^[14]. When the temperature reaches 2 K, the X_m T value is 2.098. The linear regression equation is 1/X_m = 0.3411T + 3.3263 with a correlation coefficient of 0.9961. According to the Curie-Weiss law, from X_m = C/(T−θ), the Weiss constant θ can be obtained, C = 3.914 and θ = −87.088 K. These magnetic behaviors show that the title complex exhibits antiferromagnetism. In this work, the magnetic behavior is attributed to the interaction between manganese ions and free ligands^[15].

  Figure 4

  

  Figure 4.  Temperature dependence of the magnetic susceptibility of the title complex in the form of (a) X_mT vs. T, X_m vs. T; (b) 1/X_m vs. T, X_m vs. T

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  3.4 TG and DTG analyses of 1

  The thermogravimetric analysis (Fig. 5) of 1 demonstrates that the weight loss in air from room temperature to 973 K occurs mainly in 3 stages. The first one takes place from 373 to 383 K with the weight loss of 7.70%, corresponding to the release of free and coordinated water molecules (calcd.: 7.69%). At the same time, one thermal absorption peak of DTG appears at about 375 K, indicating the decomposition of free water molecules^[16]. The second stage is found from 383 to 673 K with the weight loss of 38.50%, resulting from the departure of two phen molecules (calcd.: 38.43%). The second DTG thermal absorption peak is observed at about 609 K which is the melting point of the complex. During stage 3, the weight loss of 46.30% (theoretical value: 46.32%) presents at 673~833 K due to the loss of 28 carbon, 18 hydrogen and 5 oxygen atoms from two o-benzoylbenzoic acid molecule anions. The final product is manganese oxide, with the final residual rate to be 7.50% (calcd.: 7.56%).

  Figure 5

  

  Figure 5.  TG and DTG curves of the title complex

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• 

  Figure 1  Molecular structure of the title complex

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  Figure 2  Hydrogen bonding between adjacent molecules of the title complex

  下载: 全尺寸图片 幻灯片
  

  Figure 3  Luminescence property curves of the title complex and ligands

  a: phen; b: o-benzoylbenzoic acid; c: the title complex

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  Figure 4  Temperature dependence of the magnetic susceptibility of the title complex in the form of (a) X_mT vs. T, X_m vs. T; (b) 1/X_m vs. T, X_m vs. T

  下载: 全尺寸图片 幻灯片
  

  Figure 5  TG and DTG curves of the title complex

  下载: 全尺寸图片 幻灯片

  Table 1.  Selected Bond Lengths (Å) and Bond Angles (°)

  Bond	Dist.		Bond	Dist.		Bond	Dist.
  Mn(1)–O(1)	2.143(1)		Mn(1)–O(5)	2.143(1)		Mn(1)–N(1)	2.239(2)
  Mn(1)–N(2)	2.361(2)		Mn(1)–N(3)	2.344(2)		Mn(1)–N(4)	2.244(2)
  O(1)–C(25)	1.270(2)		O(2)–C(25)	1.243(2)		O(4)–C(39)	1.245(2)
  O(5)–C(39)	1.264(2)
  Angle	(°)		Angle	(°)		Angle	(°)
  O(1)–Mn(1)–N(1)	97.07(6)		O(1)–Mn(1)–N(2)	82.18(6)		O(1)–Mn(1)–N(3)	160.81(6)
  O(1)–Mn(1)–N(4)	93.48(6)		O(5)–Mn(1)–O(1)	114.66(6)		O(5)–Mn(1)–N(1)	91.54(6)
  O(5)–Mn(1)–N(2)	158.35(6)		O(5)–Mn(1)–N(3)	81.59(6)		O(5)–Mn(1)–N(4)	102.08(5)
  N(1)–Mn(1)–N(2)	72.14(6)		N(1)–Mn(1)–N(3)	92.38(6)		N(1)–Mn(1)–N(4)	157.45(7)
  N(2)–Mn(1)–(3)	84.91(6)		N(2)–Mn(1)–N(4)	89.73(6)		N(3)–Mn(1)–N(4)	72.27(6)

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  Table 2.  Hydrogen Bond Lengths (Å) and Bond Angles (°)

  D–H⋅⋅⋅A	d(D–H)	d(H⋅⋅⋅A)	d(D⋅⋅⋅A)	∠DHA
  O(8)–(8B)⋅⋅⋅O(2)	0.81	2.07	2.841(2)	159
  O(9)–H(9A)⋅⋅⋅O(3)a	0.85	2.17	3.004(2)	165
  O(7)–H(7A)⋅⋅⋅O(9)	0.85	2.09	2.893(2)	158
  O(7)–H(7B)⋅⋅⋅O(4)	0.85	1.97	2.760(2)	155
  O(10)–H(10A)⋅⋅⋅O(2)	0.73	2.07	2.798(2)	177
  O(10)–H(10B)⋅⋅⋅O(7)b	0.85	2.06	2.892(3)	165
  Symmetry codes: (a): 3/2–x, –1/2+y, 1/2–z; (b): –1/2+x, 1/2–y, –1/2+z

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