Chiral and Achiral Copper(II) Carboxyphosphonates Supramolecular

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Chiral and Achiral Copper(II) Carboxyphosphonates Supramolecular Structure: Synthesis, Structures, Surface Photovoltage and Magnetic Properties Chengqi Jiao, Zhou Zhao, Chao Ma, Zhen-Gang Sun, Dapeng Dong, Yan-Yu Zhu, and Jing Li Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b00197 • Publication Date (Web): 30 Aug 2016 Downloaded from http://pubs.acs.org on September 3, 2016

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Crystal Growth & Design

Chiral and Achiral Copper(II) Carboxyphosphonates Supramolecular Structure: Synthesis, Structures, Surface Photovoltage and Magnetic Properties Cheng-Qi Jiao,† Zhou Zhao,† Chao Ma,† Zhen-Gang Sun*,†, Da-Peng Dong*,‡, Yan-Yu Zhu,† and Jing Li†

†

School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, P. R. China

‡

School of Physics and Materials Engineering, Dalian Nationalities University, Dalian 116600, P. R. China

ABSTRACT: Five chiral and achiral copper(II) carboxyphosphonates, namely, [Cu(4-cppH)(2,2'–bipy)(H2O)] (1: R-1 and S-1), [Cu9(4-cpp)6(2,2'-bipy)6] (2), [Cu3(4-cpp)2(2,2'-bipy)2] (3), [Cu3(4-cpp)2(1,10-phen)2]·4H2O (4) and [Cu(4-cppH)(1,10-phen)]·H2O (5), had been hydrothermally synthesized. Among them, 1 showed an unexpected 1D chiral helical chain from achiral carboxyphosphonate ligand by spontaneous resolution. In 2, the interconnection of {CuN2O3}, {CuO4} and {CPO3} polyhedra formed a 1D chain. Such chains were further connected to a 2D layer through the carboxyphosphonates ligands. 3 and 4 were isostructural and exhibited a 2D layer, which were constructed from {CuO3N2}/{CuO4} polyhedra and the carboxyphosphonate ligands. In 5, the interconnection of neighboring {CuN2O3} polyhedra formed a dimer. These dimers were connected with the carboxyphosphonate ligands to form a chain. Interestingly, the homochiral copper(II) phosphonate (R-1 or S-1) could be obtained by utilizing the (+)-cinchonine or (-)-cinchonidine as a chiral inducing agent, confirmed by CD spectra. Besides, the surface photovoltage (SPV) properties of 1–5 revealed that they had positive SPV responses. The magnetic data indicated that 1, 2, 4 and 5 showed the presence of ferromagnetic couplings between magnetic centers.

1. INTRODUCTION Coordination polymers (CPs) have been paid much attention due to their interesting structures and potentially applications.1-10 As an important class of CPs materials, metal phosphonates have been rapidly researched in recent decades, mainly due to the diversities of structures and potential utilizations in catalysis, magnetism, ion exchange, proton conductivity, molecular recognition, photochemistry and so on.11-23 Therefore, rationally designing and synthesizing metal phosphonates with an intriguing diversity of structures and properties have become particularly important. Studies of metal phosphonates have shown that the introduction of bi- and multifunctional phosphonic acids with sub-functional groups (–NH2, –OH, and –COOH) can provide many coordination modes, resulting in new structure types of metal phosphonates and bringing interesting properties.24-30 Recently, the results of our and other groups indicate that the introduction of a second organic ligand, such as oxalate, 1

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sulfonic acid, carboxylic acid, 2, 2′-bipy, 1, 10-phen and 4, 4′-bipy, have provided an effective synthetic strategy of new metal phosphonates with interesting structures and properties.31-36 Recently, incorporating different dn electron configuration of transition metal ions into their structures can make them become ideal for use in developing new multifunctional materials. To date, a large amount of transition metal phosphonates have been synthesized, some of which display interesting properties such as magnetism, luminescence and catalysis behaviors.37-41 However, reports about the photoelectric properties of these materials are scarce. Among these photoelectric properties, surface photovoltage spectroscopy (SPS) as a useful tool can be used to study the photophysics of the excited states and the surface charge behavior of the sample.42-45 To date, reports about this aspect have mainly focused on the coordination compounds with phthalocyanines or porphyrins as ligands, however, investigating the properties of coordination polymers is not common. We reported the first example on the surface photovoltage properties of metal phosphonates.46 Following the seminal work, a serial of metal phosphonates analogues were investigated.47-49 But the systematic study about the relationships between the properties and structures is the first report. Furthermore, the mixed ligands and the other transition metal hybrid compounds with layered, chain, and 3D network structures can be built by the use of additional bidentate metal linkers such as 1, 10-phen, 2, 2′-bipy, and 4, 4′-bipy.50-53 Generally, the 1, 10-phen and 2, 2′-bipy ligands can act as the chelating ligands and provide potential sites for π–π stacking interactions which not only increase the dimensionality of the polymerization, but also improve the properties of the photovoltage and magnetic.54-56 On the other hand, chiral CPs have attracted extensive attentions for their potential utilizations in nonlinear optics, enantioselective processes and so on.57-64 Among them, metal phosphonates are good candidates for the construction of chiral materials. Despite lots of metal phosphonates have been reported in recent years, however, few chiral metal phosphonates have been obtained. There are two basic methods to obtain chiral metal phosphonates: (1) the use of enantiopure phosphonate ligands,25,65-73 (2) spontaneous resolution.22,46,74-78 The most effective method is to use enantiopure phosphonate ligand, but the chiral agent is usually expensive and often require complex synthesis. The approach for the synthesis of chiral metal phosphonates from spontaneous resolution on crystallization without any chiral auxiliary usually can result in chiral conglomerate. However, a racemic conglomerate is usefulness in an enantioselective process, therefore, it is a challenge for the chemist to make chiral crystals and control the process which obtains the excess enantiomeric of the desired chirality in the bulk solid. Recently, it has been found that the absolute chirality of the racemic conglomerate can be controlled by chiral induction in different chemical systems, in which the coordinate bonding between chiral additive and framework metal sites involved.79-81 Herein, using 2


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4–carboxyphenylphosphonic acid (4-cppH3) as the phosphonate ligand and 2, 2′-bipy or 1, 10-phen as the second metal linker, five chiral and achiral copper(II) carboxyphosphonates had been prepared, namely,

[Cu(4-cppH)(2,2'–bipy)(H2O)]

(1:

R-1

and

S-1),

[Cu9(4-cpp)6(2,2'-bipy)6]

(2),

[Cu3(4-cpp)2(2,2'–bipy)2] (3), [Cu3(4-cpp)2(1,10-phen)2]·4H2O (4) and [Cu(4-cppH)(1,10-phen)]·H2O (5). Among them, 1 is an unexpected 1D chiral helical chain, which can be synthesized as a conglomerate by spontaneous resolution. More importantly, the homochiral copper(II) phosphonate (R-1 or S-1) can be obtained by the method of chiral induction through using the (+)-cinchonine or (-)-cinchonidine chiral inducer. Here, we studied the synthesis, structures, and surface photovoltage and magnetic properties of 1, 2, 4 and 5. The structure and magnetic property of 3 have been reported by Zubieta’s group,82 therefore, the surface photovoltage property of 3 is only described.

2. EXPERIMENTAL SECTION 2.1. Materials and Physical Measurements. The 4-carboxyphenylphosphonic acid (4-cppH3) was prepared according to the literature.83All other chemicals were purchased from commercial sources and used without any further purification. IR spectra were measured on a Bruker AXS TENSOR–27 FT–IR spectrometer with KBr pellets from 4000 to 400 cm-1. The contents of Cu, P and C, H, N were determined by using an inductively coupled plasma (ICP) atomic absorption spectrometer and a PE–2400 elemental analyzer, respectively. The powder X-ray diffraction data were collected on a Bruker AXS D8 Advance diffractometer using Cu–Kα radiation (λ = 1.5418 Å) in the 2θ range from 5 to 60° with a scanning rate of 3°/min and a step size of 0.02°. Circular dichroism (CD) spectra were measured on a BioLogic MOS-500 spectrodichrometer using KBr pellets. The solid UV–Vis absorption spectra were recorded on a HITACHIU-4100 spectrophotometer. Photoelectric properties (SPS and FISPS) measurements were conducted with the sample in a sandwich cell (ITO/sample/ITO) with the light source-monochromator-lock-in detection technique. Magnetic measurements of the samples were performed on a Quantum Design SQUID (MPMSXL-7) magnetometer. Data were corrected for the diamagnetic contribution calculated from Pascal constants. 2.2. Synthesis Methods. Preparation of [Cu(4-cppH)(2,2'–bipy)(H2O)] (1). Cu(Ac)2·H2O (0.085 g, 0.43 mmol), 4-cppH3 (0.05 g, 0.26 mmol) and 2,2′-bipy (0.068 g, 0.44 mmol) were dissolved in 10 mL water, and then stirred for about 60 min at RT. The mixture (pHinitial = 4.4) was sealed in a 20 mL Teflon–lined stainless steel autoclave, and heated at 100 °C for 48 hours. Cooling to RT, blue rodlike crystals of 1 were obtained (yield 30.5 % based on Cu). Anal. Calc. for C17H15CuN2O6P: C, 46.63; H, 3.45; N, 6.40; P, 7.07; Cu, 14.51. Found: C, 46.66; H, 3.42; N, 6.43; P, 7.03; Cu, 14.56 %. IR (KBr, 3



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cm−1): 3385(br), 3103(w), 3072(w), 1575(s), 1528(s), 1427(m), 1382(s), 1305(w), 1222(w), 1110(s), 1003(w), 943(m), 842(w), 738(m), 720(w), 586(w), 535(w), 481(w), 445(w). Preparation of [Cu(4-cppH)(2,2'–bipy)(H2O)] (R-1 and S-1). Crystals of R-1 and S-1 were obtained according to the same method as that of 1 by using (+)–cinchonine (10% mole ratio relativet to the ligand) and (-)–cinchonidine (10% mole ratio relative to the ligand) as the chiral adducts, respectively. Preparation of [Cu9(4-cpp)6(2,2'–bipy)6] (2). Cu(Ac)2·4H2O (0.10 g, 0.50 mmol), 4-cppH3 (0.05 g, 0.26 mmol) and 2,2′-bipy (0.068 g, 0.44 mmol) were dissolved in 10 mL water. The resulting solution (pHinitial = 4.5) was stirred for about 60 min at RT, sealed in a 20 mL Teflon−lined stainless steel autoclave, and heated at 120 °C for 48 hours. Cooling to RT, blue block crystals of 2 were obtained (yield 38.7 % based on Cu). Anal. Calcd for C102H72Cu9N12O30P6: C, 45.32; H, 2.68; N, 6.22; P, 6.87; Cu, 21.15; Found: C, 45.23; H, 2.78; N, 6.28; P, 6.79; Cu, 21.10 %. IR (KBr, cm−1): 3435(br), 3106(w), 3042(w), 1585(s), 1534(s), 1396(s), 1310(w), 1246(w), 1147(s),1089(s), 1019(s), 846(w), 766(s), 730(m), 650(w), 599(w), 551(m). Preparation of [Cu3(4-cpp)2(2,2'–bipy)2] (3). 3 was prepared by a similar method with 1 excepting that heated at 160 °C for 48 hours. The pH value was adjusted to 4.4-6.0 by adding 1M NaOH (pHinitial = 4.4). Cooling to RT, blue block crystals of 3 were obtained (yield 50.6 % based on Cu). Anal. Calc. for C34H24Cu3N4O10P2: C, 45.32; H, 2.68; N, 6.22; P, 6.87; Cu, 21.15. Found: C, 45.35; H, 2.65; N, 6.18; P, 6.91; Cu, 21.18 %. IR (KBr, cm−1): 3043(w), 1585(s), 1533(s), 1395(s), 1147(s), 1093(s), 1018(s), 845(w), 770(m), 732(m), 603(w), 558(m), 468(m). Preparation of [Cu3(4-cpp)2(1,10-phen)2]·4H2O (4). Cu(Ac)2·H2O (0.10 g, 0.50 mmol), 4-cppH3 (0.05 g, 0.26 mmol) and 1,10-phen (0.08 g, 0.44 mmol) were dissolved in 10 mL distilled water. The pH value was adjusted to 4.4–6.0 by adding 1M NaOH (pHinitial = 4.4). The resulting solution was stirred for about 60 min at RT, sealed in a 20 mL Teflon−lined stainless steel autoclave, and heated at 160 °C for 48 hours. Cooling to RT, green block crystals of 4 were obtained (yield 62.5 % based on Cu). Anal. Calc. for C38H32Cu3N4O14P2: C, 44.69; H, 3.16; N, 5.49; P, 6.07; Cu, 18.67. Found: C, 44.73; H, 3.13; N, 5.45; P, 6.11; Cu, 18.70 %. IR (KBr, cm−1): 3391(br), 3066(w), 1585(m), 1508(s), 1427(s), 1237(m), 1176(m), 1124(w), 1086(w), 912(m), 851(m), 777(w), 723(m), 596(w), 526(w), 468(m). Preparation of [Cu(4-cppH)(1,10-phen)]·H2O (5). 5 was prepared by a similar method with 4 excepting that heated at 80 °C for 72 hours. The pH value was adjusted to 4.6–6.0 by adding 1M NaOH 4


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(pHinitial = 4.4). Cooling to RT, blue plate crystals of 5 were obtained (yield 66.3 % based on Cu). Anal. Calcd for C19H15CuN2O6P: C, 49.41; H, 3.27; N, 6.07; P, 6.71; Cu, 13.76. Found: C, 49.45; H, 3.24; N, 6.10; P, 6.68; Cu, 13.81 %. IR (KBr, cm−1):3435(br), 3066(w), 1585(s), 1540(m), 1389(s), 1140(s),1041(w), 928(w), 851(m), 777(w), 723(s), 558(w), 468(w). 2.3. Crystal Structure Determination. Data collections for 1–5 were performed on the Bruker AXS Smart APEX II CCD X–diffractometer equipped with graphite monochromated MoKα radiation (λ = 0.71073 Å) at 293 ± 2K. The empirical absorption corrections were applied by using the SADABS program. The structures were solved by direct methods and refined by full–matrix least squares fitting on F2 by SHELXS–97.84 All non–hydrogen atoms were refined anisotropically. The hydrogen atoms of organic ligands were located geometrically and fixed isotropic thermal parameters. For 4 and 5, the hydrogen atoms for the lattice water molecules were fixed through Fourier electron density and fixed isotropic thermal parameters. Crystal data and structural refinements for 1–5 were given in Table 1. Selected bond lengths were summarized in Table S1 (Supporting Information).

Table 1

3. RESULTS AND DISCUSSION 3.1. Syntheses. Five copper(II) carboxyphosphonates had been hydrothermally synthesized, utilizing 4-carboxyphenylphosphonic (4-cppH3) and similar N-donor ligands (2, 2′-bipy or 1, 10-phen). In order to obtain good crystals for X-ray diffraction analyses, the optimal method of synthesizing was researched. Firstly, the reaction temperature played an important part in the formation of five compounds. 3 and 4 were obtained at 160 °C, while 1, 2 and 5 were prepared at 100, 120 and 80 °C, respectively. Secondly, the pH value had also a strong effect on the formation of the targeted compounds. 1 and 2 were only prepared in the initial pH value (4.4 for 1 and 4.5 for 2). The other pH value would lead to the formation of 3. 3–5 could be obtained in different yields and qualities when the reaction mixture was adjusted to a certain pH value (4.4-6.0 for 3 and 4 and 4.6-6.0 for 5). The most quality crystals could be prepared when the pH value was adjusted to 5.0 for 3, 4.8 for 4 and 5.5 for 5, respectively. A lower pH (6.0) leaded to a large amount of uncharacterized precipitate and very small amount of single crystals. In the absence of (+)-or (-)-cinchonidine, the mixture of R-1 and S-1 was observed. Interestingly, homochiral crystals could be 5



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obtained by adding 10 mol % of (+)- or (-)-cinchonidine, respectively. R-1 was prepared by the addition of (+)-cinchonine whose crystal space group was the same as 1. The structural analysis of randomly selected crystals from the same batch suggested that these crystals had the same homochiral characteristic (Table S1, Supporting Information). Similarly, S-1 was got by chirality-inducing effect in the presence of (-)-cinchonidine, and the cell dimensions were similar to 1 and R-1. The powder XRD and simulated XRD patterns of 1–5 were shown in Figures S1–S5 in the Supporting Information. All the peaks of 1–5 could be indexed to their respective simulated XRD patterns, which indicated 1–5 were pure phases.

Scheme 1

Figure 1

3.2. Crystal Structures Analysis. Crystal Structures of 1 (R-1 and S-1). 1 (R-1 and S-1) crystallized in the monoclinic chiral space group P21 with Flack parameters of 0.043(18) and 0.095(17), respectively (Table 1). As depicted in Figure 1a, R-1 and S-1 had perfect mirror image; herein, we took R-1 as an example. There were one Cu(II) ion, one 4-cppH2- anion, one 2, 2'-bipy molecule and one coordinated water molecule in the asymmetric unit of R-1 (Figure 1a, left). The Cu(II) ion exhibited a distorted tetragonal pyramidal geometry. Four basal positions were occupied by N1, N2, O1A and O4 atoms from one 2, 2'-bipy molecule and two equivalent 4-cppH2- anions, respectively. The Cu–O distances were 1.910(3) and 1.978(3) Å, whereas Cu–N distances were 2.024(4) and 2.044(4) Å. The axial site was occupied by one water molecule (O6) with an elongated Cu–O6 distance [2.270(4) Å] (Table S2, Supporting Information). The Cu–O/N distances accorded with those reported for other Cu(II) phosphonates.85 The carboxyphosphonate ligand adopted a bidentate coordinated mode, which was rare in metal carboxyphosphonate (Scheme 1). It only bridged two Cu ions through para-carboxyl group and phosphonate group. Futhermore, the phosphonate oxygen atom (O3) of the 4-cppH2− anion was protonated. As shown in Figure 1b (left), the {CuN2O3} polyhedra cross-linked through the carboxyphosphonate ligands formed a 1D left-hand helical chain with the pitch of 6.96 Å along b-axis. The neighboring chains were extended together through π−π interactions between the adjacent 2, 2'-bipy rings (distances = 3.695 and 3.781 Å), resulting in a 2D supramolecular network (Figures 1c and 1d). The asymmetric unit and helical chain of S-1 were also shown in Fig. 1a and 1b (right) for comparison. 6


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Crystal Structure of 2. 2 crystallized in the triclinic space group P-1 (Table 1). There were five crystallographically independent Cu(II) ions, three 4-cpp3− anions and three 2, 2′-bipy ligands in the asymmetric unit of 2 (Figure 2). The Cu1, Cu2 and Cu4 ions were all five coordinated by two phosphonate oxygen atoms (O1 and O2A for Cu1, O7 and O11 for Cu2 and O8 and O12 for Cu4) from two separate 4-cpp3− anions, one carboxylate oxygen atom (O9B for Cu1, O15C for Cu2 and O5E for Cu4) from one 4-cpp3− anion and two nitrogen atoms (N1 and N2 for Cu1, N3 and N4 for Cu2 and N5 and N6 for Cu4) from the 2, 2′-bipy ligand. The Cu3 ion had a plane coordination environment. The four coordination positions were filled with two phosphonate oxygen atoms (O3 and O6) from two separate 4-cpp3− anions and two carboxylate oxygen atoms (O10D and O14C) from two 4-cpp3− anion. The occupancy of Cu5 ion was 0.5. The Cu5 ion was four-coordinated by four oxygen atoms (O4C, O4E, O13 and O13F) from four separate 4-cpp3−anions. The Cu–O/N distances ranged from 1.879(16) to 2.293(16) Å (Table S2, Supporting Information). All three 4-cpp3− anions adopted the same pentadentate coordinated mode. They bridged five Cu atoms through its all five oxygen atoms, therefore, all oxygen atoms were monodentate (Scheme 1).

Figure 2

The 2D Cu–phosphonate layer was observed in 2. As shown in Figure 3a, the {CuN2O3}/{CuO4} polyhedra and {CPO3} tetrahedra were alternately connected into a chain. Such chains were further connected to a 2D layer through the phosphonate ligands in the bc–plane. This kind of connections resulted in forming a regular window. The window was formed by 18–atom rings, including two Cu atoms, two P atoms, four O atoms and ten C atoms. The dimension of the window is 6.9 Å (O11–O11) × 3.5 Å (C45–C47) on the basis of structure data. These neighboring layers were further extended into a 3D supramolecular structure with assistance of the π−π interactions (distances = 3.835–3.992 Å) between the adjacent 2, 2'-bipy rings (Figure 3b).

Figure 3

Figure 4

7



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Crystal Structures of 3 and 4. 3 and 4 were isomorphous and featured a similar 2D layer structure except that the second ligands were different (2, 2'-bipy 3, 1, 10-phen 4) (Figure 5, Figures S6–S8, Supporting Information). The structure of 3 had been reported by Zubieta’s group,82 hence, only the structure of 4 would be described as an example. 4 crystallized in the triclinic space group P–1 (Table 1). Each asymmetric unit consisted of two crystallographically distinct Cu(II) ions, one 4-cpp3− anion, one 1, 10-phen molecule and two lattice water molecules (Figure 4). The Cu1 ion had a distorted square–pyramidal geometry. The four basal plane were occupied by two phosphonate oxygen atoms (O1 and O2A) from two separate 4-cpp3− anions and two nitrogen atoms (N1, N2) from one 1, 10-phen molecule. The remaining apical position was occupied by one carboxylate oxygen atom (O5) from one 4-cpp3− anion. The Cu1–O5 distance [2.263(2) Å] was apparently longer than the other Cu1–O/N distances [1.897(2)–2.039(3) Å]. The occupancy of Cu2 ion was 0.5, which had a plane coordination environment by four oxygen atoms (O3C, O3D, O4 and O4E) from four separate 4-cpp3− anions. The Cu–O distances were 1.947(2) and 1.971(2) Å (Table S2, Supporting Information). The carboxyphosphonate ligand was a pentadentate ligand, binding five Cu atoms through its all five oxygen atoms, therefore, all oxygen atoms were monodentate (Scheme 1).

Figure 5

The {CuN2O3} square–pyramidal and {CuO4} plane were interconnected through {CPO3} tetrahedra to form a 1D chain along a–axis. These neighboring 1D chains were bridged through the 4-cpp3− anions into a 2D layer in the ab–plane (Figure 5a). This kind of connections resulted in forming two types of windows. The two windows were both formed by 18–atom rings, including two Cu atoms and two 4-cpp3− ligands. Because of the coordinated environments of two Cu atoms were different, the sizes of two windows were slightly different. The dimensions of the windows are 8.6 Å (O3–O3) × 3.0 Å (C3–C3) for A window, and 7.0 Å (O2–O2) × 3.6 Å (C6–C7) for B window on the basis of structure data. Such neighboring layers were extended together through π−π interactions between the adjacent 1, 10-phen rings (distances = 3.397 Å), resulting in a 3D supramolecular strcture (Figure 5b).

Figure 6

8


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Crystal Structure of 5. 5 crystallized in the triclinic P–1 space group (Table 1). Each asymmetric unit included one crystallographically independent Cu(II) ion, one 4-cppH2− anion and one 1, 10-phen molecule (Figure 6). The Cu(II) ion displayed a distorted square–pyramidal coordination geometry. The basal positions were occupied by two oxygen atoms (O1A and O4B) from two separate 4-cppH2− anions and two nitrogen atoms (N1, N2) from one 1, 10-phen molecule. The apical position was filled with O1 from another 4-cppH2− anion. The Cu–O/N distances ranged from 1.955(2) to 2.414(2) Å (Table S2, Supporting Information). Each 4-cppH2− group in 5 served as a tridentate ligand, linking three Cu atoms using one of its three phosphonateoxygens (O1) and one carboxyl oxygen atom (O4). Furthermore, the phosphonate oxygen atom (O2) of the 4-cppH2− anion was protonated (Scheme 1).

Figure 7

As shown in Figure 7a, the interconnection of neighboring {CuN2O3} polyhedra formed a dimer. These dimers were interconnected to form a chain through the carboxyphosphonate ligands along the b-axis. As shown in Figure 7c and Figure 7d, two types of stacking interactions were found in 5: one was the point-to-face C−H−π interaction (distance = 2.681 Å) between the hydrogen atoms of the 1, 10-phen rings and the benzene rings of the carboxyphosphonate ligands along the a–axis, and the other was the π−π stacking interaction (distance = 3.513 Å) between the adjacent 1, 10-phen rings along the c-axis. As a result, the above C−H−π and π−π interactions finally resulted in forming a 3D supramolecular network structure (Figure 7b). 3.3. Structural Discussion. It was noteworthy that 1–5 showed different structures, although the same phosphonate ligand and similar N-donor ligands (2, 2′-bipy or 1, 10-phen) were applied. This could be explained as followed: Firstly, the different pH values had remarkable effects on product formation. Under the initial pH value condition (4.4/4.5), the phosphonate ligand was partly deprotonation (4-cppH2−), the expected low-dimensional structures 1 and 5 (1D) were obtained. With the increase of the pH value (4.5–6.0), the phosphonate ligand was entirely deprotonation (4-cpp3−), the resulting 2–4 showed 2D layer structures. Thus, the pH value made a difference in the formation of the final structures due to successive deprotonation of the phosphonate ligand with increasing pH value, which resulted in an increased dimensionality of the as-synthesized compounds. Secondly, it was interesting that 1 exhibited a 1D chiral helical chain by spontaneous resolution in the absence of chiral inducer. The phosphonate ligand adopted a “linear” shape86 and acted a simple bidentate bridge to link 9



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two Cu(II) ions via para-carboxyl group and phosphonate group, forming a chiral helical chain with a certain angle (O1–Cu–O4 = 94.81º). The remaining three positions were filled with one water molecule and two nitrogen atoms from one N-donor ligand. The two coordinated molecules did not affect the structure of the chiral helical chain, thus, the characteristic of chiral could be kept. This overall result indicated that the “linear” shape and suitable pH value were believed to be the main reason for the chirality of 1. 3.4. Circular Dichroism. To study the enantiomeric optical activity of the crystals, the solid-state circular dichroism spectrum (CD) were investigated. As shown in Figure S9, randomly selected single crystals of 1 from the same batch crystallized in the absence of chiral inducer displayed dichroic signal with positive or negative Cotton effect. Results of the CD spectra and single-crystal studies identified that the sample was a conglomerate which confirmed that spontaneous resolution occurred during the forming process of crystallization. The CD spectra of bulk crystals in the presence of (+)-cinchonine or (-)-cinchonidine exhibited a positive and negative mirror image dichroic signal at similar wavelength, thus it indicated that the homochiral crystallization could be controlled by chiral induction (Figure 8).

Figure 8

3.5. Surface Photovoltage Properties. The surface photovoltage spectra were measured from 300 to 800 nm, which were shown in Figure 9. The UV–Vis spectra of all compounds were also recorded in a form of solid from 200 to 800 nm (Figures S10–S14, Supporting Information). Broad response bands of 1 and 5 were similar (Figure 9a and Figure 9e). Three response bands were observed by the treatment of Origin 7.0 program. The bands at 327 and 350 nm for 1, 325 and 371 nm for 5 were identified as the LMCT transitions of the O→Cu and N→Cu, while the bands at 675nm for 1, and 705 nm for 5 were ascribed to the d→d* transitions of Cu(II) ions. Four absorption bands were observed in the UV–Vis absorption spectra of 1 and 5, respectively (Figure S10 and Figure S14, Supporting Information). The bands at 236 nm for 1, 236 nm for 5 were attributed to the π→π* transitions of ligands, while the bands at 303 and 315 nm for 1, 294 and 342 nm for 5 were identified as the LMCT transitions of the O→Cu and N→Cu. Bands at 713 nm for 1, and 666 nm for 5 were ascribed to the d→d* transitions of the Cu(II) ions. Two response bands were observed in the SPS of 2 (Figure 9b). Four response bands were obtained by the treatment of Origin 7.0: 333, 461, 470 and 652 nm. The three bands at 333, 461 and 470 nm 10


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were identified as the LMCT transitions of the O→Cu and N→Cu. The bands at 652 nm were ascribed to the d→d* transitions of Cu(II) ions. Six absorption bands of 2 were found in the UV–Vis spectrum (Figure S11, Supporting Information). The band at 236 nm was attributed to the π→π*transitions of ligands, while the bands at 301 and 423 nm were identified as the LMCT transitions of the O→Cu and N→Cu. In addition, the band at 718 nm was ascribed to the d→d* transitions of the Cu(II) ions. The SPS of 3 and 4 were also similar with two response bands within 300–800 nm. By careful differentiation through Origin 7.0 program, the response bands of 3 and 4 contained four filial bands, respectively (Figure 9c and Figure 9d). Three response bands at 322, 372 and 463 nm for 3, 337, 392 and 462 nm for 4 were ascribed to the transition caused by LMCT (O→Cu and N→Cu). The response bands at 728 nm for 3, and 657 nm for 4 were identified as the d→d* transitions of the Cu(II) ions. Five absorption bands of 3 and 4 were found in the UV–Vis spectra (Figure S12 and Figure S13, Supporting Information). The bands at 229 nm for 3, 225 nm for 4 were attributed to the π→π* transitions of ligands. Three bands at 288, 312 and 372 nm for 3, 303, 329 and 349 nm for 4 were ascribed to the LMCT transitions of the O→Cu and N→Cu. In addition, the bands at 682 nm for 3, 700 nm for 4 were identified as the d→d* transitions of the Cu(II) ions. In comparison with the SPS responses of 1–5 (Figure 9f), the conclusions were shown below: (1) All five compounds showed positive SPS response bands from 300 to 800 nm, which exhibited that they possessed certain surface photovoltage properties. The results indicated that the SPS and the UV–Vis spectra were also basically consistent; (2) The structures of compounds could affect intensity of SPS bands. The more dimensional was beneficial for supplying more electrons diffuse to the surface, resulting in the enhancement of the SPS response intensities. 2–4 possessed a 2D layer structure, while 1 and 5 exhibited an infinite 1D chain structure. Therefore, the SPS intensities of 2–4 were higher than those of 1 and 5. In addition, strong π−π stacking interactions in all five compounds made a difference in transferring electrons or holes. Compared 4 with 3, the π−π stacking interactions (3.397 Å) of 4 were stronger than those of in 3 (3.868 and 3.991 Å), which were beneficial to the increase of the SPV response intensities. However, 1 only possessed a 2D layer structure, which resulted in the lowest intensity of the SPS of 1.

Figure. 9

11



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The FISPS of 1–5 between 300 and 800 nm were measured under the condition of external electric fields at –5, 0, and +5 V, respectively (Figure 10). As seen from the figure, the SPV response intensities increased with the positive fields increasing, in contrast, they reduced with the external negative fields increasing. The FISPS confirmed that it was the typical characteristic of p-type semiconductors.

Figure. 10

3.6. Magnetic Properties. The magnetic susceptibility data of 1, 2, 4 and 5 were measured from 2 to 300 K at 1000 Oe (Figure 11). For 1, the χT value was 0.42 cm3 mol−1 K at 300K, which was slightly larger than the spin-only value of 0.38 cm3 mol−1 K expected for an uncoupled Cu(II) (S = 1/2), assuming that g = 2.00 (Figure 11a). Upon further cooling, the χT value kept a constant until 80 K. Below the temperature, it increased rapidly to 0.56 cm3 mol−1 K at 3.5 K, and then dropped abruptly. The overall magnetic behavior indicated the ferromagnetic interactions between Cu(II) and Cu(II) centers. The magnetic susceptibility data were fitted by the Curie–Weiss law at 2−300 K, which gave C = 0.42 cm3 mol−1 K and θ = 1.01 K. The positive θ value further demonstrated the ferromagnetic coupling interactions between the paramagnetic centers. The field dependence of the magnetization was measured from 0 to 50 kOe at 1.8 K (Figure S15, Supporting Information). The magnetization values at 50 kOe is 0.99 Nβ, which accorded with the ferromagnetic results of 1.00 Nβ calculated from MS = gSCu with g = 2.00. As shown in Figure 11b, the χT value at 300 K was 3.47 cm3 mol−1 K for 2, which was larger than the spin-only value of 3.38 cm3 mol−1 K for the uncorrelated nine Cu(II) (S = 1/2) with g = 2.00. Below the temperature, the χT value gradually increased to reach a maximum value of 5.20 cm3 mol−1 K at 3.7 K. Upon further lowing, the χT value decreased to 4.17 cm3 mol−1 K at 2.0 K. The magnetic susceptibility data obeyed the Curie–Weiss law at 2–300 K, which gave C = 3.33 cm3 mol−1 K and θ = 1.05 K. The positive θ value indicated the presence of ferromagnetic coupling between neighboring metal centers. As illustrated in Figure S16 (Supporting Information), the field-dependent magnetization of 2 was measured at 1.8 K in the field (0–50 kOe). The magnetization increased gradually with the applied magnetic field and reached a value of 9.23 Nβ at 50 kOe, which was in agreement with the saturation magnetization value of 9.0 Nβ expected for MS= gSCu with g = 2.00.

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Figure. 11

At 300 K, the χT value was 1.29 cm3 mol−1 K for 4 (Figure 11c), which was slightly larger than the theoretical value of 1.13 cm3 mol−1 K for the uncoupled three Cu(II) (S = 1/2, g = 2.00). Upon cooling, the χT value gradually increased to a maximum value around 2 K, indicating the presence of ferromagnetic coupling. The plot of 1/χ versus T obeyed the Curie-Weiss law at 2–300 K, which gave C = 1.28 cm3 mol−1 K and θ= 0.95 K. At 1.8 K, the isothermal magnetization gradually increased with the applied magnetic field and reached a saturated value of 3.03 Nβ at 50 kOe, which accorded with the calculated value (3.00 Nβ for three Cu(II)). This observation suggested the ferromagnetic interactions (Figure S17, Supporting Information). For 5, the χT value was 0.43 cm3 mol−1 K at 300 K, a slightly larger than the theoretical value for one independent Cu(II) assuming g = 2.00 (Figure 11d). Upon further cooling, the χT value underwent a slowly increase, and reached a maximum value at 2.0 K. The magnetic susceptibility data obeyed the Curie–Weiss law at 2–300 K with C = 0.43 cm3 mol−1 K and θ= 1.14 K. As illustrated in Figure S18 (Supporting Information), the M(H) curve indicated that the magnetization value was 1.07 Nβ at 50 kOe, which was consistent with the theoretical value calculated from MS = gSCu with g = 2.00. These behaviors indicated the presence of ferromagnetic couplings between magnetic centers.

4. CONCLUSIONS In summary, five copper(II) carboxyphosphonates had been successfully synthesized by using the 4-carboxyphenylphosphonic (4-cppH3) and similar N-donor ligands (2, 2′-bipy or 1, 10-phen) under hydrothermal conditions. The pH value and reaction temperature had a strong effect on the formation of the targeted compounds. Furthermore, the π−π stacking interactions could also make a difference in constructing the structure of compound and transferring electrons or holes of SPV. Therefore, all five compounds exhibited different supramolecular structures. 2–5 possessed 3D supramolecular structures, while 1 had a 2D supramolecular structure. It was noteworthy that 1 exhibited an unexpected 1D chiral helical chain by spontaneous resolution. Furthermore, the homochiral copper(II) phosphonate (R-1 or S-1) could be obtained by utilizing the (+)-cinchonine or (-)-cinchonidine as a chiral inducing agent. As far as we known, it was first to obtain homochiral compound through the symmetrical achiral carboxyphosphonates ligand by chiral inducer. Our results indicated that selecting the inexpensive and 13



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symmetrical achiral ligands could be also used to prepare the chiral compound. Besides, the SPS and FISPS of 1–5 indicated that they had positive SPV responses and exhibited p-type semiconductor characteristics. The results of magnetic measurement revealed that 1, 2, 4 and 5 indicated the presence of ferromagnetic couplings between magnetic centers, which showed that these compounds had the potential in semiconductor and magnetism composite materials. ASSOCIATED CONTENT Supporting Information. X−ray crystallographic files in CIF format for 1− −5. Table S1: Crystal data and refinement results for randomly selected crystals of 1, R-1 and S-1 with space group P21. Figures S1–S5: The experimental and simulated powder XRD patterns of 1–5. Figures S6–S8: ORTEP representation of a selected unit and crystal structure of 3. Figure S9: Solid-state CD spectra of 1 recorded by seven randomly selected single crystals from the same batch. Figures S10–S14: The UV–Vis absorption spectra of 1–5. Figures S15–S18: Field dependence of magnetization of 1, 2, 4 and 5 at 1.8 K. Figures S19–S23: The IR spectra of 1–5. Figures S24–S28: The TGA curves of 1–5. Table S2: Selected bond lengths [Å] for 1–5. CCDC1419419 (1), 1494081 (R–1), 1492194 (S–1), 1492193 (2), 1419420 (3), 1419421 (4) and 1419422 (5) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Center, 12, Union Road, Cambridge CB21EZ, UK; fax: (+44) 1223–336–033; e–mail: [email protected]).

AUTHOR INFORMATION Corresponding Author *(Z.S.) E-mail: [email protected]. *(D.D.) E-mail: [email protected]. Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT This work is supported by the National Natural Science Foundation of China (Grant No. 21371085 and 21301023).

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Table 1 Crystal data and structure refinements for 1−5 compounds

1

R-1

S-1

2

3

4

5

empirical formula

C17H15N2O6PCu

C17H15N2O6PCu

C17H15N2O6PCu

C102H72N12O30P6Cu

C34H24N4O10P2Cu3

C38H32N4O14P2Cu3

C19H15N2O6P

9

fw

437.82

437.82

437.82

2703.40

901.13

1021.24

461.84

crystal system

monoclinic

monoclinic

monoclinic

triclinic

triclinic

triclinic

triclinic

space group

P21

P21

P21

P–1

P–1

P–1

P–1

a (Å)

9.9344(12)

9.956(4)

9.9610(14)

12.3245(12)

8.379(8)

8.3986(2)

9.5303(6)

b (Å)

6.9602(8)

6.963(3)

6.9692(10)

12.7459(12)

9.639(8)

9.8134(3)

10.5398(6)

c (Å)

12.1272(14)

12.160(5)

12.1510(17)

17.0579(16)

9.845(9)

12.0312(3)

10.7556(6)

α (deg)

90

90

90

84.3110(10)

86.109(15)

104.270(2)

100.2730(10

β(deg)

92.614(2)

92.652(7)

92.685(2)

81.020(2)

84.481(15)

99.452(2)

105.0200(10

γ(deg)

90

90

90

64.188(2)

89.695(11)

91.452(2)

112.3810(10

V (Å3)

837.67(17)

842.1(6)

842.6(2)

2381.2(4)

789.6(12)

945.70(4)

917.27(9)

2

2

2

1

1

1

2

1.736

1.727

1.726

1.885

1.895

1.793

1.672

µ (mm )

1.439

1.432

1.431

2.163

2.174

1.835

1.320

date collected

4789

4521

4690

13693

3994

7170

5255

unique date, Rint

3084, 0.0338

2689, 0.0480

2805, 0.0400

9737,0.0461

2756, 0.0351

3322, 0.0228

3748, 0.0111

completeness to theta = 26.49

99.3 %

100.0 %

99.8 %

98.5%

99.5 %

99.8 %

98.6 %

0.994

1.010

1.015

1.036

1.008

1.016

1.070

0.0390, 0.0671

0.0436, 0.0715

0.0405, 0.0742

0.0592, 0.1175

0.0539, 0.1215

0.0331, 0.0916

0.0358, 0.09

0.0600, 0.0770

0.0520, 0.0788

0.2316, 0.1621

0.0897, 0.1316

0.0397, 0.0959

0.0456, 0.10

Z −3

ρcalcd (g·cm ) –1

GOF on F

2

R1[a],

wR2[b](I>2σ

R1[a],

wR2[b]

a

(l))

(all data)

0.0548,0.0731 b

2

R1 = Σ (|F0|–|FC|) /Σ |F0|; wR2 = [Σw (|F0|–|FC|) /Σw

F02] 1/2.

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Scheme 1. Coordination modes of the 4-cppH3 ligands in 1–5.

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Figure 1. (a) ORTEP representation of a selected unit of R-1 (left) and S-1 (right). The thermal ellipsoids are drawn at the 50% probability level. All H atoms and lattice water molecules are omitted for clarity; (b) A 1D helix chain of R-1 (left) and S-1 (right) viewed along the b–axis; (c) The 2D layer molecular structure of R-1 via the π−π stacking interactions; (d) The π−π stacking interactions between the adjacent 2, 2'-bipy rings with the face-to-face distances of 3.695 and 3.781 Å.

Figure 2. ORTEP representation of a selected unit of 2. The thermal ellipsoids are drawn at the 50% probability level. All H atoms and lattice water molecules are omitted for clarity.

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Page 22 of 28

Figure 3. (a) The layer structure of 2 viewed in bc–plane; (b) The 3D supramolecular structure of 2 via the π−π stacking interactions between the adjacent 2, 2'-bipy rings with the face-to-face distances of 3.835–3.992 Å.


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Figure 5. (a) The layer structure of 4 viewed in ab–plane; (b) The 3D supramolecular structure of 4 via the π−π stacking interactions between the adjacent 1, 10-phen rings with the face-to-face distances of 3.397 Å.


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Figure 7. (a) A 1D double chain along the b–axis; (b) The 3D supramolecular structure of 5 via the π−π stacking interactions; (c) The C−H−π stacking interactions along a–axis; (d) The π−π stacking interactions along c–axis.

Figure 8. Solid-state CD spectra of R-1 and S-1.

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Figure 9. The SPS of 1 (a), 2 (b), 3 (c), 4 (d) and 5 (e); (f) A comparative SPS of 1−5.

Figure 10. The FISPS of 1 (a), 2 (b), 3 (c), 4 (d) and 5 (e).

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(a)

(b)

(c)

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(d)

Figure 11. Temperature-dependent magnetic susceptibilities of 1 (a), 2 (b),4 (c) and 5 (d) in the temperature range of 2–300 K under an applied field of 1000 Oe.

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"For Table of Contents Use Only" Chiral and Achiral Copper(II) Carboxyphosphonates Supramolecular Structure: Synthesis, Structures, Surface Photovoltage and Magnetic Properties Cheng-Qi Jiao,† Zhou Zhao,† Chao Ma,† Zhen-Gang Sun*,†, Da-Peng Dong*,‡, Yan-Yu Zhu,† and Jing Li†

Five chiral and achiral copper(II) carboxyphosphonates with 2D/3D supramolecular structures had been hydrothermally synthesized with different reaction temperature and pH value. It was noteworthy that 1 exhibited an unexpected 1D chiral helical chain by spontaneous resolution. More importantly, the homochiral copper(II) phosphonate (R-1 or S-1) could be obtained by the method of chiral induction through using the (+)-cinchonine or (-)-cinchonidine chiral inducer. Besides, the surface photovoltage (SPV) and magnetic properties of these compounds were also investigated.

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Chiral and Achiral Copper(II) Carboxyphosphonates Supramolecular

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