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Structural Variation and Luminescence Properties of Tri-, Di-nuclear Cu and Zn Complexes Constructed from a Naphthalenediol-based Bis(Salamo)-type Ligand II

II

Le Chen, Wen-Kui Dong, Han Zhang, Yang Zhang, and Yinxia Sun Cryst. Growth Des., Just Accepted Manuscript • Publication Date (Web): 01 May 2017 Downloaded from http://pubs.acs.org on May 2, 2017

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Crystal Growth & Design

Structural Variation and Luminescence Properties of Tri-, Di-nuclear CuII ZnII

and

Complexes

Constructed

from

a

Naphthalenediol-based

Bis(Salamo)-type Ligand Le Chen, Wen-Kui Dong,* Han Zhang, Yang Zhang, and Yin-Xia Sun

School of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, P.R.China

Corresponding authors. *E-mail: [email protected]. Fax: +86-931-4938703.

Abstract: Three trinuclear complexes constructed from a naphthalenediol-based bis(Salamo)-type tetraoxime (H4L1),

ligand

[Cu3(L1)(OAc)2]·CH3OH

(1),

[Zn3(L1)(OAc)2(CH3OH)2]·4CHCl3

1

(2)

and

2

[Cu2(L )Na(NO3)(CH3OH)] (3), and one dinuclear complex, [{Cu(L )}2] (4) based on an unexpected ligand H2L2 derive from the cleavage of H4L1 have been synthesized and characterized by X-ray diffraction analyses. Different anionic sources, transition metal salts and rationally controlled reaction conditions play important roles in the construction of resulting complexes with variable coordination geometries (coordination number ranges from 4 to 7) and four types of supramolecular network were controlled by non-covalent interactions, such as hydrogen bond, π···π stacking, C–H···π, Cu···π and halogen-related interactions. The fluorescence properties of H4L1 and its complexes were investigated and 2 exhibits unique bright cyan–yellow visible fluorescent emissions in different solvents.

Introduction Salen-type ligands and their metal complexes have been extensively investigated in modern coordination chemistry for several decades.1-7 Recently, a novel Salen-type analogue, Salamo, has been developed. The self-assembly of multinuclear complexes 3d, 3d-s, 3d-4f with versatile Salamo multidentate ligands has attracted much attention and exhibit unique fluorescent and magnetic properties and ions recognition, etc.8-13 Different anions and reaction conditions play crucial roles in influencing the preparation of the coordination compound.14-16 For example, different gadolinium(III)

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salt was utilized by Nabeshima’s group to obtain two dinuclear 3-MeOsalamo CuII–GdIII complexes. With the coordination of different anions, CuII and GdIII atoms adopt different geometries with different coordination numbers.16 In recent years, this group have focused on the conversion of an acyclic molecule (bis(Salamo)-type ligand) to the corresponding cyclic metallohost, which can afford a larger C-shaped O6 site on the metalation of the N2O2 sites and effectively control the guest recognition. Alkaline-earth metal (M = Ca, Sr and Ba) or rare-earth metal (M = Sc, Y and La-Lu) can selectively occupy the central O6 site to obtain a number of attractive heteronuclear 3d-s and 3d-4f complexes [Zn2M(L)]n+ and different metal cations display variable coordination numbers (Summarized in Scheme 1).16-18 Besides, the changes in terminal salicylidene moieties may lead to changes in the coordination capability of the ligands, thereby resulting in different crystal structures. This report is based on our two novel mono- and hepta-nuclear metalII complexes constructed from new unsymmetric and symmetric Salamo-type bisoxime ligands. The mononuclear metalII complex forms a novel 2:1 ligand to metal stoichiometry and stabilized by an intermolecular C–H···π interactions to form an infinite 1-D supramolecular chain, however, the heptanuclear metalII complex shows a novel 3:7 ligand to metal stoichiometry linked by a pair of intermolecular C–H···Cl hydrogen bond interactions into a 0-D dimer.19

Scheme 1. The Summarizing of the Compounds Constructed from the Bis(Salamo)-type Ligand As part of the continuing studies focused on the construction of multinuclear metal complexes,20 we designed and synthesized a new naphthalenediol-based polybrominated bis(Salamo)-type tetraoxime ligand (H4L1) with the inclusion of naphthalene ring. Two Salamo moieties are inclined to form multinuclear metal complexes with preferable fluorescent properties. In consideration of anion effects, metal cations and reaction conditions, tri-, di-nuclear CuII and ZnII complexes, [Cu3(L1)(OAc)2]·CH3OH (1), [Zn3(L1)(OAc)2(CH3OH)2]·4CHCl3 (2), [Cu2(L1)Na(NO3)(CH3OH)] (3) and [{Cu(L2)}2] (4) with variable coordination geometries were constructed. As far as we know, this is the first time that alkali metal would be introduced into the central cavity of the bis(Salamo)-type ligands.

Experimental Section General details. Borontribromide (99.9%), pyridiniumchlorochromate (98%), methyl trioctyl ammonium chloride


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(90%) and 3,5-dibromosalicylaldehyde ( ≥ 98%) were purchased from Alfa Aesar. Hydrobromic acid 33wt% solution in acetic acid was purchased from J&K Scientific Ltd. The other reagents and solvents were analytical grade reagents from Tianjin Chemical Reagent Factory and used as received. X-ray single-crystal structures were determined on a Bruker Smart APeX CCD area detector. Elemental (C, H and N) analyses were performed on GmbH VariuoEL V3.00 automatic elemental analyzer. Elemental analyses for Cu, Zn and Na were detected by an IRIS ER/S·WP–1 ICP atomic emission spectrometer. Melting points were measured by the use of a microscopic melting point apparatus made in Beijing Taike Instrument Limited Company and the thermometer was uncorrected. FT-IR spectra were recorded on a VERTEX70 FT–IR spectrophotometer with samples prepared as KBr (400–4000 cm-1). UV–Vis absorption spectra were measured on a Hitachi U-3900H spectrophotometer. 1H NMR spectra were determined by German Bruker AVANCE DRX-400 spectroscopy. Fluorescent spectra were taken on a LS-55 fluorescence photometer. FTICR-MS were obtained on a Bruker Daltonics APEX-II 47e spectrometer.

X-ray Crystallography. Intensity data for 1–4 were collected on a Bruker Smart 1000 CCD area detector with Mo Kα radiation (λ = 0.71073 Å). Reflection data were corrected for Lorentz and polarization factors and for absorption using the multi-scan method. The structures were solved by using the program SHELXL-97 and Fourier difference techniques, and refined by the full-matrix least-squares method on F2.21,22 Hydrogen atoms of methanol molecules (O13 and O14) in 2 were located in Fourier-difference maps and the other hydrogen atoms were placed in idealized positions. Crystallographic data together with refinement details for the complexes reported in this work are summarized in Table 1 and selected structural parameters of 1–4 are listed in Tables S1–S4.

Table 1. Crystal Data and the Structure Refinement for 1–4 Synthesis of Bis(Salamo) Ligands (H4L1). 1,2-Bis(aminooxy)ethane,

2-[O-(1-ethyloxyamide)]oxime-4,6-dibromophenol

2,3-dihydroxynaphthalene-1,4-dicarbaldehyde

were

synthesized

according

to

the

and reported

procedures.23,24 2,3-Dihydroxynaphthalene-1,4-dicarbaldehyde (354.1 mg, 1.0 mmol) was added to the ethanol solution of 2-[O-(1-ethyloxyamide)]oxime-4,6-dibromophenol (432.2 mg, 2.0 mmol). The suspension solution was stirred and refluxed at 45 ºC for 3 h and then yellowish solid of the bis(Salamo)-type tetraoxime ligand (H4L1) was obtained, which was collected by suction filtration (Scheme S1, Figure S1). Yield: 750.1 mg, 85%. M.p. 205–207 ºC. Anal. calcd for C30H24Br4N4O8: C,



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40.57; H, 2.72; N, 6.31%. Found: C, 40.54; H, 2.74; N, 6.38%. 1H NMR (400MHz, DMSO-d6, 298K): δ = 4.56 (s, 8H; OCH–H), 7.38–7.40 (m, 2H; Ar–H), 7.69 (s, 2H; Ar–H), 7.81 (s, 2H; Ar–H), 8.47–8.49 (m, 2H; Ar–H), 8.51 (s, 2H; N=C–H), 9.10 (s, 2H; N=C–H), 10.59 (s, 4H; O–H). IR (cm–1, KBr): 3307 (m), 3059 (m), 2927 (m), 2904 (m), 2854 (m), 1605 (m), 1433 (s), 1278 (m), 1212 (m). UV–Vis (CHCl3/CH3OH 3:2 v/v), λmax (nm) [εmax (dm3 mol–1 cm–1)]: 341 (1.88 × 104), 362 (1.57 × 104), 380 (1.66 × 104). ESI-MS (CHCl3/CH3OH, 1:1 v/v) m/z: 888.83 [H4(L1)H]+.

Synthesis of [Cu3(L1)(OAc)2]·CH3OH (1). A methanol solution (3 mL) of Cu(OAc)2·2H2O (5.96 mg, 0.030 mmol) was added to the suspension solution of H4L1 (8.80 mg, 0.010 mmol) in chloroform (3 mL) and stirred for 10 min. The mixture turned to transparent and was then filtered. Diffraction quality single crystals were obtained after a few days on slow evaporation of the solution in open atmosphere. Dark black blocks. Yield: 7.90 mg, 64%. Anal. calcd for C35H30Br4N4O13Cu3: C, 34.32; H, 2.47; N, 4.57; Cu, 15.56%. Found: C, 34.41; H, 2.49; N, 4.48; Cu, 15.48%. IR (cm–1, KBr): 3305 (m), 3060 (m), 2927 (m), 2855 (m), 1598 (m), 1550 (m), 1442 (s), 1399 (m), 1254 (m). UV–Vis (CHCl3/CH3OH 3:2 v/v), λmax (nm) [εmax (dm3 mol–1 cm–1)]: 386 (2.29 × 104). ESI-MS (CHCl3/CH3OH, 1:1 v/v) m/z: 1034.64 [Cu2Na(L1)]+, 1012.66 [Cu2(L1)H]+. Synthesis of [Zn3(L1)(OAc)2(CH3OH)2]·4CHCl3 (2). A solution (3 mL) of Zn(OAc)2·2H2O (6.57 mg, 0.030 mmol) in methanol was added to the suspension solution of H4L1 (8.84 mg, 0.010 mmol) in chloroform (3 mL). The resulting solution was stirred for 30 min and gradually turned to transparent. The mixture was filtered and allowed to stand in open atmosphere. After one week, some single crystals suitable for X-ray crystallographic analysis were obtained. Light yellow blocks. Yield, 7.89 mg, 45%. Anal. calcd for C40H38Br4Cl12N4O14Zn3: C, 27.61; H, 2.20; N, 3.22; Zn, 11.27%. Found: C, 27.66; H, 2.25; N, 3.17; Zn, 11.15%. 1H NMR (400MHz, DMSO-d6, 298K): δ = 1.86 (s, 6H; O=CCH2–H), δ = 4.33–4.69 (m, 8H; OCH–H), 7.15 (s, 2H; Ar–H), 7.42–7.93 (m, 4H; Ar–H), 8.42 (s, 2H; Ar–H), 8.76–9.55 (m, 4H; N=C–H). IR (cm–1, KBr): 3429 (m), 3071 (m), 2928 (m), 2855 (m), 1597 (m), 1447 (s), 1258 (m). UV–Vis (CHCl3/CH3OH 3:2 v/v), λmax (nm) [εmax (dm3 mol–1 cm–1)]: 369 (2.27 × 104), 420 (1.36 × 104). UV–Vis (DMSO), λmax (nm) [εmax (dm3 mol–1 cm–1)]: 369 (1.64 × 104), 411 (1.08 × 104). UV–Vis (methylbenzene), λmax (nm) [εmax (dm3 mol–1 cm–1)]: 373 (1.72 × 104), 422 (1.07 × 104). Synthesis of [Cu2(L1)Na(NO3)(CH3OH)] (3).


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A methanol solution (3 mL) of Cu(NO3)2·3H2O (3.60 mg, 0.015 mmol) was added to the mixture suspension solution of H4L1 (4.40 mg, 0.005 mmol) and NaOH (0.80 mg, 0.020 mmol) in chloroform (3 mL) and stirred for 10 min. The mixture turned to transparent and was filtered. Single crystals for X-ray crystallographic analysis were obtained by slow evaporation at room temperature. Dark brown blocks. Yield, 3.88 mg, 68%. Anal. calcd for C31H24Br4N5O12Cu2Na: C, 33.00; H, 2.14; N, 6.21; Cu, 11.26; Na, 2.04%. Found: C, 32.85; H, 2.10; N, 6.21; Cu, 11.18; Na, 1.96%. IR (cm–1, KBr): 3302 (m), 3062 (m), 2934 (m), 2856 (m), 1592 (m), 1446 (m), 1385 (s), 1318 (m), 1272 (m). UV–Vis (CHCl3/CH3OH 3:2 v/v), λmax (nm) [εmax (dm3 mol–1 cm–1)]: 380 (2.28 × 104). ESI-MS (CHCl3/CH3OH, 1:1 v/v) m/z: 1034.64 [Cu2Na(L1)]+, 1012.66 [Cu2(L1)H]+, 971.73 [CuNa(H2L1)]+. Synthesis of [{Cu(L2)}2] (4). A methanol solution (3 mL) of Cu(OAc)2·2H2O (2.98 mg, 0.015 mmol) was added to the mixture suspension solution of H4L1 (4.40 mg, 0.005 mmol) and NaOH (0.80 mg, 0.020 mmol) in chloroform (3 mL) and stirred for 10 min. The mixture turned to transparent and was then filtered. After one week in open atmosphere, diffraction quality single crystals were obtained on slow evaporation of the solution. Dark brown blocks. Yield 2.10 mg (52%). Anal. calcd for C18H14Br4N2O6Cu2: C, 26.99; H, 1.76; N, 3.50; Cu, 15.87%. Found: C, 27.11; H, 1.72; N, 3.43; Cu, 15.76%. IR (cm–1, KBr): 3071 (m), 2947 (m), 1581 (m), 1470 (s), 1382 (m), 1260 (m). UV–Vis (CHCl3/CH3OH 3:2 v/v), λmax (nm) [εmax (dm3 mol–1 cm–1)]: 375 (1.98 × 104). ESI-MS (CHCl3/CH3OH, 1:1 v/v) m/z: 400.81 [Cu(L2)H]+.

Results and Discussion The complexation of H4L1 with copper(II) acetate dihydrate gave homotrinuclear 1 under mild conditions. Homotrinuclear 2 was synthesized by the reaction of H4L1 with zinc(II) acetate dihydrate under the same reaction conditions as 1. Heterotrinuclear 3 was prepared by the reaction of H4L1 with NaOH and copper(II) nitrate trihydrate. Copper(II) acetate was used to prepare 4 instead of copper(II) nitrate under similar reaction conditions to obtain the complex with µ–acetato as the bridging ligand. However, the complexation of the ligand H4L1 with NaOH and copper(II) acetate is unstable, giving a new NO2 tridentate ligand (H2L2) thereby forming a dialkoxo-bridged dinuclear CuII complex 4.25,26 Sometimes alkaline condition could be the reason for cleavage reaction.27 In order to obtain the desired complex with NaI atom in the O4Br2 central cavity, NaOH was replaced by NaOAc. Disappointingly, single crystal of the 1a having same structure as 1 was obtained without the coordination of NaI atoms. Construction of 1–4 derived from a bis(Salamo)-type tetraoxime ligand is shown in Scheme 2.



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Scheme 2. Construction of 1–4 Derived from a Bis(Salamo)-type Tetraoxime Ligand

We have probed the nature of these complexes 1–3 in solution using spectroscopic titration experiments and high resolution ESI mass spectrometry studies. Spectroscopic titration experiments clearly indicate the reaction stoichiometry ratio of 1:3 as shown in the homotrinuclear CuII and ZnII complexes, although the ligand H4L1 only has two Salamo chelate moieties (Figure S8 and Figure S9). The ESI mass spectrum of heterotrinuclear CuII–NaI complex in MeOH/CHCl3 shows the fragment, 1034.64 [Cu2Na(L1)]+, which proves it shows the 1:3 ligand to metal stoichiometry in the solution (Figure S12). All the results agree with the following crystallographic analyses. Crystal structure of [Cu3(L1)(OAc)2]·CH3OH (1). The crystallographic data reveals that 1 crystallizes in the monoclinic system, space group P21/n, and the crystal structure indicates that 1 is a homotrinuclear complex. The asymmetric unit consists of one [Cu3(L1)(OAc)2] neutral molecule and one lattice methanol molecule. Two terminal CuII atoms (Cu1 and Cu3) are located at the N2O2 coordination spheres of Salamo moieties. Three phenoxo donors (O4, O5 and O8) of the salamo moieties from the completely deprotonated (L1)4- unit coordinate to the central Cu2, here, Cu2 is respectively bridged by Cu1 and Cu3 through two deprotonated phenoxo donors O4 and O5 and two syn-syn bridging acetate ions in a µ2-η1:η1 fashion.28-31 The two Cu···Cu distances between the terminal and central CuII atoms are 3.235(2) and 3.223(2) Å, respectively. The average lengths of the Cu–N and Cu–O bonds are in the ranges of 1.957(7)–2.223(8) and 1.900(6)–2.185(6) Å, respectively (Figure 1a). A semicoordinate Cu–O bonds (Cu2–O8 2.759(7) Å) was found in the central Cu2 due to the Jahn-Teller effect and steric hindrance effect. The resulting geometries of Cu1, Cu2 and Cu3 are all distorted square pyramidal geometries (Figure 1b), which were deduced by calculating the value of τ5 = 0.265 (Cu1), 0.010 (Cu2) and 0.123 (Cu3).32,33 As illustrated in Figure 1, two intramolecular hydrogen bonds (C9–H9B···O9 and C22–H22A···O12), one unusual π-type halogen bond C–Br···π interaction (C2–Br4···Cg13),34,35 and one π···π stacking interaction (Cg12···Cg15) are formed. Uncoordinated methanol molecule constructs two hydrogen bonds with one coordinated acetate group as donor, O13–H13···O10 and one imine group of an adjacent complex molecule as acceptor, C10–H10···O13 forming 1D hydrogen bonded chains. C–Br···π interactions (C29–Br5···Cg13) as a π-type halogen bond link the chains into a 2D layered supramolecular structure (Figure 2). The main interactions are listed in Table S5.


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Figure 1. (a) View of the coordination geometries of CuII centres with a labelling scheme (the lattice methanol molecule and some hydrogen atoms have been omitted for clarity). (b) The coordination polyhedra of Cu1 and Cu3 centres.

Figure 2. 2D supramolecular structure of 1, mediated by intermolecular C–H···O (dark red), O–H···O (dark red) and C–Br···π (pink) interactions. Crystal structure of [Zn3(L1)(OAc)2(CH3OH)2]·4CHCl3 (2). The X-ray crystal structure determination reveals 2 crystallizes in the monoclinic system, space group P21/c, which is a homotrinuclear complex. Two terminal ZnII atoms (Zn1 and Zn3) are located at the N2O2 coordination spheres of Salamo moieties, while the third one (Zn2) is located in the central cavity. Zn2 is bridged by Zn1 and Zn3 through two deprotonated phenoxo donors O4 and O5 and two syn-syn bridging acetate ions in a µ2-η1:η1 fashion. The bond distances between Zn1 and Zn2 (3.506(1) Å) are longer than that between Zn2 and Zn3 (3.533(1) Å). The average lengths of the Zn–N and Zn–O bonds are in the ranges of 2.072(4)–2.150(5) and 1.948(4)–2.154(4) Å, respectively (Figure 3a). Unlike 1, resulting geometries of the terminal Zn1 and Zn3 are both penta-coordinated with distorted trigonal-bipyramidal geometries (τ5 = 0.721 (Zn1) and 0.742 (Zn3)). Zn2 in the central cavity has an octahedral geometry with six oxygen-donor atoms including two µ2-acetato ligands and two solvent molecules. Oxygen-donor atoms of (L1)4- and µ2-acetato ligands form the equatorial plane and the oxygen-donor atoms of the methanol molecules are placed in the apical sites (Figure 3b). The main interactions in 2 are listed in Table S6. As presented in Figure S2, two coordinated methanols hydrogen atoms as donors form hydrogen bonds with phenoxo (O1 and O8), bromine (Br1 and Br4) atoms and acetate ions (O12 and O9). Oxygen atoms (O10 and O11) of acetate ions as acceptors form two hydrogen bonds with the protons (–C8H8B and –C23H23B) of ethylenedioxime carbons in each molecule. In addition, complex molecules form a dimer structure by a pair of intermolecular hydrogen bonds (C22–H22B···O14). Each dimer connect four other dimers in the direction of the four corners by two chloroform molecules via hydrogen bonds, C–H···π and C–Cl···π

(C34–H34C···Cl9,

C39–H39···O11,

C39–Cl9···Cg11,

C7–H7···Cl15

and

C40–H40···Cg10), forming a 2D layered supramolecular structure. In addition, the other two lattice chloroform molecules that do not participate in the 2D supramolecular structure respectively form C–H···π and C–Cl···π interactions with the complex molecule (Figure 4). Figure 3. (a) View of the coordination geometries of ZnII centres with a labelling scheme (the lattice chloroform molecules and hydrogen atoms have been omitted for clarity). (b) The coordination



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polyhedra of Zn1, Zn2 and Zn3 centres.

Figure 4. 2D supramolecular structure of 2, mediated by intermolecular C–H···O (dark red), C–H···Cl (dark red), C–H···π (pink) and C–Cl···π (pink) interactions (two lattice chloroform molecules, C37 and C38, without contribution to the 2D supramolecular stucture have been omitted for clarity). Crystal structure of [Cu2(L1)Na(NO3)(CH3OH)] (3). The crystallographic data reveals that 3 is a heterotrinuclear complex, crystallizing in the monoclinic system, space group P21/c. N2O2 sites of the Salamo moieties are also occupied by two CuII atoms (Cu1, Cu2), while the four phenoxo donors (O1, O4, O5 and O8) of the completely deprotonated ligand as a central O4 site coordinate to NaI atom instead of CuII atom. In addition, coordination interaction between Na1 and Br3 was observed. Meanwhile, one methanol molecule coordinates to Cu1 as the apical site of geometry and one nitrate ion bridges Cu2 with Na1 in a µ2-η1:η2 mode. (Figure 5a). Consequently, Cu1 and Cu2 are both penta-coordinated and adopt distorted square-pyramidal geometries with the two imino nitrogen atoms and the two phenolic oxygen atoms of N2O2 Salamo moieties forming the square base, which were deduced by calculating the value of τ5 = 0.221(Cu1) and 0.090(Cu2). Na1 is hepta-coordinated with geometry of distorted capped trigonal prism, which is coordinated with four phenoxo donors and two oxygen atoms of nitrate ions to confirm the structural trigonal prism (Figure 5b). The capped site is occupied by Br3 with the bond length (Na1–Br3, 2.765(3) Å). The distances between the terminal CuII and central NaI atoms, Cu1···Na1 (3.488(1) Å) is longer than that of Cu2···Na1 (3.263(1) Å) and Cu–N, Cu–O and Na–O bonds are in the ranges of 1.945(3)–2.010(3), 1.909(2)–2.403(3) Å and 2.324(2)–3.025(3), respectively. The main interaction information for 3 is presented in Table S7. Each molecule forms two intramolecular hydrogen bonds (C23−H23A···O12 and C8−H8A···O10) as shown in Figure 5. Two adjacent molecules are connected to each other via the hydrogen bonds (C21–H21···O10 and C16–H16···O10), resulting in a dimer structure, which are further connected by C–H···π (C14–H14···Cg9) forming an infinite 1D zip-like supramolecular structure (Figure 6). Two adjacent chains are further connected by hydrogen bonds involving the C–H groups, Br atoms (C9–H9A···Br4 and C22–H22A···Br2) and methanol molecule, nitrate ion (O12–H12···O11) to form a 3D framework, as shown in Figure S3. Figure 5. (a) View of the coordination geometries of CuII and NaI centres with a labelling scheme


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(some hydrogen atoms have been omitted for clarity). (b) The coordination polyhedra of Cu1, Cu3 and Na1 centres.

Figure 6. 1D supramolecular structure of 3, mediated by intermolecular C–H···O (dark red) and C–H···π (pink) interactions. Crystal structure of [{Cu(L2)}2] (4). 4 is a dinuclear complex that crystallizes in the monoclinic, space group P21/c. The asymmetric unit of 4 consists of two moieties, containing two independent CuII atoms and two unexpected deprotonated ligands (L2)2-. Complete molecules are gotten by symmetric operation (#1 -1/2-x, 1/2+y, 3/2-z;

#2

1/2+x, 1/2-y, 1/2+z) as shown in Figure 7. Each of the molecules has two tetra-coordinate

II

Cu centers, which are linked via two alkoxy bridges. The distances between the two central Cu metals are 2.990(1) and 2.997(1) Å, which are similar to the previous reports, and show weak interactions between them.36 Geometries of CuII atoms can be best described as slightly distorted square-planar symmetry with CuN1O3 coordination and deduced by using τ4 index,37,38 τ4 = 0.127 (Cu1) and 0.118 (Cu2). Moreover, 4 is stabilized by a pair of intermolecular hydrogen bonds (C8–H8A···O5 and C17–H17B···O1), linking both molecules into a 1D linear chain. Besides, this linkage is further stabilized by three types stacking between chelating ring and benzene ring (Cg4···Cg10, Cg4···Cg12 and Cg6···Cg10) (Figure 8a). Consequently, with the help of hydrogen bonds, Cu···π, and π···π stacking interactions, the crystal structure shows an assembly of 1D step-shaped chains (Figure 8b) and self-assembles into an alternative multilayer structure with the dihedral angles 44.79° between the adjacent layers. The main interactions for 4 are listed in Table S8. Figure 7. View of the coordination environment of CuII centres with a labelling scheme (hydrogen atoms have been omitted for clarity). Symmetry transformations used to generate equivalent atoms: #1

-1/2-x, 1/2+y, 3/2-z; #2 1/2+x, 1/2-y, 1/2+z.

Figure 8. (a) 1D supramolecular structure of 4, mediated by intermolecular hydrogen bonds (dark red), π···π (pink) and Cu···π (pink) interactions. (b) Step-shaped structure by Cu···π (pink) interactions. (b) View of the packing diagram.

The impact of anions, metal cations and reaction conditions on the structures. 1–4 have various structures depending on the anions and cations used under appropriate reaction conditions. The simplified spatial coordination models of 1–4 are given in Scheme 3. CuII atoms



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

(located at the N2O2 Salamo moieties) in 1 and 3 are penta-coordinated due to additional coordination by µ–acetato in 1, a methanol oxygen atom and bridging nitrate ion in 3. The position of two µ–acetato ligands of 1 is in the same side. Compared with Cu3, Cu1 does not adopt the geometry with N2O2 Salamo moieties as the square base. It is worth noting that there is only one bridging ligand in 3. The positions of nitrate ion and methanol molecule are in the opposite side, and Cu3 and Cu1 both adopt the geometry with N2O2 Salamo moieties as the square base. For 2, two terminal ZnII atoms are also penta-coordinated, but adopt trigonal-bipyramidal geometries with additional coordination by µ–acetate in opposite side. For the central metals, the central Cu2 of 1 is penta-coordinated, Zn2 of 2 is hexa-coordinated and Na1 of 3 is hepta-coordinated. In contrast, due to the changes of ligand, CuII atoms in 4 just adopt tetra-coordination with two unexpected deprotonated ligands. In consideration of Cu···π interactions (Cu1···Cg10 and Cu2···Cg4) between the CuII centers and adjacent rings, the CuII coordination geometries expand to distorted square-pyramidal.39 The coordination number of the central metal atoms from 4 to 7 was constructed in order to reflect the impact of anions, metal cations and reaction conditions on the structures.

Scheme 3. Simplified Spatial Coordination Models of 1–4

The central site of O4Br2 of complexes is larger than the Salamo moiety. In the presence of NaOH, NaI atom as a bigger atom instead of CuII atom occupies the central O4Br2 site in 3, whereas, an unexpected 4 was obtained instead of the desired complex where NaI atom coordinates with the central O4Br2 site. According to the reported literature, a plausible mechanism for CuII catalyzed cleavage of H4L1 under alkaline condition is shown in Scheme S2.26,36 Catalysis by CuII ions with the structural factors reduced the activation energy and resulted in cleavage of N–O bonds. It is evident from IR spectra that a new peak at 2204 cm-1 appears in the solid mixtures (in the process of synthesizing 3 and 4, product and byproduct were mixed together after reaction at room temperature) as a result of the conversion of CH=N into C≡N (Figure S14).36 Compared with the condition of synthesizing 4, 3 is comparatively stable in the solution and as the main product crystallized firstly. When NaOH was replaced by NaOAc to obtain the desired complex, disappointingly, single crystal of the complex 1a shows same structure as 1 (1: a = 11.3890(4), b = 17.2449(6), c = 20.6973(9), β = 95.240(3); 1a: a = 11.3859(5), b = 17.2356(8), c = 20.7140(12), β = 95.331(5)) without the complexation of NaI atom. For 1 and 2, the ligand coordinates to central metal atom through two donors. Two terminal salicylidene moieties are dangling because they do not simultaneously coordinate to the central metal atom. However, Na1 as a bigger atom occupied the central O4Br2 cavity, which forces the structure


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of the (L1)4- moiety into a C-shaped because of the effective coordination of the four oxygen donors in 3. Interestingly, one Br atom that seldom takes part in coordination coordinates to NaI atom owing to the spatial coordinative interaction. The dihedral angles α and α′ between the benzene rings and basal planes (naphthalene ring) are defined as shown in Figure S4. The terminal benzene rings of 1 are bent to the same side and the angles α and α′ are 93.50(23) and 84.73(29)°, respectively (Figure 9a). Compared with 1, the benzene rings of 3 are bent to different sides where the angles α and α′ equal 19.85 and -29.75° (Figure 9b), respectively. Consequently, it is evident that the adoption of NaI atom into the O4Br2 cavity could enhance the coplanarity of the complex by the effective coordination of the central donors.

Figure 9. (a) Dihedral angles between the basal planes (naphthalene ring, C11–C20) and the benzene rings (C1–C5 and C25–C30) of 1. (b) Dihedral angles between the basal planes (naphthalene ring, C11–C20) and the benzene rings (C1–C5 and C25–C30) of 3.

The existence of aromatic rings and solvent molecules in 1–4 could be attributed to robust various non-covalent forces, such as hydrogen-bonding, π···π stacking, C–H···π, and halogen-related interactions, leading to different supramolecular structures and dimensional variations.40-45 1−4 were developed by the different anions and metal cations under appropriate reaction conditions. Various complex structures display some different form of intramolecular interactions that help to create self-assembled assemblies. With the help of these non-covalent forces, 1-D to 3-D dimensional variation structures for 1−4 was constructed. Surprisingly, besides the common interactions, different molecule structures self-assembled into four types vital π-related interactions, C–Br···π for 1, C–Cl···π for 2, C–H···π for 3, and Cu···π for 4, which are compared and list in Table 2.

Table 2. Characteristic π-related Interactions in 1–4 and Relevant Parameter.

As a result, the orientation of both terminals may be influenced by the slight difference in the geometry of each metal because the phenoxo groups of the terminal salicylaldoxime moiety could not completely bound to the central metal, especially, if the radius of the central atom is very small. In addition, the different coordination of the anions and reaction conditions may also affect the coordination geometries and lead to structural diversification.

Luminescence properties. The normalized fluorescent spectra of the ligand H4L1 and its complexes were compared and shown



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

in Figure S5. In comparison with the corresponding H4L1, with the maximum emission wavelength at 470 nm, 1 exhibits hypochromatic shift with the maximum emission at 433 nm. 2 exhibits bathochromic shift with the maximum emission at 515 nm and the emission peak wavelength of 3 resembles that of the free ligand. Sometimes, fluorescence emission intensity decreases upon transition metal ion complex formation with the O and N atoms of the ligand.46 Compared with its ligand, 1, 2 and 3 exhibit decrease in photoluminescence intensities in DMSO (Figure S6a). A special blue and yellow luminescence for H4L1 and 2 were shown in DMSO upon irradiation with a 365 nm UV lamp respectively, whereas, when the fluorescence titration experiments were measured in CHCl3/MeOH in order to explore the interactions between H4L1 and Zn2+, the emission spectra of the free ligand H4L1 displays a weak fluorescence intensity at ca. 484 nm, however, a prominent fluorescence enhancement was observed with a significant hypsochromic shift from 484 to 496 nm upon coordination of Zn2+, thus giving a bright cyan light which may be denoted as CHEF (chelation-enhanced fluorescence) effect.47 In addition, solvent effect also brings pivotal effect to the photoluminescence of H4L1 and 2 (Figure S6b). The fluorescence picture of 1–3 and H4L1 in DMSO and 2 and H4L1 in CHCl3/MeOH upon irradiation with a 365 nm UV lamp is shown in Figure S6c. To study the solvent effects on fluorescence spectra of 2, the fluorescence spectra of 2 in a series of solvents were examined and are shown in Figure 10a. Interestingly, upon excitation at 365nm, different fluorescence intensities were produced by solvent effects, whereas, just two extreme colors with two special emission wavelengths (481 and 513 nm) were observed (Figure 10b). In TCM, THF, Acetone, MeCN and MeOH solvents, spectra exhibited emission with close peak wavelengths at 481 nm, which showed a special bright cyan luminescence; In DMF and DMSO solvents, close peak wavelengths at 513 nm were observed and a special yellow luminescence was shown due to the bathochromic shift of the fluorescence peaks. The results indicate that 2 is active in terms of photoluminescence with solvatochromic fluorescence property. The fluorescence property of 2 in the solid state was also studied. Compared with fluorescence spectra in solvents, 2 exhibits bathochromic shift with the maximum emission at 481 (TCM, THF, Acetone, MeCN & MeOH) and 513 (DMF & DMSO) nm by solvent effects, and 522 nm in the solid state (Figure 11). Figure 10. (a) The fluorescent (λex = 365 nm) spectra of 2 (1×10-4 M) in various solvents. Inset image: the fluorescence picture of 2 in various solvents upon irradiation with a 365 nm UV lamp. (b) The normalized fluorescent spectra of 2.

Figure 11. The fluorescence property of 2 in the solid state.


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A significant difference in fluorescent emission of 2 for toluene and DMSO solvents was observed. The fluorescence response of solutions with the mixture of toluene/DMSO in different proportions was investigated. Upon addition of a little DMSO without changing the property of maternal solvent (toluene), fluorescence intensity dramatically decreased with an increase in the concentration of DMSO in the range of 0–8.2%. The exponential decrease in response as a function of the DMSO concentration indicates that 2 has different forms of aggregate in different ratios of toluene/DMSO.48 Two molecules of 2 are linked through intermolecular interaction to form supramolecular dimer. Its aggregation–deaggregation process could be affected by the properties of solvent and the polarity and tendency of intermolecular interaction of solvents, which are important factors to control supramolecular aggregation. With the changes of DMSO concentration, fluorescence peaks appeared shifted towards the longer wavelength, which resulted in the bright cyan–yellow visible fluorescent emission (Figure 12).

Figure 12. Fluorescence spectra of 2 in solutions with the mixture toluene/DMSO in different concentration of DMSO. Inset image: linear response in function of DMSO concentration and the fluorescence picture of 2 (0–100% range, from left to right) upon irradiation with a 365 nm UV lamp.

The results of the fluorescence carried out in different solutions of Zn(II) complex indicate that 2 constructed by H4L1 shows solvatochromic fluorescence properties and exhibits an unusually bright cyan–yellow visible fluorescent emission in different solvents.

Conclusion A series of Salamo-type tetraoxime tri- and di-nuclear complexes 1−4 were developed by the anions and metal cations under appropriate reaction conditions. For the central metals, CuII atom of 1 is tetra-coordinated and ZnII atom of 2 is hexa-coordinated with square pyramidal and octahedral geometries, respectively, and NaI atom of 3 is hepta-coordinated with distorted capped trigonal prism geometry. CuII atoms in 4 are tetra-coordinated with two unexpected deprotonated ligands. The coordination number of the central metal atoms ranging from 4 to 7 was constructed and four types of supramolecular architectures ranging from 1−D chains to 3−D were controlled by abundant non-covalent interactions. Luminescent properties of the complexes were investigated and 2 exhibits solvatochromic fluorescence properties, which can display unique bright cyan–yellow visible fluorescent emissions in different solvents.



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Supporting Information Selected bond distances (Å) and angles (°) and the parameters of supramolecular interactions (Å, °) for 1–4. Synthetic route to the ligand H4L. The intramolecular interactions of 2. 3-D supramolecular structure of 3. The pre-defined dihedral angles α and α′ between the benzene rings and basal planes. Plausible mechanism for CuII catalyzed cleavage of H4L1. The normalized fluorescent spectra of 1–3 upon excitation at their maximum excitation wavelength. The fluorescent (λex = 365 nm) spectra of H4L1 and 1–3 in DMSO. 1H NMR spectroscopies of H4L1 and 2. Spectroscopic titration experiments of 1 and 2. ESI-MS spectra of H4L1 and 1–4. IR spectra of H4L1 and mixtures in the process of synthesizing 3 and 4. This information is available free of charge via the Internet at http://pubs.acs.org/. CCDC reference numbers 1506119 (1), 1519557 (2), 1519556 (3) and 1519555 (4). The data can be obtained via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB21EZ, U.K.; fax (+44) 1223-336-033; or e-mail [email protected].

Acknowledgment This project was financially supported by the National Natural Science Foundation of China (21361015).


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(22) Wang, B. J.; Dong, W. K.; Zhang, Y.; Akogun, S. F. Sens. Actuators, B 2017, DOI: http://dx.doi.org/doi:10.1016/j.snb.2017.02.154. (23) Akine, S.; Taniguchi, T.; Dong, W. K.; Masubuchi, S.; Nabeshima, T. J. Org. Chem. 2005, 70, 1704–1711. (24) Tran, H. A.; Collins, J.; Georghiou, P. E. New J. Chem. 2008, 32, 1175–1182. (25) Akine, S.; Akimoto, A.; Shiga, T.; Oshio, H.; Nabeshima, T. Inorg. Chem. 2008, 47, 875–885. (26) Bu, X.; You, X.; Meng, Q. Comments Inorg. Chem. 2006, 9, 221–244. (27) R. B. Grossman, The Art of Writing Reasonable Organic Reaction Mechanisms, University of Kentucky, USA, 2002. (28) Li, Y.; Guo, Y.; Tian, H.; Hu, P.; Sun, Z.; Ma, Y.; Li, L.; Liao, D. Inorg. Chem. Commun. 2014, 43, 135–137. (29) Si, C. D.; Hu, D. C.; Fan, Y.; Wu, Y.; Yao, X. Q.; Yang, Y. X.; Liu, J. C. Cryst. Growth Des. 2015, 15, 2419–2432. (30) Si, C. D.; Hu, D. C.; Fan, Y.; Dong, X. Y.; Yao, X. Q.; Yang, Y. X.; Liu, J. C. Cryst. Growth Des. 2015, 15, 5781–5793. (31) Dong, X. Y.; Si, C. D.; Fan, Y.; Hu, D. C.; Yao, X. Q.; Yang, Y. X.; Liu, J. C. Cryst. Growth Des. 2016, 16, 2062–2073. (32) Addison, A. W.; Rao, T. N.; Reedijk, J.; van Rijn, J.; Verschoor, G. C.; J. Chem. Soc., Dalton Trans. 1984, 1349–1356. (33) Konno, T.; Tokuda, K.; Sakurai, J.; Okamoto, K. I. Bull. Chem. Soc. Jpn. 2000, 73, 2767–2773. (34) Mazik, M.; Buthe, A. C.; Jones, P. G. Tetrahedron 2010, 66, 385–389. (35) Zeng, Y. L.; Zhang, X. Y.; Li, X. Y.; Zheng, S. J.; Meng, L. P. Int. J. Quantum Chem. 2011, 11, 3725–3740. (36) Ma, J. C.; Dong, X. Y.; Dong, W. K.; Zhang, Y.; Zhu, L. C.; Zhang, J. T. J. Coord. Chem. 2015, 69, 149–159. (37) Yang, L.; Powell, D. R.; Houser, R. P. Dalton Trans. 2007, 9, 955–964. (38) Seth, P.; Ghosh, S.; Figuerolab, A.; Ghosh, A. Dalton Trans. 2014, 43, 990–998. (39) Paraginski, G. L.; Hörner, M.; Back, D. F.; Beck, J.; Rolina, A. J. J. Mol. Struct. 2015, 1104, 79–84. (40) Dong, W. K.; Li, X. L.; Wang, L.; Zhang, Y.; Ding, Y. J. Sens. Actuators, B 2016, 229, 370–378. (41) Dong, W. K.; Ma, J. C.; Zhu, L. C.; Sun, Y. X.; Akogun, S. F.; Zhang, Y. New J. Chem. 2016, 40, 6998–7010. (42) Song, X. Q.; Peng,Y. J.; Chen, G. Q.; Wang, X. R.; Liu, P. P.; Xu, W. Y. Inorg. Chim. Acta 2015, 427, 13–21.


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(43) Liu, P. P. ; Sheng, L.; Song, X. Q.; Xu, W. Y.; Liu, Y. A. Inorg. Chim. Acta 2015, 434, 252–257. (44) Zhang, H.; Xu,Y. L.; Wu, H. L.; Aderinto, S. O.; Fan, X. Y. RSC Adv. 2016, 6, 83697–83708. (45) Wu, H. L.; Wang, H.; Wang, X. L.; Pan, G. L.; Shi, F. R.; Zhang, Y. H.; Bai, Y. C.; Kong, J. New J. Chem. 2014, 38, 1052–1061. (46) Ozkan, G.; Kose, M.; Zengin, H.; Mckee, V.; Kurtoglu, M. Spectrochim. Acta, Part A 2015, 150, 966–973. (47) Huston, M. E.; Haider, K. W.; Czarnik, A. W. J. Am. Chem. Soc. 1988, 110, 4460–4462. (48) Meng, Q. H.; Zhou, P.; Song, F.; Wang, Y. B.; Liu, G. L.; Li, H. CrystEngComm 2013, 2786–2790.



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Table 1. Crystal Data and the Structure Refinement for 1–4 1

2

3

4

Formula

C35H30Br4N4O13Cu3

C40H38N4O14Br4Cl12Zn3

C31H24Br4N5O12Cu2Na

C18H14Br4N2O6Cu2

M (g·mol-1)

1224.89

1739.89

1128.26

801.03

Crystal system

monoclinic

triclinic

monoclinic

monoclinic

Space group

P21/n

P-1

P21/c

P21/c

a [Å]

11.3890(4)

14.4114(5)

9.7566(7)

7.6801(8)

b [Å]

17.2449(6)

14.6798(6)

19.1674(14)

31.084(3)

c [Å]

20.6973(9)

17.1629(7)

19.2224(14)

9.4196(12)

α [°]

90

66.452(4)

90

90

β [°]

95.240(3)

89.680(3)

96.397(2)

93.363(10)

90

72.039(3)

90

90

V [Å ]

4048.0(3)

3137.4(2)

3572.4(4)

2244.9(4)

T [K]

295.42(10)

293(2)

293(2)

290.83(10)

3.7770–22.6120

3.561–26.022

2.125–25.499

3.39–26.02

4, 2.010

2, 1.842

4, 2.098

4, 2.370

µ [mm ]

5.579

4.254

5.748

9.053

F(000)

2396

1704

2200

1528

Index ranges

-14 ≤ h ≤ 14

-17 ≤ h ≤ 17

-11 ≤ h ≤ 11

-9 ≤ h ≤ 8

-21 ≤ k ≤ 12

-18 ≤ k ≤ 18

-23 ≤ k ≤ 16

-38 ≤ k ≤ 25

-25 ≤ l ≤ 20

-19 ≤ l ≤ 21

-23 ≤ l ≤ 23

-11 ≤ l ≤ 8

Completeness (%) (θ)

99.8 (25.50)

99.4 (25.50)

98.9 (25.499)

99.8 (26.00)

Reflections collected/unique

16145/7944

22046/12276

25138/6565

8871/4428

Data/restraints/parameters

7944/12/536

12276/6/758

6565/0/497

4428/0/289

Goodness-of-fit on F

1.037

1.014

1.025

1.025

Rint

0.0569

0.0409

0.0415

0.0647

0.0714/0.1468

0.0526/0.1122

0.0302/0.0709

0.0816/0.1691

1.446, -0.884

0.841, -0.994

1.217, -0.755

1.710, -0.971

γ [°] 3

θ range [°] -3

Z, Dcalc [g·cm ] -1

2

R1a

/wR2b

[I > 2σ(I)] -3

(∆ρ)max, min [e·Å ] a

R1 = Σ||Fo| - |Fc||/Σ|Fo||. b wR2 = {Σw(Fo2 - Fc2)2/Σ[w(Fo2)]2}1/2.

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Table 2. Characteristic π-related Interactions in 1–4 and Relevant Parameter. Complex

1

2

3

4

Dimension

2-D

2-D

3-D

1-D

Characteristic π-related interactions

C–Br···π C29–Br5···Cg13

C39–Cl9···Cg11

C14–H14···Cg9

d(D–X)

1.903(10)

1.751(7)

d(X···π)

3.921(4)

d(D···π) ∠D–X···π

C–Cl···π a

C–H···π b

Cu···π c

Cu1···Cg10d

Cu2···Cg4e

0.93

––

––

3.382(5)

2.95

––

––

4.432(11)

4.368(7)

3.582(3)

3.523

3.571

92.5(3)

112.7(3)

127

––

––

Symmetry codes 1/2-x, -1/2+y, 3/2-z 1-x, 1-y, 1-z 1-x, 1-y, -z x, y, z 1+x, y, z a Cg13 are the centroids of atoms C11\C12\C13\C14\C15\C20. b Cg11 are the centroids of atoms C25–C30. c Cg9 are the centroids of atoms C1–C6. d Cg4 are the centroids of atoms Cu1\O1\C1\C6\C7\N1. e Cg10 are the centroids of atoms C10–C15.

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FIGURE LEGENDS Scheme 1. The Summarizing of the Compounds Constructed from the Bis(Salamo)-type Ligand

Scheme 2. Construction of 1–4 Derived from a Bis(Salamo)-type Tetraoxime Ligand

Scheme 3. Simplified Spatial Coordination Models of 1–4 Figure 1. (a) View of the coordination geometries of CuII centres with a labelling scheme (the lattice methanol molecule and some hydrogen atoms have been omitted for clarity). (b) The coordination polyhedra of Cu1 and Cu3 centres.

Figure 2. 2D supramolecular structure of 1, mediated by intermolecular C–H···O (dark red), O–H···O (dark red) and C–Br···π (pink) interactions. Figure 3. (a) View of the coordination geometries of ZnII centres with a labelling scheme (the lattice chloroform molecules and hydrogen atoms have been omitted for clarity). (b) The coordination polyhedra of Zn1, Zn2 and Zn3 centres.

Figure 4. 2D supramolecular structure of 2, mediated by intermolecular C–H···O (dark red), C–H···Cl (dark red), C–H···π (pink) and C–Cl···π (pink) interactions (two lattice chloroform molecules, C37 and C38, without contribution to the 2D supramolecular stucture have been omitted for clarity). Figure 5. (a) View of the coordination geometries of CuII and NaI centres with a labelling scheme (some hydrogen atoms have been omitted for clarity). (b) The coordination polyhedra of Cu1, Cu3 and Na1 centres.

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Figure 6. 1D supramolecular structure of 3, mediated by intermolecular C–H···O (dark red) and C–H···π (pink) interactions. Figure 7. View of the coordination environment of CuII centres with a labelling scheme (hydrogen atoms have been omitted for clarity). Symmetry transformations used to generate equivalent atoms: #1

-1/2-x, 1/2+y, 3/2-z; #2 1/2+x, 1/2-y, 1/2+z.

Figure 8. (a) 1D supramolecular structure of 4, mediated by intermolecular hydrogen bonds (dark red), π···π (pink) and Cu···π (pink) interactions. (b) Step-shaped structure by Cu···π (pink) interactions. (b) View of the packing diagram.

Figure 9. (a) Dihedral angles between the basal planes (naphthalene ring, C11–C20) and the benzene rings (C1–C5 and C25–C30) of 1. (b) Dihedral angles between the basal planes (naphthalene ring, C11–C20) and the benzene rings (C1–C5 and C25–C30) of 3. Figure 10. (a) The fluorescent (λex = 365 nm) spectra of 2 (1×10-4 M) in various solvents. Inset image: the fluorescence picture of 2 in various solvents upon irradiation with a 365 nm UV lamp. (b) The normalized fluorescent spectra of 2.

Figure 11. The fluorescence property of 2 in the solid state.

Figure 12. Fluorescence spectra of 2 in solutions with the mixture toluene/DMSO in different concentration of DMSO. Inset image: linear response in function of DMSO concentration and the fluorescence picture of 2 (0–100% range, from left to right) upon irradiation with a 365 nm UV lamp.

Wen-Kui Dong et al.



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Scheme 1.

Wen-Kui Dong et al.


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O O

Cu

N

OO

O

N O

N O

O

Cu

Cu O Br

O

N

O

O

N

Cu

O O

O O

Br

Br

O

Cu N O O Na O O HOMe Br Br Br Complex 3

Cu(OAc)2

Cu(NO3)2 / NaOH

Br

Br

N O Br

O N

OH

N O HO

O N

OH

HO

Br

O

N

N

N Cu

O

O Na

O

O

Cu N O

Br O N

O

O

O

Br

Cu

Cu O

Br Br

N O

O

Br Br

Br

H 4L 1

Zn(OAc)2

Cu(OAc)2 / NaOH

O

O

O

Br

Br Complex 1

Cu(OAc)2 / NaOAc

N

N

Br

Br

Complex 4

O O N N O O O O Zn Zn N N Zn OO O O OO HOMe Br Br HOMe Complex 2

O N OH

Br

OH H 2L2

Br

Scheme 2.

Wen-Kui Dong et al.


Br


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

N

O

O

Cu

Complex 4

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Cu

O

O

N

4 O

N

N O

Cu

Cu N O

Complex 1

O

O

Cu

N

O

O

O

5

O sov

N Complex 2

Zn N

O

O

O Zn

O

O

N

Zn N

O O

sov

6

O N O O

O

N Complex 3

Cu N

O O

N Cu

Na

O

N

Br sov

5

Scheme 3.

Wen-Kui Dong et al.


7

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Figure 1.

Wen-Kui Dong et al.



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Figure 2.

Wen-Kui Dong et al.


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Figure 3.

Wen-Kui Dong et al.



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Figure 4.

Wen-Kui Dong et al.


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Figure 5.

Wen-Kui Dong et al.



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Figure 6.

Wen-Kui Dong et al.


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Figure 7.

Wen-Kui Dong et al.



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Figure 8.

Wen-Kui Dong et al.


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Figure 9.

Wen-Kui Dong et al.



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Figure 10.

Wen-Kui Dong et al.


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Figure 11.

Wen-Kui Dong et al.



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Figure 12.

Wen-Kui Dong et al.


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For Table of Contents Use Only

Structural Variation and Luminescence Properties of Tri-, Di-nuclear CuII and

ZnII

Complexes

Constructed

from

a

Naphthalenediol-based

Bis(Salamo)-type Ligand Le Chen, Wen-Kui Dong,* Han Zhang, Yang Zhang, and Yin-Xia Sun

School of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, P.R.China

Corresponding authors. *E-mail: [email protected]. Fax: +86-931-4938703.

Graphical Abstract In consideration of anion effects, metal cations and reaction conditions, tri-, di-nuclear CuII and ZnII complexes constructed from naphthalenediol-based bis(Salamo)-type ligand with variable coordinated geometries were designed and constructed. 2 exhibits unique bright cyan–yellow visible fluorescent emissions in different solvents.


and Dinuclear CuII and ZnII Complexes ... - ACS Publications

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