Anion-induced chiral binuclear and one-dimensional Ag(I) complexes: Synthesis, CD spectra and luminescence

    Anion-induced chiral binuclear and one-dimensional Ag(I) complexes: Synthesis, CD spectra and luminescence Jun Wang, Qi Qi, Lin Cheng, Hai-Yan Yu, Shao-Hua Gou PII: DOI: Reference:

S1387-7003(15)00201-4 doi: 10.1016/j.inoche.2015.05.013 INOCHE 5994

To appear in:

Inorganic Chemistry Communications

Received date: Revised date: Accepted date:

2 April 2015 30 April 2015 14 May 2015

Please cite this article as: Jun Wang, Qi Qi, Lin Cheng, Hai-Yan Yu, Shao-Hua Gou, Anion-induced chiral binuclear and one-dimensional Ag(I) complexes: Synthesis, CD spectra and luminescence, Inorganic Chemistry Communications (2015), doi: 10.1016/j.inoche.2015.05.013

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ACCEPTED MANUSCRIPT Anion-induced chiral binuclear and one-dimensional Ag(I) complexes: Synthesis, CD spectra and luminescence

Pharmaceutical Research Center, School of Chemistry and Chemical Engineering,

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Jun Wang,a,b,# Qi Qi,a,# Lin Cheng,a,b,* Hai-Yan Yua,b and Shao-Hua Goua,b,*

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Southeast University, Nanjing 211189, China

Jiangsu Province Hi-Tech Key Laboratory for Bio-medical Research, Southeast

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University, Nanjing 211189, China

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Abstract

Two new anion-induced chiral complexes have been synthesized via a chiral

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bis-chelating organic bridging ligand and changing the counteranions, in which 1

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displays a one-dimensional linear chain, while 2 is a binuclear structure. Circular

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dichroism (CD) spectra confirm that they are of structural chirality in the bulk samples. The luminescence properties indicate that they may have potential

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applications as optical materials. The present study demonstrates that the anion is a crucial factor for the construction of coordination polymers. Keywords: anion-induced; chiral Ag(I) complex; circular dichroism spectra; luminescence # 

The authors contributed equally to this work and should be considered as co-first authors. Corresponding author: [email protected] (L.Cheng), [email protected] (S.H. Gou). Tel/Fax: +86-025-83272381

The rational design and synthesis of chiral coordination polymers (CCPs) have attracted remarkable attention from chemists in view of their diverse structures and topologies as well as many potential applications [1,2]. Usually, these CCPs can be synthesized by the introduction of chiral ligands or chiral templates or chiral physical 1

ACCEPTED MANUSCRIPT environments, or via spontaneous resolution from achiral materials without any chiral auxiliaries [3,4]. The most straightforward method is the application of chiral bridging

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ligands, which will ensure the chirality of the resultant network structures. Chiral

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1,2-diaminocyclohexane derivatives are a type of chiral ligands with considerable interests because their sophisticated supramolecular combinations with metal ions have fascinating structural topologies and potential uses in asymmetric catalysis,

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molecular magnets, magnetic and optical switching, and biosimulation [5-7]. We have

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focused our interest on the synthesis of Ag(I) and Cd(II) CCPs by designing a series of (1R,2R)-N1, N2-bis(pyridinylmethyl)cyclohexane-1,2-diamine derivatives (Scheme

Scheme 1

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1a and 1b) [6,7].

On the other hand, how to rationally design and synthesize coordination polymers

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(CPs) with desired properties has been a long term challenge because their assembly process is highly influenced by many factors, in which the anion has been verified to

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be an important role, because it can be directly coordinated to the metal centers or only act as templates that preorganize the organic building blocks [8]. Among the anions, we focus our interests on the effects of the NO3- and ClO4- anions on the resultant structures of CCPs under the following considerations: (1) they are both monovalent anions but have different geometries with typical planar triangle and tetrahedron, respectively; (ii) they are preferable hydrogen bond acceptors but can form different numbers and directions of hydrogen bonds; (iii) in contrast to the halogen anions, their larger volume are more preferable to the crystallization of CCPs. As

a

part

of

our

continuous

work 2

in

developing

CCPs

with

chiral

ACCEPTED MANUSCRIPT 1,2-cyclohexanediamine derivatives, herein we have designed a flexible bis-chelating ligand,

N,N'-((1R,2R)-cyclohexane-1,2-diyl)di-2-naphthamide

[abbreviated

to

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(1R,2R)-cdna] (Scheme 1c) to allow the construction of Ag(I) CCPs based on the

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different anions (NO3- and ClO4-). It is of note that the ligand has the following features (Scheme 2): (i) it has an inherent chirality with two chiral carbon atoms in the 1,2-diaminocyclohexyl skeleton; (ii) the two carbonyl quinoline motities can easily

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chelate two metal ions, resulting that the ligand adopts bis-chelating fashion: (iii) it

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has flexibility over three planes, including those made by the two quinoline rings and the least square plane of rigid chairlike chiral cyclohexane-1,2-diamine motiety [9];

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(iv) the angles,  and , in the ligand can be tuned by changing the reaction

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conditions during the self-assembly, which may have an important effect on the

ClO4-),

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structures of the resultant CCPs. As expected, by changing the anions (NO3- and two

new

CCPs,

{[Ag((1R,2R)-cdna)]·NO3}n

(1)

and

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[Ag2((1R,2R)-cdna)2]·2ClO4·2H2O (2) were obtained, in which 1 is a chiral one-dimensional (1D) linear chain and 2 is a chiral binuclear complex. To our knowledge, this is the first example of CCPs based on the chiral (1R,2R)-cdna ligand. Scheme 2

Infrared spectra of 1 and 2 display strong peaks at 2935 and 2854 cm-1 for 1, as well as 2930 and 2859 cm-1 for 2, which can be attributed to the C-H stretching vibration [6,7]. Meanwhile, the strong broad absorption band at 1384 cm-1 for 1 is consistent with the vibration of the nitrate groups [6a], while the strong absorption band at 1087 cm-1 for 2 can be ascribed to the vibration of perchlorates [6b]. The strong absorption bands at 1644 cm-1 for 1 and 1655 cm-1 for 2 are in accordance with 3

ACCEPTED MANUSCRIPT the vibrations of C=O groups in the complexes [7b,10]. 1 crystallizes in tetragonal P4122 chiral space group, with the asymmetric unit of

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half of (1R,2R)-cdna ligand, half of Ag(I) and half of nitrate. Each Ag(I) ion displays

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a distorted tetrahedral geometry and is surrounded by two chelating carbonyl quinoline groups from two organic ligands with Ag-N and Ag-O distances of 2.235(6) and 2.482(7) Å, respectively. Meanwhile, each (1R,2R)-cdna ligand has a η4,μ2

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-tetradentate (cis bis-chelating) mode in 1 and bridges the adjacent Ag(I) ions to form

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a 1D linear chain running along the crystallographic a axis (Fig. 2) with the shortest intrachain Ag···Ag distance of 9.110(2) Å. In the ligand, the corresponding angles of

Fig. 1

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 and  are 78.44 and 73.05 °, respectively.

Complex 1 further forms a three-dimensional (3D) supramolecular network via

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N-H···O hydrogen bonds (N2···O3 = 3.002(7) Å) between the amines of the (1R,2R)-cdna ligands of the one-dimensional chains and free nitrate anions (Fig. S1).

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By replacing AgNO3 with AgClO4 during the synthesis of CCPs, a binuclear [Ag2((1R,2R)-cdna)2]·2ClO4·2H2O (2) was obtained (Fig. 2). Complex 2 crystallizes in an monoclinic system with the chiral space group P21, consisting of two Ag(I) ions, two (1R,2R)-cdna ligands, two uncoordinated perchlorates and two free water molecules in an asymmetric unit. There are two crystallographically independent Ag(I) ions in 2. Both Ag1 and Ag2 display a slightly distorted planar geometry, being surrounded by two chelating carbonyl quinoline groups from two organic ligands, in which Ag2 is very weakly coordinated by O2 atom with the Ag···O distance of 3.007(1) Å. Each (1R,2R)-cdna ligand in the dimmer also has a η4,μ2-tridentate 4

ACCEPTED MANUSCRIPT mode and the intradimer Ag···Ag distance is 3.790(1) Å, being much shorter than that in 1 (9.110(2) Å). In the ligand, the corresponding angles of  and  are 48.71-55.69

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and 9.50-10.31 °, respectively, also being much smaller than those in 1. Especially,

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the small  values of 9.50-10.31 ° in 2 show that the two carbonyl quinoline arms of the chiral ligand are nearly parallel to each other, which may be the main factor of the difference of the structures of 1 and 2. The axial position of the coordinated planar of

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each Ag(I) outside each dimer is weakly coordinated to the O(=C) atom from the

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adjacent dimer with Ag···O distance of 2.736(1) or 2.913(4) Å, resulting in a 1D linear chain along the crystallographic a axis (Fig. S2).

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Fig. 2

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One uncoordinated perchlorate and one free water molecule are linked via O-H···O hydrogen bonds (O2W···O7a 3.031(15), O2W···O8 2.849(14) Å, symmetry code: a,

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-1+x, y, z) into a 1D hydrogen bonding chain (Fig. S3a). These 1D coordination chains and hydrogen bonding chains, as well as other free perchlorates were finally

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constructed into a 3D supramolecular network by weak C-H···O hydrogen bonds between the perchlorates and the ligands, as well as between the free water molecules and the ligands with C···O distances of 2.847(9)-3.354(11) Å (Fig. S3b). The luminescent spectra of the ligand, as well as the complexes 1 and 2 in the solid state were investigated at room temperature, as shown in Fig. 3. The ligand exhibits an intense UV radiation with λmax at 421 nm upon excitation at 274 nm, which may be attributed to π–π* transition. Upon excitation at 260 nm, 1 exhibits similar purple luminescence emission at 427 nm, which may be attributed to intraligand luminescent emissions (π–π*) [11], while 2 exhibits a purple luminescence emission at 397 nm 5

ACCEPTED MANUSCRIPT upon excitation at 234 nm. Compared to the ligand and 1, the blue-shifted and weakened luminescence of 2 may be due to the different configurations of the ligand

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with different  and  values [7b].

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Fig. 3

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Circular dichroism (CD) spectroscopy is widely used in the construction of CCPs to check the chirality of bulk crystals [6-7,12]. The chiral nature of the ligand, 1 and 2

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was confirmed by solid state CD spectroscopy using powdered bulk crystals in a KBr matrix between 200 nm and 450 nm at room temperature (Fig. 4). The ligand, 1 and 2

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were found to display similar dichroic signals in their CD spectra with three positive

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Cotton effects at frequencies of 220, 307 and 347, and 226, 331 and 392, as well as

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220, 307 and 365 nm, and two negative Cotton effects at frequencies of 248 and 321, and 253 and 360, as well as 252 and 319 nm, which exhibits that the chirality of the

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compounds is in agreement with the chiral space groups of 1 and 2. Fig. 4

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In summary, we have synthesized two chiral complexes under the same conditions except for the different ions, in which 1 is a 1D chiral linear chain, while 2 is a chiral binuclear complex. CD spectra confirm that the bulk samples of 1 and 2 are chiral. The complexes display luminescent properties indicating that they may have potential application as optical materials. This work demonstrates that the anion is a very important factor for the construction of CCPs. Acknowledgements The authors are grateful to the financial support from National Natural Science Foundation of China (No. 21001024 and 21471031), the Natural Science Foundation

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ACCEPTED MANUSCRIPT of Jiangsu Province (BK2011587 and BK20131289), and the Teaching and Research Program for the Excellent Young Teachers of Southeast University (2242015R30026).

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Appendix A. Supplementary material

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Fig S1-3, XRD and X-ray crystallographic files in CIF format of 1 and 2. CCDC reference number: 1056872-1056873. The data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic

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Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; Fax: (internat.)

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+44-1223/336-033; E-mail: [email protected]]. Supplementary data associated with this article can be found, in the online version, at doi:xx.xx/j.inoche.xxxx.xx.xxx.

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References

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[1] (a) D. Bradshaw, J.B. Claridge, E.J. Cussen, T.J. Prior, M.J. Rosseinsky, Design,

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chirality, and flexibility in nanoporous molecule-based materials, Acc. Chem. Res. 38 (2005) 273-282.

AC

(b) J. Crassous, Chiral transfer in coordination complexes: towards molecular materials, Chem. Soc. Rev. 38 (2009) 830-845. (c) M. Yoon, R. Srirambalaji, K. Kim, Homochiral metal-organic frameworks for asymmetric heterogeneous catalysis, Chem. Rev. 112 (2012) 1196-1231. [2] (a) B. Kesanli, W.B. Lin, Chiral porous coordination networks: rational design and applications in enantioselective processes, Coord. Chem. Rev. 246 (2003) 305-326. (b) J. Zhang, S.M. Chen, T. Wu, P.Y. Feng, X.H. Bu, Homochiral crystallization of microporous framework materials from achiral precursors by chiral catalysis, J. Am. Chem. Soc. 130 (2008) 12882-12883.

7

ACCEPTED MANUSCRIPT (c) Y.H. Wen, T.L. Sheng, Z.H. Sun, Z.Z. Xue, Y.L. Wang, Y. Wang, S.M. Hu, X. Ma, X.T. Wu, A combination of the “pillaring” strategy and chiral induction: an approach

IP

T

to prepare homochiral three-dimensional coordination polymers from achiral

SC R

precursors, Chem. Commun. 50 (2014) 8320-8323.

[3] (a) M.H. Zeng, B. Wang, X.Y. Wang, W.X. Zhang, X.M. Chen, S. Gao, Chiral magnetic metal-organic frameworks of dimetal subunits: magnetism tuning by

NU

mixed-metal compositions of the solid solutions, Inorg. Chem. 45 (2006) 7069-7076.

MA

(b) F. Li, T.H. Li, X.J. Li, X. Li, Y.L. Wang, R. Cao, Synthesis of chiral coordination polymers by spontaneous resolution, Cryst. Growth Des. 6 (2006) 1458-1462.

D

(c) Y. Ma, Z.B. Han, Y.K. He, L.G. Yang, A 3D chiral Zn(II) coordination polymer

CE P

(2007) 4107-4109.

TE

with triple Zn-oba-Zn helical chains (oba = 4,4’-oxybis(benzoate)), Chem. Commun.

(d) Y.T. Wang, G.M. Tang, W.Z. Wan, Y. Wu, T.C. Tian, J.H. Wang, C. He, X.F. Long,

AC

J.J. Wang, S.W. Ng, New homochiral ferroelectric supramolecular networks of complexes constructed by chiral S-naproxen ligand, CrystEngComm 14 (2012) 3802-3812.

(e) X. Tan, J.X. Zhan, J.Y. Zhang, L. Jiang, M. Pan, C.Y. Su, Axially chiral metal-organic frameworks produced from spontaneous resolution with an achiral pyridyl dicarboxylate ligand, CrystEngComm 14 (2012) 63-66. [4] (a) Y.L. Zhou, F.Y. Meng, J. Zhang, M.H. Zeng, H. Liang, Mononuclear, tetra-, penta-3d

molecular

clusters

based

on

the

variability

of

SS-1,2-bis(1H-benzimidazole-2-yl)-1,2-ethanediol ligand arising from hydroponic and

8

ACCEPTED MANUSCRIPT hydrothermal conditions: structure, crystal growth, and magnetic properties, Cryst. Growth Des. 9 (2009) 1402-1410.

octanuclear

Ag(I)

coordination

networks

with

yellow

luminescence,

SC R

and

IP

T

(b) C.F. Yan, L. Chen, R. Feng, F.L. Jiang, M.C. Hong, Thermally stable helical chain

CrystEngComm 11 (2009) 2529-2535.

(c) Z.B. Han, B.Y. Li, J.W. Ji, Y.E. Du, H.Y. An, M.H. Zeng, A 3D chiral porous In(III)

NU

coordination polymer with PtS topological net, Dalton Trans. 40 (2011) 9154-9158.

MA

(d) T.H. Zhou, J. Zhang, H.X. Zhang, R. Feng, J.G. Mao, A ligand-conformation driving chiral generation and symmetry-breaking crystallization of a zinc(II)

D

organoarsonate, Chem. Commun. 47 (2011) 8862-8864.

TE

(f) Y.Q. Hu, M.H. Zeng, K. Zhang, S. Hu, F.F. Zhou, M. Kurmoo, Tracking the

CE P

formation of a polynuclear Co16 complex and its elimination and substitution reactions by mass spectroscopy and crystallography, J. Am. Chem. Soc. 135 (2013)

AC

7901-7908.

[5] (a) Z.W. Yang, C.F. Zhu, Z.J. Li, Y. Liu, G.H. Liu, Y. Cui, Engineering chiral Fe(salen)-based metal-organic frameworks for asymmetric sulfide oxidation, Chem. Commun. 50 (2014) 8775-8778. (b) S.Y. Lin, C. Wang, L. Zhao, J.K. Tang, Enantioselective self-assembly of triangular Dy3 clusters with single-molecule magnet behavior, Chem. Asian J. 9 (2014) 3558-3564. (c) D.P. Zhang, S.P. Zhuo, H.Y. Zhang, P. Wang, J.Z. Jiang, Synthesis, crystal structures and magnetic properties of mer-cyanideiron(III)-based 1D heterobimetallic

9

ACCEPTED MANUSCRIPT cyanide-bridged chiral coordination polymers, Dalton Trans. 44 (2015) 4655-4664. [6] (a) L. Cheng, L.M. Zhang, S.H. Gou, Q.N. Cao, J.Q. Wang, L. Fang,

IP

T

Metal-directed one-dimensional chiral zigzag chains and right-handed 61 helix with

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multiple chiral components: luminescence and NLO properties, CrystEngComm 14 (2012) 3888-3893.

(b) L. Cheng, L.M. Zhang, S.H. Gou, Q.N. Cao, J.Q. Wang, L. Fang, Two

NU

temperature-controlled chiral Ag(I) coordination polymers with dual chiral

MA

components: synthesis, luminescence and SHG properties, CrystEngComm 14 (2012) 4437-4443.

D

(c) L. Cheng, L.M. Zhang, Q.N. Cao, S.H. Gou, X.Y. Zhang, L. Fang,

TE

Temperature-induced chiral Ag(I) coordination polymers with structural variation

7502-7510.

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from 1D to 2D: synthesis, luminescence and SHG response, CrystEngComm 14 (2012)

AC

(d) L. Cheng, Q.N. Cao, X.Y. Zhang, S.H. Gou, L. Fang, A left-handed 21 helix with triple chiral components: synthesis, luminescence and SHG response, Inorg. Chem. Commun 24 (2012) 110-113. (e) L. Cheng, Q.N. Cao, L.M. Zhang, X.Y. Zhang, S.H. Gou, L. Fang, Two chiral mononuclear

and

one-dimensional

cadmium(II)

complexes

constructed

by

(1R,2R)-N1,N2-bis(pyridinylmethyl)cyclohexane-1,2-diamine derivatives: effect of positional isomerism, Solid State Sci. 16 (2013) 34-38. [7] (a) L. Cheng, J. Wang, X.Y. Zhang, S.H. Gou, L. Fang, A trinuclear copper(II) complex derived from a chiral [3 + 3] phenol-based macrocycle: synthesis, structure

10

ACCEPTED MANUSCRIPT and magnetic properties, Inorg. Chem. Commun. 47 (2014) 144-147. (b) L. Cheng, J. Wang, Q. Qi, X.Y. Zhang, H.Y. Yu, S.H. Gou, L. Fang,

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Temperature-induced one-dimensional chiral Ag(I) linear chains and left-handed 21

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helices: DFT studies, luminescence and SHG response, CrystEngComm 16 (2014)

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10056-10065.

(c) X.Y. Zhang, L. Cheng, J. Wang, S.H. Gou, L. Fang, Four chiral Ag(I) complexes with dual chiral components: effect of positional isomerism, luminescence and SHG

NU

response, Inorg. Chem. Commun. 40 (2014) 97-102.

(d) L. Cheng, J. Wang, H.Y. Yu, X.Y. Zhang, S.H. Gou, L. Fang, Five chiral Cd(II)

MA

complexes with dual chiral components: effect of positional isomerism, luminescence and SHG response, J. Solid State Chem. 221 (2015) 85-94. [8] (a) S.H. Zhang, L.F. Ma, H.H. Zou, Y.G. Wang, H. Liang, M.H. Zeng, Anion

D

induced diversification from heptanuclear to tetranuclear clusters: syntheses,

TE

structures and magnetic properties, Dalton Trans. 40 (2011) 11402-11409.

CE P

(b) S. Hou, Q.K. Liu, J.P. Ma, Y.B. Dong, Cd(II)-coordination framework: synthesis, anion-induced structural transformation, anion-responsive luminescence, and anion

AC

separation, Inorg. Chem. 52 (2013) 3225-3235. (c) Q.L. Zhang, G.W. Feng, Y.Q. Zhang, B.X. Zhu, Syntheses, structures, and luminescence properties of anion-controlled heterometal modular coordination polymers based on a metalloligand, RSC Adv. 4 (2014) 11384-11392. (d) Y.Q. Zhao, K. Yu, L.W. Wang, Y. Wang, X.P. Wang, D. Sun, Anion-induced supramolecular isomerism in two preyssler P5W30 polyoxometalate-based hybrid materials, Inorg. Chem. 53 (2014) 11046-11050. [9] M. Barz, M.U. Rauch, W.R. Thiel, New Schiff bases derived from trans-pyrazolylcyclohexanol: synthesis, co-ordination chemistry and structural

11

ACCEPTED MANUSCRIPT features, Dalton Trans. (1997) 2155-2161. [10] K. Zhou, C. Qin, X.L. Wang, K.Z. Shao, L.K.Yan, Z.M. Su, Unexpected 1D

IP

T

self-assembly of carbonate-templated sandwich-like macrocycle-based Ag20S10

SC R

luminescent nanoclusters, CrystEngComm 16 (2014) 7860-7864.

[11] (a) L. Cheng, H.Y. Hu, L.M. Zhang, S.H. Gou, A multifunctional three-dimensional uninodal eight-connected metal-organic framework based on

NU

pentanuclear cadmium subunits: New topology, fluorescent and NLO properties,

MA

Inorg. Chem. Commun. 15 (2012) 202-207.

(b) L. Cheng, Q.N. Cao, X.Y. Zhang, S.H. Gou, A 3-D lanthanide coordination

D

polymer constructed from biphenyl-2,2’,6,6’-tetracarboxylic acid: synthesis of a

TE

trinodal (3,4,5)-connected topology and luminescence, J. Coord. Chem. 66 (2013)

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481-489.

(c) F. Sun, Z. Yin, C.G. Sun, M. Kurmoo, M.H. Zeng, Design, structure and

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luminescent properties of a novel two-dimensional Cd(II) coordination polymer constructed

from

in

situ

generated

1-methyl-2-(3H-[1–3]triazol-4-yl)-1H-benzoimidazole, Inorg. Chem. Commun. 43 (2014) 78-80. [12] H.P. Wang, S.Y. Yin, M. Pan, K. Wu, L. Chen, Y.X. Zhu, Y.J. Hou, Circular dichroism enhancement by the coordination of different metal ions with a pair of chiral tripodal ligands, Inorg. Chem. Commun. 54 (2015) 92-95. Figure Captions Fig. 1. The 1D chiral linear chain of 1.

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Fig. 2. The chiral binuclear structure of 2.

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Fig. 3. Luminescent spectra of the ligand, 1 and 2 in the solid state at room temperature.

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Fig. 4. CD spectra of the ligand, 1 and 2 in the solid state at room temperature.

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Scheme 1. Structures of (1R,2R)-1,2-diaminocyclohexane derivatives that we have used to

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construct CCPs (a, b) and the chiral (1R,2R)-cdna ligand (c).

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Scheme 2. The bis-chelating fashion of (1R,2R)-cdna, in which  is the angle between the

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carbonyl quinoline plane and the least square plane of rigid chairlike cyclohexane-1,2-diamine

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motiety, and  is the angle between the two carbonyl quinoline planes in the ligand.

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Graphical abstract Two anion-induced chiral Ag(I) complexes have been synthesized by using a chiral bis-chelating organic bridging ligand and changing the counteranions. Their CD spectra and luminescence properties have been discussed.

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ACCEPTED MANUSCRIPT Highlights

• Two anion-induced chiral Ag(I) complexes have been synthesized.

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• The complexes display luminescent properties.

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• CD spectra of the bulk samples have been measured.

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