Tuning Photoluminescent Properties of Silver(I)-Based Coordination

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Tuning Photoluminescent Properties of Silver(I)-Based Coordination Networks through their Supramolecular Interactions Catiucia R. M. O. Matos, Flavia G. A. Monteiro, Fabio da S. Miranda, Carlos B. Pinheiro, Andrew D. Bond, and Célia M. Ronconi Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b01082 • Publication Date (Web): 28 Sep 2017 Downloaded from http://pubs.acs.org on October 4, 2017

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Crystal Growth & Design

Tuning Photoluminescent Properties of Silver(I)Based Coordination Networks through their Supramolecular Interactions Catiúcia R. M. O. Matos,† Flávia G. A. Monteiro,‡ Fabio da S. Miranda,† Carlos B. Pinheiro,§ Andrew D. Bond,|| Célia M. Ronconi*,† †

Universidade Federal Fluminense (UFF), Departamento de Química Inorgânica, Niterói, RJ,

Brazil ‡

Instituto Federal de Educação, Ciência e Tecnologia (IFRJ), Unidade Maracanã, Rio de

Janeiro, RJ, Brazil §

Universidade Federal de Minas Gerais (UFMG), Departamento de Física, Belo Horizonte, MG,

Brazil ||

Department of Chemistry, University of Cambridge, Cambridge, UK

ABSTRACT: Eight novel luminescent silver(I)-based coordination networks have been selfassembled from two flexible dicyanomethylene ligands bearing diethylene (L1) and triethylene glycol (L2) spacers and silver salts (AgClO4 or AgBF4) in dichloromethane/toluene or dichloromethane/benzene solvents. Single-crystal X–ray diffraction reveals a variety of geometries around the silver(I) ion, resulting in mono, bi and tetranuclear networks with rare topologies. The coordination networks show 2D architectures through coordination of the cyano

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and glycolic groups to the silver(I) ions. The 3D supramolecular arrangement is formed through weak π···π and Ag···π interactions as well as hydrogen bonds between water molecules and ClO4— and BF4— counterions. The silver(I)-based coordination networks display green to yellow emissions in the solid state, with quantum yields (Φem) varying from 1.1 to 8.5 %. The emission properties are attributed to intraligand charge transfer and metal-perturbed intraligand transitions. Supramolecular interactions, such as Ag···π and π···π interactions play an import role in the photophysical properties of these compounds.

INTRODUCTION Silver(I)-based coordination networks (CNs) have attracted much attention due to their structural diversity and remarkable properties, such as luminescence,1–4 antibacterial,5–13 catalytic,14,15 photocatalytic,16 conductivity,17 and gas sorption.18–20 These properties can be modulated via ligand flexibility or rigidity, functional groups, as well as by the coordination sphere around silver(I) centers. Fluorescent CNs are of particular interest because they have potential applications in light-emitting diodes, sensors, and biomedicine.21–24 The majority of silver(I) complexes or CNs have weak luminescence at room temperature due to the heavy atom effect of silver(I), which produces strong spin-orbital coupling.25–27 Notably, low-energy emissions of monomeric or polymeric silver(I) complexes at room temperature emerge from intraligand (IL) charge transfer rather than on the silver(I) ions; whereas high-energy emissions are related to metal-perturbed intraligand transitions (MPIL), e.g. Ag(I) → π*.28–35 The presence of argentophilic interactions Ag(I)···Ag(I) [4d → 5s] can also enhance the intensity and/or redshift emission.36–41


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The self-assembly of flexible or rigid multitopic ligands containing pyridyl,42–47 imidazole,48– 50

carboxylate51–54 functional groups and silver(I) ions has been extensively investigated.

However, the assembly of flexible multitopic ligands bearing cyano groups and silver(I) ions has been much less explored.55,56 Among cyano ligands, those possessing the electron-withdrawing dicyanomethylene groups have strong absorption and electron mobility.57,58 As part of our ongoing research on the supramolecular assemblies of cyano compounds,59–61 we have previously investigated the crystal packing and the photophysical properties of a series of dicyanomethylene compounds (Fig. 1) obtained by Knoevenagel condensation reaction between the appropriated aldehyde and malononitrile.61 The compounds exhibit 3D crystal packing structures dictated by a number of weak hydrogen interactions and showed an interesting evenodd effect. They have been demonstrated to be bright blue emitters in solution and in the solid state. The electronic structures and transitions assignments of the dicyanomethylene compounds were obtained from time-dependent density functional theory (TD-DFT) calculations and showed that the [(2-methoxyphenyl)methylene]propanedinitrile fragment controls their photophysical properties.

Fig. 1. Dicyanomethylene ligands used to synthesize silver(I)-based coordination networks.

Herein, we report the synthesis of a series of silver(I)-based CNs by the self-assembly of the dicyanomethylene ligands (Fig. 1) bearing diethylene (L1) and triethylene glycol (L2) spacers


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and silver salts (AgClO4 or AgBF4). The effect of the glycol spacer length, counterions and solvents on the structures of silver(I)-based CNs and the relationship with their photophysical properties in the solid state are evaluated and discussed. We found out the presence of supramolecular interactions, such as Ag(I)···π and π···π stacking interactions can tune their emissions from green to yellow. In addition, coordinated water molecules to the silver(I) ion can affect their emission intensities.

RESULTS AND DISCUSSION Synthesis and characterization of the silver(I)–based coordination networks (CNs). The CNs were synthesized at 25 oC using a metal-ligand molar ratio of 2:1 in each case (Scheme 1). The reactions were carried out using a slow diffusion method, in which a low polarity solvent (C6H6 or PhMe) containing the desired silver salt was layered onto a higher polarity solvent (CH2Cl2) containing the dicyanomethylene ligands L1 and L2. All CNs were obtained after approximately seven days as yellow air–stable crystals. Due to their mild light sensitivity, the compounds were stored in the dark. The FTIR spectra of all compounds and the assignments of the main absorptions are provided in Fig. S1, S2 and Table S1 (Supporting Information). The wavenumbers of the ν(C≡N) mode of the free dicyanomethylene ligands are in the range of 2221–2227 cm–1 (Table S1, Supporting Information). The coordination of the cyano groups to silver(I) ions in the CNs did not significantly change the wavenumbers of the ν(C≡N) mode from those of the corresponding ligands. These results indicate an end-on coordination of the silver(I) ions to the nitrogen atom of the cyano group62 and are consistent with previously reported values of ν(C≡N) for CNs


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containing polydentate cyano ligands.63,64 Strong absorption bands in the range of 1083–1085 cm–1 are assigned to ν(ClO4–) and ν(BF4–) anions.65

Scheme 1. Schematic Representation of the Syntheses of Silver(I) Coordination Networks

Powder X-ray diffraction (PXRD) studies were carried out to verify the phase purity of the CNs (Fig. S3−S6, Supporting Information). PXRD patterns of all compounds are in good agreement with the simulated patterns generated from the crystal structures, indicating that their crystal structures are truly representative of the bulk crystal products. PXRD shows that the selfassembly of the L1 and L2 ligands with silver(I) ions (AgClO4 and AgBF4) using different solvents (CH2Cl2/C6H6 and CH2Cl2/PhMe) (Scheme 1) yielded eight crystalline CNs, of which some are isostructural (Table 1). We discuss below the crystal structures of the three nonisostructural CNs (1.B, 1.T, 3.B). The crystal and refinement data for 1.B, 2.B, 1.T, 3.B and 4.B


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as well as selected bond distances/angles are summarized in Tables S4−S15 (Supporting Information). 66


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Table 1. Coordination Networks (CNs) Synthesized in this Work ligand

CN

isostructural CN

powder X-ray diffraction analysis

1.B

2.B and 2.T

Fig. S3

1.T

-

Fig. S4

3.B

3.T, 4.B and 4.T

Fig. S5 and S6

L1

L2

Structural analyses of the coordination networks obtained from ligand L1. The reaction of L1 with AgClO4 in C6H6/CH2Cl2 and PhMe/CH2Cl2 solvents and AgBF4 in C6H6/CH2Cl2 and PhMe/CH2Cl2 solvents yielded four coordination networks (CNs) named 1.B, 1.T, 2.B and 2.T (Scheme 1, Table 1). The mononuclear CNs 1.B, 2.B and 2.T are isostructural, with closely comparable unit-cell dimensions (Table S2 and Fig. S3, Supporting Information). They are described by the triclinic space group P1. The bond distances and angles for each silver(I) center in 1.B and 2.B are shown in Tables S4 to S6 (Supporting Information). The CN 1.T is tetranuclear with symmetry described by the monoclinic space group P21/c (Table S2 and Fig. S4, Supporting Information). The structure of 1.B, as a representative of the isostructural series (Table 1) and 1.T will be further described. Structure of 1.B. The asymmetric unit of 1.B contains one silver(I) ion, one ligand L1, one H2O molecule, and a free ClO4– anion (Fig. S7a, Supporting Information). The asymmetric unit of the isostructural CN 2.B is shown in Fig. S7b (Supporting Information) for comparison. The silver(I) ion is five-coordinated in a distorted square-pyramidal geometry (Fig. 2a and b) rather than a


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trigonal bipyramid geometry, as shown by the resulting structural index (τ = 0.27).67 In this geometry, the silver(I) center is coordinated to three cyano groups from three different L1 ligands, an oxygen atom (O2) from the glycolic spacer of the ligand and one H2O molecule (O4). Comparing the ligand L1 conformation in the CN 1.B to the free ligand L1, 61 its structure is drastically changed upon coordination to Ag1 (Fig. S8, Supporting Information). The V-shaped arrangement of the phenyl rings observed in the free ligand L1 is no longer present in the 1.B structure. The CN 1.B contains two silver(I)-macrocycles, a small 12-membered and a large 22membered ring (Fig. S9, Supporting Information). The presence of silver(I)-based macrocycle motifs have been found in some CNs constructed with flexible and elongated ligands. These motifs can provide affinity to guest molecules through coordination or supramolecular interactions.68 The distances Ag1···Ag1 in the 12-membered and in the 22-membered rings are ca. 7.24 Å and 10.4 Å, respectively; thus, no argentophilic interactions are present in these silver macrocycles. The crystal packing of 1.B consists of 2D chains formed by the coordination of silver(I) ion to the cyano groups (Fig. 2c). Topological analysis69 using ToposPro 5.0.2.1 was carried out considering silver(I) ion as a node. The extended network is a 9-connected uninodal net with point (Schläfli) symbol of {315.418.53}, resulting in a two-dimensional 63Ia topology (Fig. 2d),70 which is not listed in the Reticular Chemistry Structure Resource (RCSR).


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(a)

(b)

(c)

(d)

Fig. 2. (a) Molecular geometry and atomic labeling scheme used in the description of 1.B. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen atoms are omitted for clarity. (b) View of the coordination environment around silver(I) ion represented as a polyhedral model. (c) 2D Network of 1.B. (d) The simplified 63Ia topology.


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Structure of 1.T. The reaction of L1 with AgClO4 in CH2Cl2/PhMe yielded the tetra-nuclear coordination network 1.T (Table S2, Supporting Information). The bond distances and angles for each silver(I) center are shown in Tables S7 to S9 (Supporting Information). The asymmetric unit contains two ligands L1, four silver(I) centers, three coordinated H2O molecules, and four coordinated ClO4– anions (Fig. S10, Supporting Information). Both Ag1 and Ag2 centers are penta-coordinated leading to distorted trigonal bipyramidal geometries with structural index τ = 0.73 and 0.57,67 respectively (Fig. 3a). In this geometry, each Ag center is coordinated by two cyano groups from two different ligands L1, one oxygen atom from the glycolic spacer and two oxygen atoms from ClO4– anions. The Ag3 center is tetra-coordinated in a square planar geometry (τ = 0.03)71 by two cyano groups from two different ligands L1 and two oxygen atoms from two water molecules. The Ag4 center has a trigonal planar geometry coordinated by two cyano groups from two different ligands L1 and one oxygen atom from an H2O molecule (Fig. 3a). The V-shaped arrangement of the phenyl rings observed in the free L1 ligand61 is also no longer present in the 1.T structure (Fig. S11, Supporting Information). The glycolic spacer of the ligand L1 and six cyano groups from three different ligands L1 links Ag1 and Ag3 centers and generate a 32-membered silver(I)-macrocycle (Fig. 3b). The 32-membered silver(I)-macrocycle extends in one dimension resulting in a twisted 1D chain along the c axis (Fig. 3c). In addition, one ligand L1, which is present in another identical 1D chain, is threaded through the 32membered silver(I)-macrocycle (Fig. 3b and c), resulting in a 2D layered polycatenated structure (1D + 1D → 2D) along the bc plane (Fig. 3c). The entangled structure is stabilized by Ag···π interactions between Ag3 or Ag4 and the phenyl ring of the ligand (Fig. S12, Supporting Information). The distances and other geometrical parameters of the Ag···π interaction are listed


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in Table S16 (Supporting Information) and are consistent with the values reported in the literature.72,73 Interestingly, CN 1.T contains two crystallographically independent 2D polycatenated layers in the bc planes. One layer contains penta-coordinated Ag1 centers and tetra-coordinated Ag3 centers; whereas the other layer has penta-coordinated Ag2 centers and tri-coordinated Ag4 centers. Ag3 and Ag4 occupy corresponding positions within the 2D layers, but apparently can accommodate either tri- or tetra-coordination. The 2D polycatenated layers are stacked along the a axis by π···π stacking interactions through the centroids formed between the phenyl rings of L1 (Fig. S13, Supporting Information). The centroid-to-centroid (Cg1···Cg2) distance is 3.570(4) (Fig. S13 and Table S17 Supporting Information) and are consistent with the values reported in the literature.74 Topological analysis of the 1.T resulted in the same point (Schläfli) symbol for both 2D crystallographically independent 2D polycatenated layers with point (Schläfli) symbol of {314.410.54}{319.422.54}, in which each 2D layer is a 2-nodal net (Fig. 3d). To the best of our knowledge, we have not observed any similar polycatenated topology in the literature.


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(a)

(b)

(c)

(d)

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Fig. 3. (a) Molecular geometry and atomic labeling scheme used in the description of 1.T. Displacement ellipsoids are drawn at the 50% probability level. (b) Ball stick representation of the ligand L1 threaded through the 32membered silver(I)-macrocycle. (c) a-Axis view of 1D + 1D → 2D polycatenated structure. (d) The simplified topology of 1.T.


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Structural analysis of the CNs obtained from ligand L2: 3.B. The self-assembly of the ligand L2 with AgClO4 or AgBF4 in mixed solvent (CH2Cl2/C6H6 or CH2Cl2/PhMe) resulted in four binuclear isostructural coordination networks 3.B, 3.T, 4.B and 4.T (Scheme 1, Table 1, Fig. S5 and S6, Supporting Information) with symmetry described by the triclinic space group P1 (Table S3, Supporting Information). Only the structure 3.B will be discussed as follows. The asymmetric unit of 3.B is formed by two silver(I) centers (Ag1 and Ag2), one ligand L2, one coordinated ClO4– anion, one uncoordinated ClO4–, one water molecule and one solvent molecule (C6H6) (Fig. S14a, Supporting Information). The asymmetric unit of 4.B and 3.B are overlaid for comparison (Fig. S14b, Supporting Information). The ion Ag1 is five-coordinated in a distorted square-pyramidal geometry rather than trigonal bipyramid geometry as shown by the resulting structural index (τ = 0.27).66 The geometry is formed by the coordination of two oxygen atoms from the glycolic spacer, two cyano groups from two L2 ligands and two ClO4– anions (Fig. 4a). The ion Ag2 is in a tetrahedral geometry (τ = 0.74) formed by the coordination of two cyano groups from two L2 ligands, one oxygen atom from ClO4– anion and a molecule of C6H6 (Fig. 4a). The Ag···π interaction distance between Ag2 and the centroid (C27-C32) is 3.401(3) Å (Fig. S15a, Supporting Information) and is consistent with the values reported in the literature for this interaction.74 CN 3.B presents a 22-membered silver(I)-macrocycle formed by the coordination of two oxygen atoms from the glycolic spacer to two Ag1 centers and two cyano groups from two L2 ligands (Fig. S15a, Supporting Information). In the silver(I)-macrocycle there are two different π···π stacking interactions (Fig. S15b, Supporting Information). One interaction is between the phenyl rings of the ligand L2 and the second one is between the phenyl ring and the double bond of the dicyanomethylene fragment. The distances and the parameters of the π···π interactions in


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3.B are listed in Tables S17 and S18 (Supporting Information). The 22-membered silver(I)macrocycle extends in a 2D network (Fig. 4b and c). The same π···π interactions are present in CN 4.B (Fig. S16 and Tables S17 and S18, Supporting Information). (a)

(b)

(c)

(d)

Fig. 4. (a) Molecular geometry and atomic labeling scheme used in the description of 3.B. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen atoms are omitted for clarity. (b) Representation of the extended 22-membered silver(I)-macrocycle in the 3.B structure. (c) a-Axis view of the 2D structure. (d) Topological representation of the 2D 2-nodal net.


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Topological analysis of 3.B reveled a two-dimensional 2-nodal net with point (Schläfli) symbol of {312.47.58.6}{318.420.57} (Fig. 4d). CN 4.B is isoreticular to 3.B (Fig. S17, Supporting Information).

Solid-state photophysical properties. We have previously investigated the photophysical properties of the dicyanomethylene ligands used in this work.61 Their absorption and emission properties were interpreted aided by TD-DFT calculations at B3LYP/6-31G(d,p) level. The UVVis absorption bands of the ligands L1 and L2 involve the e1g orbital of the phenyl ring (HOMO) and the double bond of the methylenic group (LUMO), therefore, a π–π* transition. The HOMO-LUMO electronic transition increased the C7–C8 bond length and decreased both the C1–C2 and C6–O11 bond lengths (Fig. 5).61

Fig.

5.

Selected

bonds

involved

in

the

electronic

transition

of

the

fragment

[(2-

methoxyphenyl)methylene]propanedinitrile.

Normalized UV-Vis absorption spectra measured by diffuse reflectance spectroscopy of the ligands L1 and L2 and their respective CNs are shown in Fig. S20 and S21 (Supporting Information). The CNs show absorption bands in the region of 229 to 239 nm, 293 to 311 nm, 370 to 410 nm. The UV-Vis absorption spectra of silver(I)-based CNs are similar to the ligands


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L1 and L2 in the solid state; therefore, these electronic transitions in silver(I)-based CNs might be

related

to

π–π*

transition

involving

the

orbitals

of

the

[(2-

methoxyphenyl)methylene]propanedinitrile fragment of the ligands (Fig. 5). Furthermore, a small shoulder at approximately 420 to 453 nm for all silver(I)-based CNs, which is not present in the ligands, can be assigned as metal-perturbed intraligand π−π* transition.75 The bandgap values for the silver(I)-based CNs were calculated from the absorption edges (using the inflection point in the first derivatives of the absorption spectra).76 The bandgap values of all CNs decreased compared to the ligands L1 and L2 in the solid state (Table 2), indicating the semiconducting nature of these materials improved upon coordination to silver(I) ions.


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Table 2. Photophysical Properties of the Ligands L1 and L2 and their Respective Ag (I) Based CNs compounds

λexc/nm

λem/nm

∆λem/nma

∆λ/eVb

band gap/eVc

quantum yield (Φ)/%

a

L1

382

465

-

14.93

2.69

2.0

1.B

378

492

27

10.87

2.39

4.4

1.T

380

526

61

8.492

2.41

1.3

2.B

370

494

29

9.998

2.50

7.1

2.T

373

490

25

10.59

2.50

8.5

L2

380

454

-

16.75

2.68

4.1

3.B

378

522

68

8.610

2.43

2.3

3.T

372

521

67

8.321

2.43

1.6

4.B

396

553

99

7.897

2.45

2.4

4.T

391

535

81

8.610

2.45

1.1

The difference between the maximum emission of the ligands and their respective silver(I)-based CNs. bThe Stokes

shift. cEstimated from the optical absorption edge.

Fig. 6 shows the normalized photoluminescence (PL) spectra in the solid state at room temperature, the Commission Internacionale d’Eclairage (CIE) chromaticity diagram and the digital photographs of the ligands L1 and L2 and their respective CNs irradiated (λ = 365 nm) in an UV viewing cabinet. The photophysical data for all compounds are summarized in Table 2.


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(a)

(b)

(c)

(d)

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Fig. 6. (a and b) The solid-state emission spectra obtained at room temperature of the ligands L1 and L2 and their respective silver(I)-based CNs. (c) CIE Chromaticity diagram. (d) Digital photographs of the ligands and their respective silver(I)-based CNs irradiated with UV light (λ = 365 nm).

The PL spectra of the silver(I)-based CNs and the ligands L1 and L2 have similar patterns (Fig. 6a and b), indicating that the electronic transitions of the CNs might be associated with


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intraligand (IL) charge transfer π*→π due to the [(2-methoxyphenyl)methylene]propanedinitrile fragment (Fig. 5). Analyzing the CIE chromaticity (Fig. 6c) diagram of silver(I)-based CNs in the solid state at room temperature, we can clearly see two groups of light emitters, one green and another yellow; whereas the ligands L1 and L2 are blue emitters. An emission band at approximately 670 nm for all CNs is due to light scattering of the crystalline solid samples. The green emitters, 1.B, 2.B, 1.T and 2.T are obtained from the ligand L1. The CN 1.T is a polycatenated tetranuclear network; whereas the series 1.B, 2.B and 2.T are isostructural mononuclear networks (Fig. 2 and Fig. S3 and S7, Supporting Information). The emission of 1.T is red-shifted and its fluorescence is quenched (Φ = 1.3%) compared to the isostructural series (Fig 6a and Table 2) and to the ligand L1. The presence of Ag(I)···π and π···π stacking interactions, as well as coordinated water molecules in both Ag3 and Ag4 centers of 1.T (Fig. 3a) can decrease the energy emission and quantum yield via vibrational motion, leading to nonradiative energy transfer.77 Interestingly, the isostructural series 1.B, 2.B and 2.T do not show either Ag(I)···π interactions or water molecules bound to the silver(I) centers (Fig. 2 and Fig. S3 and S7, Supporting Information). All yellow emitters, 3.B, 3.T, 4.B and 4.T obtained from the ligand L2, show Ag(I)···π and π···π stacking interactions in their structures, as well as coordinated water molecules in their silver(I) centers, which can explain their red-shifted energies and lower quantum yields compared to the CNs obtained from the ligand L1 (1.B, 2.B and 2.T ), in which these interactions are not present.77,78 Therefore, the emission of the silver(I)-based CNs synthesized in this work can be tuned from green to yellow when supramolecular interactions, such as Ag···π and π···π stacking interactions and coordinated water molecules to the silver centers are present in their


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structures. Additionally, even thought the compounds 3.B, 3.T, 4.B and 4.T are isostructural they do not have the same composition, e.g. the counter ions and crystallized solvent molecules in their structures are not the same (Scheme 1). The small differences in their compositions might affect the supramolecular interactions around the fluorophore, therefore, resulting in slightly different emissions (Table 2 and Fig. 6).79,80

Conclusions Eight new silver(I)-based CNs have been constructed by self-assembly from two flexible dicyanomethylene ligands (L1 and L2) with two different silver salts (AgClO4 and AgBF4) and solvent mixtures (CH2Cl2/C6H6 or CH2Cl2/PhMe). Single crystal X-ray diffraction revealed 2D structures for all CNs. Also Ag···π and π···π stacking interactions between the aromatic units were observed in the supramolecular array of the CNs 1.T, 3.B, 3.T, 4.B and 4.T. The crystal data show that the compounds synthesized from the ligand L1 and AgClO4 or AgBF4 salts using CH2Cl2/C6H6 or CH2Cl2/PhMe resulted in isostructural mononuclear CNs 1.B, 2.B and 2.T. Using the ligand L1 and AgClO4 in CH2Cl2/PhMe, however, a tetranuclear CN 1.T is formed. The isostructural series 1.B, 2.B and 2.T revealed 63Ia topology, whereas 1.T resulted in a 2D layered polycatenated structure (1D + 1D → 2D) with unique topology. Silver(I)-based CNs constructed from the longer ligand L2 using AgClO4 or AgBF4 in CH2Cl2/C6H6 or CH2Cl2/PhMe resulted in isostructural binuclear CNs with the same structure and topology. Solid-state absorption spectra of all silver(I)-based CNs might be related to π–π* electron transfer involving the orbitals of the [(2-methoxyphenyl)methylene]propanedinitrile fragment of the ligands as well as metal-perturbed intraligand π−π* transition.


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Upon excitation, the silver(I)-based CNs displayed green (1.B, 2.B, 2.T and 1.T) and yellow emissions (3.B, 4.B, 3.T and 4.T). Redshift features for 1.T and the binuclear CNs 3.B, 4.B, 3.T and 4.T were attributed to the presence of Ag···π and π···π stacking interactions. This result suggests that these supramolecular interactions might decrease the emission energy by vibrational motion, compared to the isostructural series 1.B, 2.B, and 2.T obtained from the ligand L1, in which these interactions are not present. In addition, water molecules coordinated to the silver(I) centers in the structures of 1.T, 3.B, 4.B, 3.T and 4.T might explain their lower quantum yields compared to the isostructural series 1.B, 2.B and 2.T obtained from the ligand L1, in which these molecules are not present.

EXPERIMENTAL SECTION Materials and Methods. All chemicals were used without further purification: AgClO4 (Acros organics), AgBF4 (Aldrich), CH2Cl2 (Vetec), PhMe (Vetec) and C6H6 (Riolab). Melting points were determined on a Thermo Scientific 9100 and were reported without corrections. Elemental analyses were conducted using a Perkin Elmer CHN 2400 analyzer at the Analytical Center, Institute of Chemistry, USP-São Paulo, Brazil. Fourier transform infrared spectra (FTIR) were recorded from 4000–500 cm—1 as KBr pellets on a Varian FTIR–7000. Diffuse reflectance UVVisible spectra of the samples diluted in BaSO4 (Aldrich) were recorded on a Cary 5000 UVVIS-NIR absorption spectrometer. Emission spectra of the solid samples were acquired on a FLS980 Fluorescence Spectrometer from Edinburgh Instruments and fluorescence quantum yields were determined using an integration sphere. X-ray Crystallography. Single crystal X-ray diffraction data for coordination networks 1.B, 2.B, 3.B were carried out on a Nonius KappaCCD diffractometer using graphite-Enhance Source


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MoKα radiation (λ = 0.7107 Å) at room temperature. Data integration and scaling of the reflections were performed with EvalCCD.81 Unit-cell parameters were obtained using Dirax/lsq.82 Single crystal X-ray diffraction data for extended network 1.T was recorded on a Bruker APEX-II CCD diffractometer at 250.05(10) K. The data integration and scaling of the reflections and cell refinement were performed using APEX-II software (Bruker 2012, APEX-II . Bruker AXS Inc., Madison, Wisconsin, USA). No absorption correction was employed in the data sets. The space group identification for all compounds was done with the XPREP program.83 The structures were solved by direct methods using SIR-92.84 For each compound, the positions of all, except hydrogen, atoms could be unambiguously assigned on consecutive difference Fourier maps. Refinements were performed with SHELXL-2013 based on F2 through a full-matrix least squares routine. The hydrogen atoms were added to the structure in idealized positions and were further refined according to the riding model.85 For organic moieties C–H = 0.97 Å and Uiso(H) = 1.2 Ueq(C) for methylene groups and aromatic carbon atoms. Methyl groups C–H = 0.97 Å and Uiso(H) = 1.5 Ueq(C). Crystal data as well as details of data collection and refinement are shown in Table S2 and S3. Powder XRD patterns were collected on a Bruker D8 Advance X-ray diffractometer equipped with a LynxEye detector and using CuKα radiation (λ = 1.54056 Å). The scanning rate was fixed at 0.2°/s with a step size of 0.02° with 2θ ranges from 5 to 50° for phase identification. Synthesis. The syntheses of dicyanomethylene ligands L1 and L2 used in this work to obtain the coordination networks (CNs) were previously described.61 All CNs were prepared using a similar procedure. A solution of AgX (0.1370 mmol, X = ClO4— and BF4— in 8 mL of C6H6 or PhMe was layered onto a solution of the ligands (0.0658 mmol ) in 8 mL CH2Cl2. In each case the


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mixture was allowed to diffuse into each other in a capped vial for 7 days at room temperature in the dark. Fig. S1-S2 and Table S1 (Supporting Information) show the FTIR. 1.B. M.p.: 128-130 °C. Elemental analysis calculated for {[AgClO4(L1)(H2O)]}n: 45.34% C; 3.17 % H and 8.81% N; found: 45.91% C; 2.30% H and 8.77% N. FTIR data (KBr, cm-1): 3485(w), 2941(w), 2928(w), 2226(m), 1579(s), 1483(vs), 1442(m), 1362(m), 1313(m), 1260(vs), 1139(s), 1116(s), 1082(vs), 1048(s), 957(m), 860(w), 748(w) 739(w), 614(w). (Fig. S1, Supporting information). 1.T. M.p.: 131°C. Elemental analysis calculated for {[Ag4(ClO4)4(L1)2(H2O)3]}n: 33.83% C; 2.48 % H and 6.58% N; found: 36.51% C; 2.74% H and 7.00% N. FTIR data (KBr, cm-1): 3479(w), 3039(w), 2951(w), 2937(w), 2908(w), 2843(w), 2225(m), 2216(w), 1585(s), 1485(s), 1450(m), 1361(w), 1313(m), 1261(s), 1139(s), 1085(s), 1047(m), 956(w), 858(w), 748(m), 626(m), 601(w). (Fig. S1, Supporting information). 2.B. M.p.: decomposes before melting. Elemental analysis calculated for {[AgBF4(L1)(H2O)]}n: 46.26% C; 3.24% H and 8.99% N; found: 46.05% C; 3.37% H and 9.12% N. FTIR data (KBr, cm-1): 3573(w), 3514(w), 3350(w), 3245(w), 3039(w), 2952(w), 2908(w), 2843(w), 2248(m), 2225(m), 1580(s), 1485(s), 1451(m), 1363(m), 1313(m), 1260(s), 1140(s), 1084(s), 1047(s), 957(m), 859(w), 748(m), 625(w), 615(w). (Fig. S1, Supporting information). 2.T. M.p.: decomposes before melting. Elemental analysis calculated for {[AgBF4(L1)(H2O)]}n: 46.26% C; 3.24% H and 8.99% N; found: 41.75% C; 3.17% H and 8.77% N. FTIR data (KBr, cm-1): 3513(w), 3037(w), 2951(w), 2935(w), 2906(w), 2843(w), 2227(m), 2216(w), 1579(s),


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1485(s), 1450(s), 1361(m), 1313(m), 1261(s), 1161(w), 1139(s), 1112(s), 1083(s), 1047(s), 857(w), 742(s), 615(m). (Fig. S1, Supporting information). 3.B. M.p.: 128-129 °C. Elemental analysis calculated for {[Ag2ClO4(L2)(H2O)(C6H6)]ClO4}n: 39.82% C; 3.13 % H and 5.80% N; found: 39.60% C; 3.10% H and 5.61% N. FTIR data (KBr, cm-1): 3043(w), 2968(w), 2947(w), 2916(w), 2900(w), 2877(w), 2834(w), 2216(s), 1579(s), 1564(w), 1480(m), 1448(m), 1366(m), 1314(m), 1296(w), 1256(s), 1138(s), 1085(s), 1048(s), 956(m), 875(m), 845(w), 788(w), 735(w), 613(m) (Fig. S2, Supporting information). 3.T. M.p.: 88°C. Elemental analysis calculated for {[Ag2ClO4(L2)(H2O)(PhMe)]ClO4}n: 40.48% C; 3.29% H and 5.72% N; found: 35.28% C; 3.06% H and 5.92% N. FTIR data (KBr, cm-1): 3041(w), 2968(w), 2947(w), 2916(w), 2900(w), 2877(w), 2221(m), 1579(s), 1492(w), 1462(m), 1448(m), 1367(m), 1313(m), 1296(w), 1257(s), 1166(s), 1139(s), 1089(s), 1058(m), 1047(m), 956(w), 860(w), 750(s), 613(w). (Fig. S2, Supporting information). 4.B.

M.p.:

120-121

°C.

Elemental

analysis

calculated

for

{[Ag2BF4(L2)(H2O)(C6H6)](H2O)(BF4)}n: 40.12% C; 3.37% H and; 5.85% N; found: 40.52% C; 3.26% H and 6.05% N. FTIR data (KBr, cm-1): 3042(w), 2969(w), 2926(w), 2917(w), 2900(w), 2877(w), 2222(s), 1581(s), 1481(s), 1448(m), 1414(w), 1368(m), 1313(m), 1296(w), 1257(s), 1084(s), 1059(w), 957(w), 860(w), 750(s), 612(w). (Fig. S2, Supporting information). 4.T. M.p.: 85 °C. Elemental analysis calculated for {[Ag2BF4(L2)(H2O)(PhMe)](H2O)(BF4)}n: 40.78% C; 3.53% H and 5.76% N; found: 33.72% C; 3.19% H and 5.96% N. FTIR data (KBr, cm-1): 3043(w), 2970(w), 2947(w), 2916(w), 2900(w), 2877(w), 2833(w), 2221(m), 1579(s),


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1481(m), 1448(m), 1367(m), 1327(w), 1313(m), 1257(s), 1083(s), 1058(s), 1047(s), 1031(s), 956(w), 875(w), 750(s), 613(w). (Fig. S2, Supporting information).

ASSOCIATED CONTENT The Supporting Information is available free of charge on the ACS Publications website. FTIR spectra, PXRD data, additional structural figures and tables, UV−vis absorption and emission spectra. Accession Codes CCDC 1555834 (1.B), 1532615 (1.T), 1555848 (2.B), 1555849 (3.B), and 1555850 (4.B) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

AUTHOR INFORMATION Corresponding Author Universidade Federal Fluminense (UFF), Departamento de Química Inorgânica, Outeiro São João Batista, s/n, Campus do Valonguinho, Centro, 24020-141, Niterói, RJ, Brazil *E-mail: [email protected] ORCID Célia M. Ronconi: 0000-0001-9736-9661 Carlos B. Pinheiro: 0000-0002-8674-1779


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Notes The authors declare no competing financial interest.

AUTHOR CONTRIBUTIONS The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. These authors contributed equally.

ACKNOWLEDGMENTS The authors gratefully acknowledge the National Council for Scientific and Technological Development (CNPq Jovens Cientistas em Nanotecnologia, grant number 550572/2012-0 and research fellowships), the Brazilian Federal Agency for Support and Evaluation of Graduate Education (CAPES) for the C.R.M.O. Matos fellowship, the Rio de Janeiro Research Foundation (FAPERJ JCNE grant number E-26/103.213/2011). We are grateful to the Material Characterization (http://www.uff.br/lamate/), Molecular Spectroscopy (http://www.uff.br/lame/), NMR (http://www.laremn.uff.br) and X-ray Diffraction (http://www.ldrx.uff.br) Multiuser Laboratories from Universidade Federal Fluminense. We also thank Prof. Faruk José Nome Aguilera (UFSC) for assistance for helpful discussions.


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“For Table of Contents Use Only”

Tuning Photoluminescence Properties of Silver(I) Coordination Networks Based on Dicyanomethylene Ligands through their Supramolecular Interactions Catiúcia R. M. O. Matos,† Flávia G. A. Monteiro,‡ Fabio da S. Miranda,† Carlos B. Pinheiro,§ Andrew D. Bond,|| Célia M. Ronconi*,†

Eight novel silver(I)-based coordination networks have been self-assembled from two flexible dicyanomethylene ligands. They can be green and yellow emitters depending on their supramolecular interactions.


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Tuning Photoluminescent Properties of Silver(I)-Based Coordination

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