Silver coordination polymers based on newly designed bis(cyanobenzyl)bipiperidine ligand: Synthesis, anion exchange, guest inclusion, electrochemical, and photoluminescence properties

Article abstract of DOI:10.1021/acs.cgd.6b00151

A new flexible ligand, bis(cyanobenzyl)bipiperidine (L), has been synthesized and structurally characterized. Nine novel silver(I) coordination polymers (CPs), the dimensionality of which depends on the counteranion, [Ag₂(L)(NO₃)₂]_n (1), [Ag₂(L)(NO₃)₂]_n (2), {[Ag₂(L)(NO₃)₂)](C₁₆H₁₀)}_n (3), {[Ag₂(L)(NO₃)₂)](C₂₀H₁₂)}_n (4), [Ag₂(L)(ClO₄)₂]_n (5), [Ag₂(L)(CF₃SO₃)₂(C₄H₈O)₂]_n (6), [Ag₂(L)(CF₃SO₃)₂(C₃H₆O)₂]_n (7), {[Ag₂(L)₂]·(BF₄)·2(C₃H₆O)}_n (8), and [Ag₂(L)₃(PF₆)₂]·x(C₃H₆O) (9), have been prepared by self-assembly of L with AgX (X = NO₃^-, ClO₄^-, CF₃SO₃^-, BF₄^-, and PF₆^-) and aromatic guest molecules. Reactions of L with AgNO₃ in acetone in either 1:2 or 1:1 stoichiometric ratio occurred rapidly at room temperature, yielding topologically different structural isomers of the three-dimensional (3D) CPs 1 and 2. Additional reactions of linker L with AgNO₃ in the presence of aromatic guest molecules (pyrene, perylene) formed CPs of 3 and 4 with the inclusion of the corresponding guest in the crystal lattice associated with the reduction of dimensionality of the self-assembled product from 3D to two-dimensional (2D). Reaction of L with AgTf (Tf = CF₃SO₃^-) in acetone and THF gave two structurally related 2D CPs (6 and 7). Compound 8 represents a one-dimensional (1D) coordination polymer where the BF₄ anions are not linked to the silver nodes, while 9 is a discrete coordination complex. Anion exchange accompanying an irreversible structural conversion from 7 to 1 and 7 to 8 was monitored in the crystalline state by IR and PXRD techniques. On the other hand, a reversible anion exchange process was observed between 1 and 8. The electrochemical and solid-state photoluminescence properties of these Ag(I) CPs were also characterized.

Full text of DOI:10.1021/acs.cgd.6b00151

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Article
Silver coordination polymers based on newly designed bis-
(cyanobenzyl)bipipyridine ligand: synthesis, anion exchange, guest
inclusion, electrochemical and photoluminescence properties
Sandipan Roy, Hatem M Titi, Bharat Kumar Tripuramallu, Nisith Bhunia, Roli Verma, and Israel Goldberg
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b00151 • Publication Date (Web): 05 Apr 2016
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Silver coordination polymers based on newly designed bis-
(cyanobenzyl)bipiperidine ligand: synthesis, anion exchange, guest
inclusion, electrochemical and photoluminescence properties
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Sandipan Roy, Hatem M. Titi, Bharat Kumar Tripuramallu, Nisith Bhunia, Roli Verma and
Israel Goldberg*
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School of Chemistry, Sackler Faculty of Exact Sciences, TelꢀAviv University, RamatꢀAviv, 69978
TelꢀAviv, Israel. Eꢀmail: sandipanroy06@gmail.com, goldberg@post.tau.ac.il
Abstract
A new flexible ligand, bisꢀ(cyanobenzyl)bipiperidine (L), has been synthesized and
structurally characterized. Nine novel silver(I) coordination polymers (CPs), the
dimensionality of which depends on the counterꢀanion; [Ag2(L)(NO3)2]n (1), [Ag2(L)(NO3)2]n
(2), {[Ag2(L)(NO3)2)](C16H10)}n (3), {[Ag2(L)(NO3)2)](C20H12)}n (4), [Ag2(L)(ClO4)2]n (5),
[Ag2(L)(CF3SO3)2(C4H8O)2]n
(6),
[Ag2(L)(CF3SO3)2(C3H6O)2]n
(7),
{[Ag2(L)2]ꢁ(BF4)ꢁ2(C3H6O)}n (8) and [Ag2(L)3(PF6)2]ꢁx(C3H6O) (9) have been prepared by
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selfꢀassembly of L with AgX (X = NO3 , ClO4 , CF3SO3 , BF4 and PF6 ), and aromatic
guest molecules. Reactions of L with AgNO3 in acetone in either 1:2 or 1:1 stoichiometric
ratio occurred rapidly at room temperature, yielding topologically different structural isomers
of the threeꢀdimensional (3D) CPs 1 and 2. Additional reactions of linker L with AgNO3 in
the presence of aromatic guest molecules (pyrene, perylene) formed CPs of 3 and 4 with the
inclusion of the corresponding guest in the crystal lattice associated with the reduction of
dimensionality of the selfꢀassembled product from 3D to 2D. Reaction of L with AgTf (Tf =
ꢀ
CF3SO3 ) in acetone and THF gave two structurally related twoꢀdimensional (2D) CPs (6 and
7). Compound 8 represents a 1D coordination polymer where the BF4 anions are not linked to
the silver nodes, while 9 is a discrete coordination complex. Anion exchange accompanying
an irreversible structural conversion from 7 to 1 and 7 to 8 was monitored in the crystalline
state by IR and PXRD techniques. On the other hand, a reversible anion exchange process
was observed between 1 and 8. The electrochemical and solidꢀstate photoluminescence
properties of these Ag(I)ꢀCPs were also characterized.
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INTRODUCTION
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Research towards the exploration of coordination polymers (CPs) has rapidly progressed over
the past decades because of the versatile utility of such materials in a wide range of potential
applications, e.g. as solidꢀstate luminescence sensors, light emitting diodes, proton
conductors, heterogeneous catalysts, gas sorbants and supercapacitors.1ꢀ18 Many different
factors play an important role in the synthesis of such materials, including nature
(coordination preferences of the metal ions, functionality and flexibility of the organic
linkers) and stochiometric ratio of the reacting partners, reaction conditions/environment, and
the solvents used. Possible inclusion of guest components within the coordination lattice
provides an additional important parameter that may further influence the properties of the
resulting product.19ꢀ25 In this context, several rigid multitopic organic ligands and transitional
metal ions have been used to explore CPs with predictable and well defined porous
frameworks that can undergo reversible guest or anion exchange, with or without losing their
structural integrity.26ꢀ35 The structural features of coordination polymers with flexible multiꢀ
topic organic ligands appear to be less predictable. Yet the use of flexible linkers could be
advantageous in other respects, as such coordination networks are more adaptive to guestꢀ
inclusion, more responsive to external stimuli and may reveal higher propensity to singleꢀ
crystalꢀtoꢀsingleꢀcrystal transformation.36ꢀ38
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The coordination chemistry of multiꢀtopic organic ligands bearing pyridine,
carboxylate and/or imidazole functionalities have been widely investigated in relation to the
construction of coordination polymeric networks.39ꢀ44 Several rigid organic ligands
substituted with nitrile groups have been successfully utilized as well in the formation of both
porous or nonꢀporous CPs with silver(I) ions as nodes. This has been facilitated by the ready
availability of nitriles, low cost of silver (with its soft Lewis acid character), and the
simplicity of the Ag(I) ̶
N≡C interaction.30,45ꢀ54 On the other hand, very few flexible ligands
containing nitrile groups have been explored for construction of CPs with silver(I) ions.25,55
Among those nitrileꢀbased silver(I) CPs, some showed supramolecular structural
transformations in the crystalline state, concomitant with anion exchange, while other CP
compounds exhibited solidꢀstate photoluminescence.22,25,56ꢀ61 Issues of guest inclusion and
electrochemical behaviour of nitrileꢀbased silver(I) CPs deserved lesser attention.25,62
In this work we report on the synthesis of a new divergent heterotopic flexible ligand,
namely bisꢀ(cyanobenzyl)bipiperidine, L, which contains both amine and nitrile nitrogen
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donors (Scheme 1). The two nitrile groups along with the two sp3 Nꢀatoms of the molecule
provide attractive sites for metal coordination. Due to the presence of interꢀconnecting
aliphatic methylene spacers, L has conformational degrees of freedom primarily about the Nꢀ
CꢀCaromatic bonds (Scheme 1).
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ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
Coordination
CN
sites
Rotation
Center
N
N
NC
Scheme 1. Molecular framework of the flexible diꢀtopic ligand (L).
Scheme 2. Schematic representation of the synthesis of the Ag(I) coordination polymers of
ligand (L) in question with the variation of anions, reaction stoichiometry, and the aromatic
guest molecules.
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We then reacted this ligand with a series of silver salts and explored the resulting
coordination polymers (Scheme 2) in order to study the influence of anions on the
dimensionality of the coordination networking. Indeed, the structures of the polymeric
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products were found to be affected by the nature of the counter anions (NO3 , ClO4 ,
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CF3SO3 , BF4 and PF6 ), reaction stoichiometry and possible insertion of large aromatic
guests into the crystallizing materials. The available compounds (which are not porous) have
been examined, therefore, with respect to postꢀsynthetic anionꢀinduced structural
transformations (Scheme 3) and guest inclusion. While compounds 1 and 2 represent 3D
coordination frameworks, upon inclusion of a large aromatic guest (as pyrene in 3 or perylene
in 4) the dimensionality of the polymeric ensemble is reduced to 2D, exhibiting the same
metalꢀligand connectivity features in 3 and 4. The inclusion of large aromatic guests is
expected to affect the interlayer πꢀπ stacking in the corresponding structures and thus their
emission properties. Correspondingly, solidꢀstate photoluminescence study was conducted for
both of the guestꢀincluded CPs, in relation to the guest free CPs, and the free ligand. The
organic linker L used in this study contains nitrile functions and exhibits redoxꢀactive
behaviour. This led us to explore also the electrochemical properties of the coordinationꢀ
polymeric compounds presented here; there is only a rare literature example reporting on the
electrochemical performance of such nitrileꢀbased Ag(I)ꢀCPs.62,63
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ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
Scheme 3. Schematic representation for the structural transformation of the products via
postꢀsynthetic anion exchange procedures.
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RESULTS AND DISCUSSION
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Synthesis and crystal structure of bis-(cyanobenzyl)bipiperidine (L). L was
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synthesized by reaction of 4,4’ꢀbipiperidine with 4ꢀ(bromomethyl) benzonitrile under reflux
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condition. The structure of L was determined by H NMR, IR, and singleꢀcrystal Xꢀray
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diffraction (crystallization from acetone). Compound L crystallises in the monoclinic space
group P21/n and the asymmetric unit consists of one and a half molecules of L (the latter
being located on inversion) The two crystallographically independent units (depicted in green
and red in Figure 1b, respectively) have an extended conformation, the antiꢀperiplanar
CaromaticꢀCmethyleneꢀCmethyleneꢀCaromatic torsion angles being near 180°. They overlay almost
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perfectly, both displaying similar hydrogen bonding R2 (10) patterns (Figure 1a). The N•••Hꢀ
C intermolecular contact distances are 2.61 and 2.71 Å for the green molecules and 2.56 Å
for the red moieties. The two entities exhibit zigꢀzag type 1D 'hydrogenꢀbonding polymers',
the Hꢀbonded chains of the red molecules being interspaced by two parallel chains of the
green species (Figure 1b). There is no apparent hydrogen bonding between the 'polymeric'
chains. It has been anticipated that the preferred antiꢀperiplanar conformation of L will be
preserved in the reaction of this ligand with silver salts.
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
Figure 1. (a) The intermolecular hydrogen bonding synthon along the zigꢀzag 'polymeric
chains'. (b) Crystal packing viewed down the aꢀaxis, showing the two crystallographically
independent molecules of L in green (located on general positions and red (on centers of
inversion) colours.
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Self-assembly of bis-(cyanobenzyl)bipiperidine (L) with silver(I) ions. Ligand L
was reacted with a series of silver(I) salts at room temperature in acetone/THF solution. Five
different reagents (AgNO3, AgClO4, AgCF3SO3, AgBF4, AgPF6) were employed, also in
order to assess the effect of the different anions on the topology of the resulting networks.
The preparative procedures were carried out with varying ligandꢀtoꢀmetal stoichiometric
ratios, but only crystallizations of L with AgNO3 (but not with the other reagents) led to two
different products. In some syntheses large aromatic guest molecules were also added to the
reaction mixture to induce their coꢀcrystallization with the coordination polymeric ensembles.
Crystallization of L with AgNO3 in 1:1 and 1:2 ratios in acetone at room temperature
afforded within 30ꢀ60 minutes single crystals of [Ag2(L)(NO3)2]n, 1 (Figure 2) and 2 (Figure
3) respectively. The two structures reveal 3D coordination frameworks, but are characterized
by different topologies. When L was reacted with silver nitrate (1:2) in the presence of
different polycyclic aromatic hydrocarbons as possible guest entities, single crystals suitable
for Xꢀray diffraction were obtained with pyrene {[Ag2(L)(NO3)2)](C16H10)}n (3), and
perylene {[Ag2(L)(NO3)2)](C20H12)}n (4). Inclusion of the guest components reduced the
dimensionality of the silverꢀligand coordinationꢀpolymeric ensemble from 3D to 2D in 3
(Figure 4) and 4 (Figure 5). Selfꢀassembly of L with the other Ag(I) salts in acetone or
tetrahydrofuran at room temperature afforded within 24 hours single crystals of
[Ag2(L)(ClO4)2]n (5), [Ag2(L)(CF3SO3)2(C4H8O)2]n (6), [Ag2(L)(CF3SO3)2(C3H6O)2]n (7),
{[Ag2(L)2]ꢁ(BF4)ꢁ2(C3H6O)}n, (8) and [Ag2(L)3(PF6)2]ꢁx(C3H6O) (9). Compound 5 was
found to exhibit 3D networking pattern, while 6 and 7 show 2D coordination networks. 1D
coordination polymerization was found in 8, and discrete complexes compose crystals of
compound 9 (Scheme 2). All the crystalline samples (1-9) were stored in the dark; yet no
strong light sensitivity has been observed.
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Structural description of the 3D coordination polymers in (1) and (2). Colourless
blockꢀlike crystals of 1, were readily formed within 30 minutes. This type of rapid formation
of CPs is quite rare in the literature.64 The asymmetric unit of 1 contains half molecule of L,
one Ag(I) ion and one nitrate (NO3ꢂ) anion. Each silver ion exhibits a distorted tetrahedral
geometry, being coordinated by two nitrate Oꢀatoms, one bipiperidine Nꢀatom and one
nitrogen atom from a nitrile group (Figures 2a and 2b). The coordination distances of the
Ag(I)ꢀO contacts are 2.48 and 2.57 Å, while the Ag(I)ꢀN bond lengths are 2.32 and 2.25 Å.
Every ligand (in its characteristic antiꢀperiplanar conformation) is bound through its four Nꢀ
sites to four Agꢀcenters, and every nitrate anion connects along the aꢀaxis between two silver
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nodes. The shortest distance between the silvers ions is 5.75 Å. The interꢀconnected ligands
are arranged in the crystals in a herringbone fashion (Figure 2c).
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Figure 2. 3D coordination polymer 1, [Ag2(L)(NO3)2]n. (a) View of the ligand coordination
environment. (b) View of the metal coordination environment. (c) Perspective view of the 3D
framework and its coordination connectivity (Ar represents the aromatic part of the ligand. Hꢀ
atoms and parts of the ligands were omitted for clarity). (d) The simplified topological
illustration of the network (mot topology) where blue nodes represent the Agꢀions and the
green linkers represent the ligands.
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
The two nodal net can be simplified by a nodeꢀandꢀlinkerꢀtype representation, using
the TOPOS 4.0 software.65 It exhibits a known motꢀtype topology; a 4,4ꢀconnected network
with a point symbol of {64.82}2{66} (Figure 2d). In the TOPOS Topological Database (TTD)
there are fifteen crystal structures (their CCDC ref. codes are: AGAYOW, AGONIU,
ASAYOJ, AWIDIU, CEBJAV, DAKNAG, KIYMIP, LUJPUC, MIJNAU, PUNSOH,
RESSAK, SEHZUB, SEJBAL, UPERAJ, XANMIJ)66,67 identified as mot networks. Among
these frameworks only one of them (CEBJAV)68 exhibits a silver node coordinated to nitrate
and nitrile groups, and its connectivity pattern is similar to that observed in 1.
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Figure 3. a) Comparison between the nitrate's bridging mode in 1 (right) and 2 (left). The
silver spheres represent the Ag(I)ꢀatoms. b) Illustration of 3D framework (viewed along aꢀ
axis) of 2 and its simplified net (green depicts the organic linkers and blue are the silver
nodes).
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
Changing the metalꢀligand stoichiometry to 1:1 in the reaction mixture afforded
colourless blockꢀlike crystals of 2 within 1ꢀ2 hours (Figure 3). The chemical and structural
composition of 1 and 2 is identical in terms of the content of the asymmetric unit in the two
structures and nodeꢀlinker coordination connectivity. Yet, from the topological point of view
the two polymeric structures belong to different topological types, and thus represent
structural polymorphs. The silver nodes in 2 coordinate to two different Ls and two nitrate
anions in a severely distorted tetrahedral geometry. As in the previous example, every ligand
binds four different Ag ions, which in turn are also interconnected through the nitrate counter
ions. The observed AgꢀN and AgꢀO bond distances are 2.31 and 2.30 Å, and 2.53 and 2.48 Å,
respectively. The coordination framework in 2 belongs to the topological type bbf, alongside
with 24 other crystalline materials (analyzed by TTD) (The CCDC ref. codes are: AHADUJ,
AHAFAR, AVAQOD, DIPGAK, EXIDAR, EXIDEV, FAKJAE, FEZWAJ, IMIXEI,
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ISIKOL, ISIKUR, ISILAY, ISILIG, ISIMAZ, ISIMED, ISIMIH, LISBEV, LISBOF,
OWUGAP, QUPHIT, RAVKEG, SOCXEO, UHUNEQ, UJARIH)53,54 (Figure 3b). It
represents a (4,4)ꢀconnected binodal network with point symbol of {64.82}{66}2.
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ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
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Figure 4. Illustrations of the polymeric chains (ID) and intermolecular interactions in (a) 3
and (b) 4. The dashed blue lines represent interactions of the silver cations (depicted as
spheres) and nitrate anions.
Structural description of the guest-included coordination polymers in (3) and (4).
Although several reactions were tried in the presence of different aromatic solid guest
molecules, single crystals suitable for Xꢀray diffraction studies were obtained only in case of
pyrene (3) and perylene (4). The structures of compounds 3 and 4 can be best described as
composed of 1D coordination Agꢀligand chains (Figures 4a and 4b), which are further interꢀ
linked via the nitrate anions into quasiꢀ2D sheets. In 3 the Ag(I)ꢀcations bind to two L linkers
through Nsp3 and nitrile functions (at 2.24 and 2.34 Å), as well as to (in a monoꢀdentate
fashion) the nitrate anion at 2.24ꢀ2.33 Å (Figure 4a). In 4 there are two crystallographically
independent metal ions Ag(I) with different coordination environments (Figure 4b). The first
metal center Ag1 is linked to only one L via the Nsp3 site and to the nitrate anion. The second
cation Ag2 is engaged in 1D coordination polymeric array by bridging between two adjacent
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Ls through the nitrile function of one linker and the Nsp3 site of another linker. In addition,
the Ag2 ion is coordinated to a nitrate group in a bidentate manner. The corresponding
interaction distances AgꢀNnitrile, AgꢀNsp3 and AgꢀNnitrate are respectively 2.30, 2.27 and 2.28,
2.36ꢀ2.57 Å. Noteworthy, only one (out of two) nitrile sites of L is involved in coordinative
bonds with the silver ions.
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ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
Figure 5. Illustrations of the quasiꢀ2D sheet with inclusion of (a) pyrene in 3 (structure
viewed down the bꢀaxis of the crystal), and (b) perylene in 4 (structure viewed down the aꢀ
axis).
----------------------------------------------------------------------------------------------------------------
Inclusion of the aromatic guest molecules between the coordinationꢀpolymeric layers
in 3 and 4 is depicted in Figures 5a and 5b. In 3 the neighbouring pyrene moieties are
laterally displaced one with respect to the other along the 2D sheets without any apparent
π…π interactions between them (Figure 5a). The adjacent perylene molecules in 4, show
partial πꢀstacking with an interplanar distance of 3.38 Å (Figure 5b). The interaction of the
pyrene and perylene guests with the surrounding coordination polymers is mainly by van der
Waals forces between the contact surfaces of the parallel layers. These appear to compensate
for breaking the crossꢀlinking AgꢀNnitrate interactions (as observed in 1 and 2) that result from
the aromatic guest inclusion in 3 and 4.
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Structural description of silver(I) CPs incorporating different anions.
Crystallization of L with AgClO4 led to the formation of 3D network of [Ag2(L)(ClO4)2]n (5),
shown in Figure 6a. In structure of 5, the asymmetric unit consists of half a ligand moiety
(located on crystallographic inversion), one ClO4‾ anion and a silver node. The framework
shows a distorted tetrahedral Ag(I) metal centres, where the liganꢀmetalꢀligand bond angles
are within 84–142˚. The observed bond distances of AgꢀOClO4 bonds are 2.53 and 2.71 Å,
while the AgꢀNligand bonds are considerably shorter 2.27 and 2.18 Å (Figure 6b). The 4ꢀ
connected Ag(I) nodes are coordinated to two different L linkers and two bridging ClO4‾
anions. The Ag(I)ꢁꢁꢁAg(I) separation distance between the ClO4‾ꢀbridged cations
(approximately along the cꢀaxis of the crystal) is 5.64 Å. Every ligand L is coordinated to
four Ag(I) ion centres through both Nsp3 and Nnitrile positions, forming a 3D motꢀtype
framework of similar topology than that in structure 1. The specific torsion angle of L is
about 180˚ and it is coordinated from two different directions creating the 3D network.
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ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
Figure 6. 3D silver(I) perchlorate coordination polymer 5. (a) Connectivity of the silver
nodes (depicted as spheres). Red balls represent the perchlorate anions, and Ar stands for the
aromatic fragment of the ligand. (b) Perspective view (down the aꢀaxis) of the 3D network.
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
When silver(I) triflate was used in the reaction with L, in tetrahydrofuran or acetone
at room temperature, it afforded 2ꢀD networks of the [Ag2(L)(CF3SO3)2(C4H8O)2]n (6),
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[Ag2(L)(CF3SO3)2(C3H6O)2]n (7) composition. The two structures 6 and 7 are pseudoꢀ
isostructural in their network geometry. The asymmetric unit of 6 contains one Ag(I) ion, a
triflate anion, one tetrahydrofuran (THF) and half of the L molecule. Each Agꢀcenter has a
pseudoꢀtetrahedral coordination environment, being linked to Nnitrile and Nsp3 of two different
linkers, as well as to Otriflate and OTHF sites. Association of the ligands through the Nsp3 and
nitrile sites with the silver ions (at AgꢀN = 2.21 and 2.24 Å) led to the formation of 2D
coordination layers with parallelogramꢀlike cavities (Figure 7), the latter being
accommodated by the Tf‾ anions and THF ligands (with AgꢀOtriflate and AgꢀOTHF contact
distances of 2.55 and 2.59 Å, respectively). Coordination 2D networking of similar topology
characterize structure 7, where acetone molecules replace the THF entities in the coordination
environment of the silverꢀion nodes (the asymmetric unit of 7 contains two Ag(I) ions, two
triflate anions, two acetone moieties and one L molecule). The corresponding coordination
distances in 7 are: AgꢀN = 2.16ꢀ2.27 Å, AgꢀOtriflate = 2.47 Å, and AgꢀOacetone = 2.56 and 2.61
Å.
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ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
Figure 7. Perspective view of 2Dꢀnetwork of the silver(I) triflate coordination polymers in 6.
Hydrogen atoms are omitted for clarity. The silver cation and atoms of the triflate
anion are depicted as spheres.
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Figure 8. Perspective view of 1D helical chains of silver(I) tetrafluroborate coordination
polymers in 8. Hydrogen atoms are omitted for clarity. The silver•••BF4‾ interactions are
indicated by green lines. The Ag cations and atoms the tetrfluoroborate anions are depicted as
spheres.
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
A similar reaction of L with silver(I) tetrafluoroborate afforded 1D wavy coordination
chains of {[Ag2(L)2]ꢁ(BF4)ꢁ2(C3H6O)}n composition (8) (Figure 8). The asymmetric unit of 8
contains one Ag(I) ion, a tetrafluoroborate anion, two acetone moieties and one molecule of
L. The two organic linkers are bonded to one silver cation via the Nsp3 functions in a nearly
linear geometry (NꢀAgꢀN = 177˚), where the corresponding AgꢀN contact distances are 2.18
and 2.19 Å. The BF4‾ anion is positioned near, and weakly associated with, Ag at Ag•••Fꢀ
BF3‾ distance of 2.84 Å. Acetone and anion molecules are surrounding the helical
coordination chains, hindering possible engagement of the nitrile groups in coordination to
the cation centres.
Finally, reaction of silver(I) hexafluorophosphate with L afforded the oligomeric
complex [Ag2(L)3(PF6)2]n (9) (Figure 9). The asymmetric unit of 9 contains one Ag(I) ion, a
hexaflurophosphate anion, and one and half of L molecule. In this oligomer, each of the two
Ag(I) centers coordinates to two organic linkers through one of their Nsp3 functions (at 2.20
and 2.21 Å), as well as to the bulky PF6‾ anion group via one of the Fꢀatom (at FꢀAg = 2.47
Å, as opposed to 2.84 Å in the previous example). The terminal nitrile groups are involved in
weak intermolecular hydrogen bonds. The Cambridge Crystallographic database (CCDC,
ConQuest Version 1.17, 2014) contains 944 entries of complexes involving the Ag(I) and
PF6‾ ion pair.54 Out of them only four exhibit directional AgꢀF coordination between the two
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ions at (2.54 ꢀ 2.55 Å).69ꢀ72 as compared to the Ag(I)ꢀF coordination bond distance of 2.47 Å
in 9. The coordination geometry around the Ag ions is of the Tꢀshape type with two NꢀAgꢀF
bond angles of 97 and 99˚, and the NꢀAgꢀN angle of 164˚. A similar Tꢀshape coordination to
two transꢀrelated Nꢀsites and an Fꢀ ion has been observed by Bu et al. in a silver
tetrafluorobrate complex with an Nꢀligand (CCDC refcode ETOPIM: AgꢀF bond distance
2.53 Å).73
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ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
Figure 9. Illustration of the oligomeric structure of silver(I) hexafluorophosphate
coordination complex 9 (Ag centres are depicted as spheres). Pꢀatoms are shown in orange,
Fꢀatoms in green, Nꢀatoms in blue and Cꢀatoms in black. Hydrogen atoms are omitted for
clarity.
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
The influence of the various silver salts on the polymeric assembly. The above
observations provide interesting insights regarding the kinetics, anionic coordination ability
ꢀ
and steric effects in the available structures. As expected, the polyꢀdentate Oꢀanions (NO3 ,
ꢀ
ClO4 ) have the capacity of coordinating simultaneously to at least two silver ions, and are
readily incorporated into the polymeric assembly. This feature along with the multiꢀdentate
nature of the organic linker led to the formation of 3D frameworks. The NO3‾ anions have a
dramatic effect on the crystallization process. Reactions to obtain crystals of 1 and 2 (with 1:2
and 1:1 ligandꢀtoꢀAg salt ratios, respectively) are very fast (30ꢀ60 minutes). When the silver
salt concentration is increased with respect to that of the ligand, e.g. to 4:1, rapid precipitation
of either polycrystalline or amorphous solids occurs. It appears that the small nitrate anions
engage readily in the construction of 3D polymeric assemblies. When the ClO4‾ anions of
large size were used (in 5), the reaction times increased to 24 hours or more, although still the
3D supramolecular connectivity was preserved in the resulting product. Raising further the
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anionic size by reacting the organic ligand with silver triflate salt (in 6 and 7) yielded only 2D
coordination patterns, the bulkier Tf‾ ions showing only a monoꢀdentate (rather than
bridging) coordination mode to the silver ions. In the above context, a survey of the
Cambridge Crystallographic Database was made to learn about the relative abundance of
polymeric structures based on component species with similar functionalities. The search
model used involved molecules with phenylꢀnitrile coordination ligands and nitrate,
perchlorate or triflate silver salts. Examples with PhꢀCNꢀAg coordination modes, where the
given anion bridges between two or more silver ions, were searched for. Of the
correspondingly retrieved crystal structures: one out of fifteen structures of perchlorate salts
contain a bridging ClO4‾ anion between silver centers,44 three out of eight structures of nitrate
salts contain a bridging NO3‾ anion,74 and 15 out of 50 structure with triflate salt contain
bridging Tf‾ ions. Structures 8 and 9 involved fluorinated anions, which show much lower
propensity to act as a bridging component between the silver nodes. Correspondingly, the
intermolecular coordination in 8 and 9 yielded only 1D chain and 0D oligomeric entities,
respectively, wherein the nitrile functions are not linked to metal ions. The use of the
fluorinated anions of weaker coordination affinity in this work was intended to invoke the
formation of polymeric structures with direct metallic Ag(I)ꢀAg(I) bridging between the
silver nodes, but this effort turned out to be unsuccessful.
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Anion exchange and structural transformations. Anion exchange reactions were
attempted with coordination complexes 1, 7 and 8 of different connectivity patterns (3D, 2D
and 1D). The experiments were carried out by immersing the crystalline samples of the
corresponding CPs in a 3 M aqueous sodium salt solution of the replacement anion and left
undisturbed at ambient temperature to allow anionꢀexchange. The possible anionꢀexchangeꢀ
induced structural transformations were investigated by IR spectra and PXRD patterns, as the
exchanged product were found unsuitable for single crystal Xꢀray diffractions due to their
poor/deteriorated crystallinity. Evidently, in particular cases the anionꢀexchange procedure
led to significant modification of the coordination pattern in the crystal. For example, when a
crystal of 7 was immersed in an aqueous solution of 3 M NaNO3 (in which it is insoluble) and
left undisturbed at ambient temperature, the IR spectra for the solid sample collected after 0.5
−
and 1 h manifested fast generation of a new intense band at 1338 cm−1 for NO3 (green
−
asterisk in Figure 10a) and consequently the disappearance of an intense CF3SO3 peak at
−
1173 cm−1 (purple asterisk in Figure 10a). Eventually, the CF3SO3 peak disappeared
completely after 2 h, and the consequent IR spectrum is almost similar with that of compound
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−
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1. This implies that the CF3SO3 ion is quantitatively displaced by the NO3 ion (Figure 10a).
In addition, the PXRD pattern obtained after 2h was coincident with that of 1, indicating that
the 2D coordination polymer in 7 was converted to the 3D polymeric structure of 1 by the
−
−
exchange of CF3SO3 with NO3 (Figure S1 in the Supporting Information). In another
example, crystals of 1 and 7 were immersed in an aqueous solution of 3 M NaBF4 and left
undisturbed at ambient temperature to allow for the anticipated anion exchange. IR spectra
collected for these samples after 1 h and 2 h were found to be almost coincident with the IR
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ꢀ
spectrum of 8, evidencing a complete exchange of the CF3SO3 and NO3 ions by BF4
(Figure 10b and Figure S2 in the Supporting Information). The reverse anion exchange
between 8 and 1 was also performed successfully (Figure S2 in the Supporting Information).
(b)
(a)
Figure 10. (a) IR spectra of 7 after anionꢀexchange employing 3M NaNO3 aqueous solution for 0.5,
1, and 2 h. The top and bottom curves represent the IR spectra for 7 and 1 as prepared by direct
synthesis. (b) IR spectra of 7 after anionꢀexchange employing 3M NaBF4 aqueous solution for 0.5, 1,
and 2 h. The top and bottom curves represent the IR spectra for 7 and 8 as prepared by direct
synthesis.
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
Electrochemical behaviour. The electrochemical behaviour of complexes 1, 3, 4 and
7-9, as well of ligand L, were investigated by cyclic voltammetry (CV) using 0.2 M 1ꢀethylꢀ
3ꢀmethylimidazolium bis(trifluoromethylsulfonyl)imide (EMIM TFSI) ionic liquid/CH3CN
nonꢀaqueous electrolyte (Figure 11). The experiments were carried out using three electrode
system with Platinum (Pt) foil as working electrode, Pt wire as counter electrode and
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saturated calomel electrode (SCE) as a reference electrode. The analysed complexes were
dispersed in dimethylacetamide (1 mg/mL) and then deposited on the working electrode in a
suspension state. Subsequently, 0.02 mL nafion solution (as a binder) was deposited over the
dried samples on the working electrode. Figure 11 shows the cyclic voltammograms of
complexes 1, 3, 4 and 7-9, along with that of L at 100 mV/s. Ligand L was found to exhibit
good redoxꢀactive behaviour with the appearance of first reversible oxidation wave at ꢀ0.55 V
vs. SCE, followed by irreversible one at 0.49 V vs. SCE. After complexation of L with Ag(I),
in complexes of 1, 3, 4 and 7-9, the reduction peak of silver (I) is not present, indicating that
reduction of silver (I) when coordinated to the Nꢀsites of the ligand is difficult.63,75 Along the
opposite course, the characteristic first reversible oxidation wave in the complexes was found
to occur in the range of ꢀ0.46 V~ 0.50 V vs. SCE, followed by irreversible oxidation wave in
the range of 0.63 V~ 0.66V vs. SCE which can involve the ligand as well. With respect to the
oxidation of L, all the oxidation peaks in the complexes shifted towards positive potentials by
about 0.05 ~ 0.10 V for the reversible oxidation wave and by 0.14 ~ 0.1V vs. SCE for the
irreversible oxidation wave.
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ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
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-5
Ligand
1
3
4
7
-10
-15
8
9
-20
-25
-1.5
-1.0
-0.5
0.0
0.5
1.0
1.5
Potential (V) vs. SCE
Figure 11. Cyclic voltammograms of ligand L and complexes 1, 3, 4 and 7-9 (in CH3CN),
using 0.2 M EMIM TFSI as the supporting electrolyte.
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We have further studied the cyclic voltammograms of L as well as of their Ag(I)
complexes at different scan rates, varying from 10 mV/s to 200 mV/s (Figures S3 to S8 in the
Supporting Information). The CV curves of all the samples appear well maintained with the
cathodic and anodic peaks almost unchanged even at high scan rate, indicating that stability
of L and its silver (I) complexes is retained. The electrochemical properties of the redox
active materials (CPs) were calculated in terms of specific capacitance (SC) from the area
under the CV curve. Specific capacitance of the samples at different scan rates is shown in
Figures S3 to S8. Interestingly, the Ag(I) complexes exhibit higher specific capacitance as
compared to that of L. This may be due to the existence of favourable diffusion channels in
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the solid complexes that allow cations and anions to transport 76
.
In order to assess the stability of the complex during CV tests, we have monitored the
electrochemical performance of complex 1 during 50 cycles (Figure S9 in the Supporting
Information). It has been observed that the CV curves after 5th, 10th, 20th, 30th, 40th and 50th
cycles are well maintained (in relation to the 1st cycle) and that the cathodic and anodic peaks
are almost unchanged after the 50th cycle, attesting to the remarkable stability of the
compound. Estimation of the specific capacitance from the area under the CV curves showed
retention of 96.7% of the initial specific capacitance even after 50 cycles.
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
1.0
0.8
0.6
0.4
L
1
3
0.2
4
0.0
350
400
450
500
Wavelength (nm)
Figure 12. Solidꢀstate photoluminescence spectra (PL) of L (black line), 1 (red line), 3 (blue
line) and 4 (dark cyan line) at room temperature (excitation at 275 nm).
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Luminescent properties. The development of new luminescent materials is of
particular interest for potential application as lightꢀemitting diodes.77 Recently, a study of
solidꢀstate luminescent properties of organic nitrile ligands and their Ag(I) coordination
polymers revealed that the emission wavelengths of organic nitrile ligands strongly depend
on their crystal packing.25,78 In this study, the luminescent properties of the crystalline solids
of L, 1, 3 and 4 were investigated at room temperature by exciting at wavelength of 275 nm
(Figure 12). Ligand L was found to exhibit a strong emission at 451 nm. Its complexation
with Ag(I) significantly affected the emission, which for 1 was found to be redꢀshifted to 470
nm. For 3 and 4 emission bands were observed at 465ꢀ470 nm. Compound 4 showed also a
green emission with a maximum at 530 nm. The generation of this new emission band in 4 is
most probably due to of the interlayer πꢀπ stacking interactions between aromatic units of
guest molecules in the solidꢀstate (Figure 5b).79ꢀ83
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SUMMARY
We have designed and synthesized a new flexible ditopic ligand namely bisꢀ
(cyanobenzyl)bipiperidine (L), which was then utilized in the synthesis of its coordination
−
−
−
−
−
polymers with different silver salts AgX (X = NO3 , ClO4 , CF3SO3 , BF4 and PF6 ). In the
given reaction conditions the resulting coordination patterns and their dimensionality were
−
−
found to depend on the anion type: 3D with X = NO3 and ClO4 ,(1, 2 and 5) 2D with X =
−
−
−
CF3SO3 (6 and 7), 1D with X = BF4 (8) and 0D with X= PF6 (9). Large aromatic guests
could be coꢀcrystallized with L and AgNO3 in a layered fashion (3 with pyrene and 4 with
perylene), reducing the metalꢀligand coordination networking from 3D to 2D). Anion
exchange reactions in the crystalline state have been demonstrated for coordination polymers
1, 7 and 8, including reversible transformation between 1 and 8. All the compounds exhibited
good redoxꢀactive behaviour with higher specific capacitance of the CPs in relation to L.
Among the polymeric species, 4 showed a redꢀshifted peak (530 nm) with green emission,
reflecting the presence of the interlayer π−π stacking interactions between the aromatic units
in the solidꢀstate.
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EXPERIMENTAL SECTION
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General. All the chemicals were received as reagent grade and used without any
further purification. Fourierꢀtransform (FT)ꢀIR spectra were recorded on a Bruker Tensor 27
system spectrophotometer in ATR mode. Powder Xꢀray diffraction data were recorded on
Bruker D8 Advance diffractometer using Cu Kα radiation (λ = 1.54056 Å) over a 2θ range of
5−40° at a scan rate of 1° min−1. 1H NMR (400 MHz) spectra were recorded on BrukerꢀAC
400MHz spectrometer. Photoluminescence measurements were carried out by using a
Fluorologꢀ3, HORIBA Scientific commercial setꢀup.
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Synthesis of 4,4’-(4,4’-bipiperidine-1,1’-diylbis(methylene)dibenzonitrile (L). A
roundꢀbottomed flask with a reflux condenser was charged with 4,4’ꢀbipiperidine (0.2 g, 1.18
mmol), 4ꢀ(bromomethyl) benzonitrile (0.52 g, 2.65 mmol), potassium carbonate (0.7g, 5.06
mmol) and potassium iodide (0.0015 g, 0.009 mmol). Then, acetonitrile (50 mL) was added
to the flask under nitrogen and the reaction mixture was stirred with reflux at 70° C for
overnight. After cooling, the mixture was filtered, and the residue which comprised a mixture
of the product and inorganic salts, was added to 50 mL water and stirred for 30 minutes. The
resulting precipitate was collected by filtration, washed with water, and dried under vacuum.
The final product was purified by recrystallization from acetone to afford colourless needleꢀ
like single crystals of compound L suitable for Xꢀray diffraction, ~65–70% yield within one
day. 1H NMR (CDCl3, ppm): 7.58 (d, 4H, 8Hz), 7.42 (d, 4H, 8Hz), 3.49 (s, 4H), 2.82 (d, 4H,
12Hz), 1.19 (t, 4H, 12Hz), 1.64 (d, 4H, 6Hz), 1.25 (q, 4H, 8Hz), 1.05 (m, 2H).
IR (KBr,
pellet): 2933, 2904, 2804, 2358, 2226, 1504, 1362, 1342, 1260, 1121, 1035, 972, 820, 705,
652, 563, 526 cm−1. Elem. Anal. (%) Calcd (found) for C26H30N4: C, 78.36 (78.07); H, 7.59
(7.69); N, 14.06 (14.11).
In all the following procedures the solution mixtures containing the given amounts of
the corresponding reactants were allowed to stand in a sealed vial covered entirely by
aluminium foil, and were left at room temperature to crystallise until the appearance of
sizeable crystals suitable for Xꢀray diffractions analysis.
Synthesis of 1, [Ag2(L)(NO3)2]n. A solution of AgNO3 (8.52 mg, 0.050 mmol) in
acetone (2 mL) was added to a solution of L (10 mg, 0.025 mmol) in acetone (3 mL).
Colourless blockꢀlike crystals were obtained in about 65− 70% yield within 30 minutes. IR
(KBr, pellet): 3188, 2922, 2241, 2127, 1585, 1338, 1294, 1117, 1083, 1018, 971, 862, 850,
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820, 785, 643, 566, 527 cm−1. Elem. Anal. (%) Calcd (found) for C13H15AgN3O3: C, 42.30
(42.43); H, 4.10 (4.04); N, 11.38 (11.41).
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Synthesis of 2, [Ag2(L)(NO3)2]n. A solution of AgNO3 (4.26 mg, 0.025 mmol) in
acetone (2 mL) was added to a solution of L (10 mg, 0.025 mmol) in acetone (3 mL).
Colourless needleꢀlike crystals were obtained in about 65− 70% yield within one hour. IR
(KBr, pellet): 2946, 2907, 2850, 2357, 2241, 1604, 1501, 1297, 1202, 1117, 1063, 1018, 962,
862, 850, 782, 744, 643, 566, 531 cm−1. Elem. Anal. (%) Calcd (found) for C13H15AgN3O3:
C, 42.30 (42.46); H, 4.10 (4.02); N, 11.38 (11.43).
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Synthesis of 3, {[Ag2(L)(NO3)2)](C16H10)}n. A solution of AgNO3 (8.52 mg, 0.050
mmol) in acetone (2 mL) was added to a solution of L (10 mg, 0.025 mmol) in acetone (3
mL). Then, three equivalent of pyrene (15.18 mg, 0.075 mmol) was dissolved in 2ꢀ3 mL of
acetone and added to that previous solution of AgNO3 and L. Yellow colour needleꢀlike
poorꢀquality crystals were obtained in about 70% yield within 12 hours. IR (KBr, pellet):
2946, 2907, 2849, 2358, 2241, 2049, 1607, 1297, 1109, 1036, 1018, 969, 862, 850, 782, 744,
643, 566, 550, 531 cm−1. Elem. Anal. (%) Calcd (found) for C26H30Ag2N6O6ꢁC16H9: C, 53.63
(54.03); H, 4.18 (4.22); N, 8.94 (9.02).
Synthesis of 4, {[Ag2(L)(NO3)2)](C20H12)}n. A solution of AgNO3 (8.52 mg, 0.050
mmol) in acetone (2 mL) was added to a solution of L (10 mg, 0.025 mmol) in acetone (3
mL). Then three equivalent of perylene (18.98 mg, 0.075 mmol) was dissolved in 2ꢀ3 mL of
acetone and added to that previous solution of AgNO3 and L. Yellow colour needleꢀlike
crystals were obtained in about 75% yield within 12 hours. IR (KBr, pellet): 2963, 2843,
2358, 2234, 1762, 1590, 1297, 1228, 1109, 1082, 1034, 965, 853, 817, 776, 650, 571, 487,
460 cm−1. Elem. Anal. (%) Calcd (found) for C26H30Ag2N6O6ꢁC20H12: C, 55.77 (56.15); H,
4.27 (4.33); N, 8.48 (8.60).
Synthesis of 5, [Ag2(L)(ClO4)2]n. A solution of AgClO4 (10.41 mg, 0.050 mmol) in
acetone (2 mL) was added to a solution of L (10 mg, 0.025 mmol) in acetone (3 mL).
Colourless blockꢀlike crystals were obtained in about 65− 70% yield within 1ꢀ2 days. IR
(KBr, pellet): 2940, 2872, 2358, 2255, 1607, 1439, 1372, 1261, 1230, 1091, 1047, 967, 852,
785, 654, 617, 533, 453 cm−1. Elem. Anal. (%) Calcd (found) for C13H15AgClN2O4: C, 38.40
(38.56); H, 3.72 (3.69); N, 6.89 (6.84).
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Synthesis of 6, [Ag2(L)(CF3SO3)2(C4H8O)2]n. A solution of AgCF3SO3 (13 mg,
0.050 mmol) in tetrahydrofuran (2 mL) was added to a solution of L (10 mg, 0.025 mmol) in
tetrahydrofuran (3 mL). Colourless needleꢀlike single crystals were obtained in about 65%
yield within 1ꢀ2 days. IR (KBr, pellet): 3446, 2938, 2840, 2360, 2340, 2246, 2078, 1608,
1447, 1238, 1163, 1061, 973, 864, 758, 634, 571, 515 cm−1. Elem. Anal. (%) Calcd (found)
for C36H46Ag2F6N4O8S2: C, 40.92 (40.34); H, 4.39 (4.50); N, 5.30 (4.36).
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Synthesis of 7, [Ag2(L)(CF3SO3)2(C3H6O)2]n. A solution of AgCF3SO3 (13 mg,
0.050 mmol) in acetone (2 mL) was added to a solution of L (10 mg, 0.025 mmol) in acetone
(3 mL). Colourless rectangularꢀlike single crystals were obtained in about 65% yield within
1ꢀ2 days. IR (KBr, pellet): 2881, 2380, 2076, 1466, 1359, 1240, 1148, 1098, 1060, 960, 841,
634, 571, 529 cm−1. Elem. Anal. (%) Calcd (found) for C17H21AgF3N2O4S: C, 39.70 (39.04);
H, 4.12 (4.35); N, 5.45 (4.67).
Synthesis of 8, {[Ag2(L)2](BF4)(C3H6O)}n. A solution of AgBF4 (9.7 mg, 0.049
mmol) in acetone (2 mL) was added to a solution of L (10 mg, 0.025 mmol) in acetone (3
mL). Colourless rectangularꢀlike single crystals were obtained (as acetone solvate) in about
60% yield within 2ꢀ3 days. IR (KBr, pellet): 2851, 2360, 2230, 1706, 1605, 1443, 1345,
1223, 1051, 930, 841, 763, 571, 529 cm−1. Elem. Anal. (%) Calcd (found) for
C26H30AgN4ꢁBF4ꢁ2(C3H6O): C, 54.18 (52.60); H, 5.97 (5.15); N, 7.90 (9.38) (the marked
discrepancies between the calculated and found values are most probably due to evaporation
of the acetone crystallization solvent during the analysis).
Synthesis of 9, [Ag2(L)3(PF6)2]n. A solution of AgPF6 (12.68 mg, 0.050 mmol) in
acetone (2 mL) was added to a solution of L (10 mg, 0.025 mmol) in acetone (3 mL).
Colourless blockꢀlike single crystals were obtained (as acetone solvate) in about 60% yield
within 2ꢀ3 days. IR (KBr, pellet): 2895, 2380, 2253, 1696, 1605, 1395, 1247, 1178, 1049,
838, 747, 689, 571, 537 cm−1. Elem. Anal. (%) Calcd (found) for C78H90Ag2F12N12P2: C,
55.07 (54.99); H, 5.33 (5.27); N, 9.88 (9.83).
Anion-exchange experiments. The anionꢀexchange experiments were carried out
with the freshly prepared crystals of 1, 7, 8 (5 mg) by immersing in 3 M aqueous solution (2
mL) of each corresponding sodium salt, and leaving undisturbed for 30 min to 3 h at ambient
temperature. The resultant anionꢀexchanged solid was collected by filtration, washed several
times with water, and then dried in air. The crystalline materials obtained from the anionꢀ
exchange experiments were not suitable for singleꢀcrystal Xꢀray diffraction because of their
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loss of transparency during the immersion. The products associated with the anion exchange
were thus analysed by IR and PXRD.
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Electrochemical measurements. CV Analysis for L and the CPs of 1, 3, 4 & 7-9.
The electrochemical measurements were performed with a CH760D electrochemical
workstation (CH Instruments, USA) using a standard three electrode cell setup. The
experiments were carried out using three electrode system where Platinum (Pt) foil as
working electrode, Pt wire as counter electrode and saturated calomel electrode (SCE) as
reference electrode.
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Single-crystal structure determinations. The Xꢀray measurements [Brukerꢀ
ApexDuo diffractometer, IꢃS microfocus MoKα radiation] were carried out at ca. 110(2) K
on crystals coated with a thin layer of amorphous oil. These structures were solved by direct
and Fourier methods and refined by fullꢀmatrix leastꢀsquares (using standard crystallographic
software (SHELXTꢀ2014, SHELXLꢀ2014)).84,85 Compound 9 was found to contain severely
disordered crystallization solvent (mostly acetone) within the intraꢀlattice voids, which
couldn't be modeled by discrete atoms. Correspondingly, the contribution of the disordered
solvent moieties was subtracted from the diffraction pattern by the Squeeze procedure and
PLATON software.86 The TOPOS software package was used to analyze the topological
features of the available coordination networks.57 The integrity of the crystalline products 1ꢀ9
was confirmed in each case by repeated measurements of the unitꢀcell dimensions from
different single crystallites, inspection of their morphologies, as well as by routinely
matching between the simulated and experimental powder Xꢀray diffraction patterns. The
crystal data of the available structures are:
(L) C26H30N4, Mr = 398.54, monoclinic, space group P21/n (No. 14), a = 7.1553(5), b =
28.203(2), c = 16.4056(13) Å, β = 98.339(3)°, V = 3275.7(4) Å3, T = 110 K, Z = 6,
µ(MoKα) = 0.07 mmꢀ1, ρ(calcd) = 1.21 g·cmꢀ3, 23110 reflections measured to θ = 25.0°, of
which 5771 were unique (Rint = 0.037) and 4476 with I > 2σ(I). Final R1 = 0.041 (wR2 =
0.096) for the 4476 data above the intensity threshold, and R1 = 0.058 (wR2 = 0.106) for all
unique data. CCDC 1449780.
(1) C13H15AgN3O3, Mr = 369.15, monoclinic, space group P21/c (No. 14), a = 5.7530(6), b =
16.9877(14), c = 13.3029(12) Å, β = 90.020(6)°, V = 1300.1(2) Å3, T = 110 K, Z = 4,
µ(MoKα) = 1.56 mmꢀ1, ρ(calcd) = 1.87 g·cmꢀ3, 11063 reflections measured to θ = 28.39°, of
which 3234 were unique (Rint = 0.044) and 2843 with I > 2σ(I). Final R1 = 0.027 (wR2 =
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0.067) for the 2843 data above the intensity threshold, and R1 = 0.032 (wR2 = 0.070) for all
unique data. CCDC 1449781.
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(2): C13H15AgN3O3, Mr = 369.15, monoclinic, space group P21/c (No. 14), a = 8.6992(4), b =
9.4145(4), c = 17.7035(8) Å, β = 104.214(2)°, V = 1405.50(11) Å3, T = 110 K, Z = 4,
µ(MoKα) = 1.44 mmꢀ1, ρ(calcd) = 1.74 g·cmꢀ3, 21931 reflections measured to θ = 28.45°, of
which 3543 were unique (Rint = 0.032) and 3236 with I > 2σ(I). Final R1 = 0.018 (wR2 =
0.041) for the 3236 data above the intensity threshold, and R1 = 0.021 (wR2 = 0.042) for all
unique data. CCDC 1449782.
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(3): C26H30Ag2N6O6ꢁC16H9, Mr = 939.53, orthorhombic, space group Pca21 (No. 29), a =
16.861(2), b = 15.8050(16), c = 13.9131(17) Å, V = 3707.7(7) Å3, T = 110 K, Z = 4,
µ(MoKα) = 1.12 mmꢀ1, ρ(calcd) = 1.68 g·cmꢀ3, 19865 reflections measured to θ = 25.0°, of
which 6442 were unique (Rint = 0.045) and 5296 with I > 2σ(I). Final R1 = 0.056 (wR2 =
0.131) for the 5296 data above the intensity threshold, and R1 = 0.073 (wR2 = 0.143) for all
unique data. CCDC 1449783.
(4): C26H30Ag2N6O6ꢁC20H12, Mr = 990.59, orthorhombic, space group Pbca (No. 61), a =
15.2465(6), b = 18.3060(9), c = 28.5486(15) Å, V = 7968.0(7) Å3, T = 110 K, Z = 8,
µ(MoKα) = 1.04 mmꢀ1, ρ(calcd) = 1.65 g·cmꢀ3, 30531 reflections measured to θ = 25.02°, of
which 7033 were unique (Rint = 0.049) and 5223 with I > 2σ(I). Final R1 = 0.042 (wR2 =
0.072) for the 5223 data above the intensity threshold, and R1 = 0.067 (wR2 = 0.081) for all
unique data. CCDC 1449784.
(5): C13H15AgClN2O4, Mr = 406.59, monoclinic, space group P21/c (No. 14), a = 5.6448(6),
b = 16.1137(16), c = 15.8133(16) Å, β = 95.090(6)°, V = 1432.7(3) Å3, T = 110 K, Z = 4,
µ(MoKa) = 1.61 mmꢀ1, ρ(calcd) = 1.88 g·cmꢀ3, 11970 reflections measured to θ = 28.33°, of
which 3562 were unique (Rint = 0.038) and 2850 with I > 2σ(I). Final R1 = 0.036 (wR2 =
0.077) for the 2850 data above the intensity threshold, and R1 = 0.051 (wR2 = 0.082) for all
unique data. CCDC 1449785.
(6): C36H46Ag2F6N4O8S2, Mr = 1056.63, monoclinic, space group C2/c (No. 15), a =
32.192(3), b = 10.4571(13), c = 13.8435(15) Å, β = 110.552(5)°, V = 4353.6(9) Å3, T = 110
K, Z = 4, µ(MoKa) = 1.07 mmꢀ1, ρ(calcd) = 1.61 g·cmꢀ3, 14398 reflections measured to θ =
25.01°, of which 3839 were unique (Rint = 0.028) and 2921 with I > 2σ(I). Preliminary R1 =
0.11 for the 2921 data above the intensity threshold. Due to the poor quality of the crystals
and of the diffraction pattern (resulting from disorder of the triflate anions and THF ligands),
as well as very low percentage of significant experimental data, this structure could not be
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fully refined with acceptable precision, and further calculations were interrupted at this
preliminary stage. Yet, the coordination pattern in this structure (with THF species
coordinated to the Ag centers) is very similar to that in the isostructural compound 7 (with
acetone molecules attached instead to the silver ions).
(7): C17H21AgF3N2O4S, Mr = 514.29, monoclinic, space group Cc (No. 9), a = 33.327(3), b =
10.3153(10), c = 13.3212(11) Å, β = 112.453(4)°, V = 4232.4(7) Å3, T = 110 K, Z = 8,
µ(MoKa) = 1.10 mmꢀ1, ρ(calcd) = 1.61 g·cmꢀ3, 18592 reflections measured to θ = 28.40°, of
which 8609 were unique (Rint = 0.020) and 8203 with I > 2σ(I). Final R1 = 0.050 (wR2 =
0.147) for the 8203 data above the intensity threshold, and R1 = 0.052 (wR2 = 0.151) for all
unique data. Flack parameter = 0.05(5). CCDC 1449786.
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(8): C26H30AgN4ꢁBF4ꢁ2(C3H6O), Mr = 709.37, triclinic, space group Pꢀ1 (No. 2), a
=9.3940(14), b = 14.0082(16), c = 15.0044(19) Å, α = 116.249(4), β = 106.520(4), γ =
91.906(4)°, V = 1668.5(4) Å3, T = 110 K, Z = 2, µ(MoKa) = 0.66 mmꢀ1, ρ(calcd) = 1.41
g·cmꢀ3, 11907 reflections measured to θ = 25.09°, of which 5866 were unique (Rint = 0.025)
and 5314 with I > 2σ(I). Final R1 = 0.029 (wR2 = 0.065) for the 5314 data above the
intensity threshold, and R1 = 0.034 (wR2 = 0.067) for all unique data. CCDC 1449787.
(9): C78H90Ag2F12N12P2, Mr = 1701.30, monoclinic, P21/c (No. 14), a = 13.3243(14), b =
12.6404(13), c = 28.098(3) Å, β = 101.448(5)°, V = 4638.3(8) Å3, T = 110 K, Z = 2,
µ(MoKa) = 0.52 mmꢀ1, ρ(calcd) = 1.22 g·cmꢀ3, 53248 reflections measured to θ = 27.33°, of
which 10373 were unique (Rint = 0.030) and 8744 with I > 2σ(I). Final R1 = 0.035 (wR2 =
0.087) for the 8744 data above the intensity threshold, and R1 = 0.045 (wR2 = 0.093) for all
unique data. CCDC 1449788.
ASSOCIATED CONTENT
Supporting information
IRꢀspectra, PXRD patterns, CV and Xꢀray crystallographic files (CIFs). CCDC 1449780ꢀ
1449788 (compounds L, 1ꢀ5 and 7-9, respectively) contain the supplementary
crystallographic data for this paper. These data can be obtained free of charge from the
Cambridge Crystallographic Data Center via www.ccdc.cam.ac.uk/data_request/cif. The
Supporting Information is available free of charge on the ACS Publication website at DOI:
10.1021/acs.cgd.0000000.
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Acknowledgement
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The authors gratefully acknowledge financial support from the Israel Science Foundation
(grant no. 108/12).
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