Macrocyclic dinuclear, helical, layered and 3-D Ag(i) complexes constructed from AgX (X = NO3- and ClO4-) and flexible bis(pyridyl) ligands with a chelating spacer: Syntheses, structures and photoluminescence properties

Article abstract of DOI:10.1039/c5dt00265f

Reaction of AgX (X = NO₃^- and ClO₄^-) and three flexible bis(pyridyl) ligands with a chelating spacer leads to the formation of eight novel Ag(i)-bis(pyridyl) coordination complexes: {[Ag₂L1(NO₃)₂]_n·2nH₂O} (1), {[AgL1]_n·nClO₄} (2), {[AgL2]_n·nNO₃} (3), {[AgL2]_n·nClO₄} (4), [Ag₂(H₂L2)₂]·6ClO₄·9H₂O (5), {[AgL3]_n·nNO₃·nH₂O} (6), {[AgL3]_n·nClO₄·nH₂O} (7), and {[Ag₃(L3)₂(ClO₄)]_n·2nClO₄} (8) (L1 = N,N′-bis(pyridin-2-ylmethyl)propane-1,3-diamine, L2 = N,N′-bis(pyridin-3-ylmethyl)propane-1,3-diamine, L3 = N,N′-bis(pyridin-4-ylmethyl)propane-1,3-diamine), which have been characterized by elemental analysis, IR, TG, UV-Vis DRS, PL, powder and single-crystal X-ray diffraction. Complex 1 presents a (4,4) layered motif which is furnished by the bridging of L1 molecules and nitrate anions in μ₄ (κ¹N1:κ¹N2:κ¹N3:κ¹N4) and μ₂ (κ¹O4:κ¹O6) modes. With a different μ₂ (κ¹N1:κ¹N2:κ¹N3:κ¹N4) mode, L1 molecules in complex 2 join the adjacent Ag(i) cations to form a helical chain structure. Complexes 3 and 4 also show helical chain structures with the L2 molecules displaying the same μ₃ (κ¹N1:κ¹N2:κ¹N3:κ¹N4) mode. The protonation of -NH- groups in the chelating spacer leads to the formation of H₂L2²⁺ cations which further results in a macrocyclic dinuclear motif in complex 5. Complexes 6 and 7 are 3-D svi-x nets with the counter-anions and lattice water molecules being encapsulated in the 1-D channels. Complex 8 exhibits a snake-shaped chain with the L3 molecules presenting μ₃ (κ¹N:κ¹N′:κ¹N″:κ¹N) mode. The structural diversities of complexes 1-8 can be attributed to the coordination modes and conformations of L1-L3. The photoluminescence properties demonstrate that complexes 1, 2 and 5 exhibit ligand-based blue emission maxima from 455 to 462 nm at room temperature in the solid state. This journal is

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PAPER
Macrocyclic dinuclear, helical, layer and 3-D Ag(I) complexes
-
-
constructed from AgX (X = NO3 and ClO4 ) and flexible bis(pyridyl)
ligands with chelating spacer: syntheses, structures and
photoluminescent properties †
5
Jing Huang,ab Zhao-Peng Deng,a Ying-Hui Xiao,a Li-Hua Huo,*a Shu-Nan Zhao,a Fa-Yuan Gea and Shan
Gao*a
Received (in XXX, XXX) Xth XXXXXXXXX 200X, Accepted Xth XXXXXXXXX 200X
DOI: 10.1039/b000000x
ꢀ
Reaction of AgX (X = NO3ꢀ and ClO4 ) and three flexible bis(pyridyl) ligands with chelating spacer leads
10 to the formation of eight novel Ag(I)ꢀbis(pyridyl) coordination complexes, {[Ag2L1(NO3)2]n·2nH2O} (1),
{[AgL1]n·nClO4} (2), {[AgL2]n·nNO3} (3), {[AgL2]n·nClO4} (4), [Ag2(H2L2)2]·6ClO4·9H2O (5),
{[AgL3]n·nNO3·nH2O} (6), {[AgL3]n·nClO4·nH2O} (7), and {[Ag3(L3)2(ClO4)]n·2nClO4} (8) (L1 =
N,N’ꢀbis(pyridinꢀ2ꢀylmethyl)propaneꢀ1,3ꢀdiamine, L2 = N,N’ꢀbis(pyridinꢀ3ꢀylmethyl)propaneꢀ1,3ꢀ
diamine, L3 = N,N’ꢀbis(pyridinꢀ4ꢀylmethyl)propaneꢀ1,3ꢀdiamine), which have been characterized by
15 elemental analysis, IR, TG, UVꢀVis DRS, PL, powder and singleꢀcrystal Xꢀray diffraction. Complex 1
presents (4,4) layer motif which is furnished by the bridging of L1 molecules and nitrate anions in ꢀ4
(κ1N1 : κ1N2 : κ1N3 : κ1N4) and ꢀ2 (κ1O4 : κ1O6) modes. With a different ꢀ2 (κ1N1 : κ1N2 : κ1N3 : κ1N4)
mode, L1 molecules in complex 2 join adjacent Ag(I) cations to form helical chain structure. Complexes
3 and 4 also show helical chain structure with the L2 molecules displaying the same ꢀ3 (κ1N1 : κ1N2 :
20 κ1N3 : κ1N4) mode. The protonation of –NH– groups in the chelating spacer leads to the formation of
H2L22+ cations which further results in macrocyclic dinuclear motif in complex 5. Complexes 6 and 7 are
3ꢀD svi-x net with the counterꢀanions and lattice water molecules being encapsulated in the 1ꢀD channels.
Complex 8 exhibits snakeꢀshaped chain with the L3 molecules presenting ꢀ3 (κ1N : κ1N’ : κ1N’’ : κ1N’’’)
mode. The structural diversities of complexes 1-8 can be attributed to the coordination modes and
25 conformations of L1-L3. The photoluminescent properties demonstrate that complexes 1, 2 and 5 exhibit
ligandꢀbased blue emission maximum from 455 to 462 nm at room temperature in the solid state.
45 ligands which involve different spacers, such as aliphatic
hydrocarbon,16 amide,17 ether18 and so on. However, these
spacers play the role of tuning the degrees of freedom. Only few
examples19 concerned such spacers that modulate the target
architectures by coordinating to the metal centers. Therefore,
50 modulating the structures and properties of Ag(I)ꢀbis(pyridyl)
coordination complexes through the coordination of designed
spacers would be a worth and interesting work.
Introduction
Research of Ag(I) coodination complexes with the rigid or
flexible bis(pyridyl) ligands has attracted intensive interests in
30 crystal engineering and coordination chemistry,1ꢀ7 which is not
only ascribed to the potential applications in the fields of gas
storage, catalysis and photoluminescence, but also attributed to
their intriguing architectures resulted from the unique properties
of the two types of components. On the one hand, Ag(I) is noted
35 for its rather pliant coordination sphere due mainly to a d10
electronic configuration.8ꢀ10 Coordination numbers from two to
eight have been observed (without considering the Ag···Ag
interaction).11ꢀ13 Along with its soft Lewis acidic properties, Ag(I)
ion is a particularly good match for the flexible coordinative
40 tendencies of bis(pyridyl) ligands. On the other hand, bis(pyridyl)
ligand, especially the flexible bis(pyridyl) ligands, have many
degrees of freedom and hence few conformational constraints, as
well as the unpredictable nature of such systems.14,15 Up to date,
many studies have been carried out using flexible bis(pyridyl)
In previous work, our groups reported two series of Ag(I)ꢀ
bis(pyridyl) coordination complexes assembled from AgX (X =
ꢀ
ꢀ
55 NO3 and ClO4 ) and flexible bis(pyridyl) cations with
symmetrical –NH–CH2–C6H4–CH2–NH–20 and unsymmetrical –
CH2–NH–21,22 spacer. For the long aromatic –NH–CH2–C6H4–
CH2–NH– spacer, macrocyclic dinuclear, helical chains, (4,4)
layer and 3ꢀD nonꢀinterpenetrating diamond framework were
60 obtained. In contrast, short aliphatic –CH2–NH– spacer was
inclined to form helical chain structures. Subsequently, we
propose an assumption according to these results: whether novel
structures could be obtained by using such ligands that combine
the merits of the two types of spacers? Bear this conception in
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mind, we designed and synthesized three flexible bis(pyridyl)
molecules with long aliphatic –CH2–NH–CH2–CH2–CH2–NH–
CH2– spacer, N,N’ꢀbis(pyridinꢀ2ꢀylmethyl)propaneꢀ1,3ꢀdiamine
integration sphere diffuse reflectance attachment. A pressed
barium sulfate powder tablet was used as the reference.
Luminescence spectra were measured on a Perkin Elmer LS 55
(L1), N,N’ꢀbis(pyridinꢀ3ꢀylmethyl)propaneꢀ1,3ꢀdiamine (L2), and 60 luminance meter.
N,N’ꢀbis(pyridinꢀ4ꢀylmethyl)propaneꢀ1,3ꢀdiamine (L3) (Scheme
5
Preparation of complexes
1). In contrast to the aforementioned bis(pyridyl) molecules, these
three molecules keep the original characteristics of flexible spacer
and variable position of pyridyl N atoms. Meanwhile, the pyridyl
N atom and neighbouring aliphatic N atom in L1, the propane
Syntheses of complexes 1-4 and 6-8. Equal amounts (2 mmol)
ꢀ
ꢀ
of AgX (X = NO3 and ClO4 ) and L1-L3 were mixed in 15 mL
mixed H2O/MeCN (v/v = 1 : 1) solution. The mixture was stirred
65 at room temperature for 5 min followed by filtration. Single
crystals of these seven complexes suitable for Xꢀray diffraction
were isolated from the filtrate after avoiding illumination for
several days. It should be indicated that complexes 7 and 8 are
accidentally obtained in the same reaction system with different
70 colour and shape, which have also been demonstrated by single
crystal Xꢀray diffraction. Their properties are finished with the
samples selected under the microscope. There yield is calculated
with 50% percentage of the reactants.
Complex 1 (66% yield based on Ag). Anal. Calcd for
75 C15H24N6O8Ag2: C 28.50, H 3.83, N 13.29%; Found: C 28.46, H
3.88, N 13.31%. IR (ν/cmꢀ1): 3490m, 3205m, 2927m, 2850m,
1598m, 1569m, 1479m, 1434m, 1380s, 1097m.
Complex 2 (72% yield based on Ag). Anal. Calcd for
C15H20N4O4ClAg: C 38.86, H 4.35, N 12.08%; Found: C 38.84,
80 H 4.41, N 12.05%. IR (ν/cmꢀ1): 3268m, 2923m, 2846m, 1594s,
1569m, 1477s, 1436s, 1091s, 1003m.
10 diamine unit in the spacer could coordinate to Ag(I) cations in
monodentate mode or chelate to the Ag(I) cations, forming stable
fiveꢀ and sixꢀmembered ring, which then effectively modulate the
topological structures of target complexes. Moreover, the three
ligands present the unique feature that the propane diamine unit
15 and the pyridine unit have different alkalinity (Pkb1 of propane
diamine, 3.53; Pkb of pyridine, 8.80). Therefore, the propane
diamine units can be firstly protonated to prevent its coordination
to Ag(I) cations and further induce different structures. More
interestingly, due to the long flexible 2,6ꢀdiazaheptane spacer,
20 linear, ‘L’ shaped, ‘W’ shaped, ‘V’ shaped, even other intriguing
conformations will be formed for L1-L3 during the assemble
process. In this case, various structural types could be generated
with the linkage of Ag(I) cations and the above comformations.
Under the guidance of these ideas, we reported in this paper the
25 syntheses, structures and luminescent properties of eight novel
Ag(I)ꢀbis(pyridyl) coordination complexes based on the reaction
ꢀ
ꢀ
Complex 3 (70% yield based on Ag). Anal. Calcd for
C15H20N5O3Ag: C 42.27, H 4.73, N 16.43%; Found: C 42.23, H
4.77, N 16.45%. IR (ν/cmꢀ1): 3235m, 2921m, 2846m, 1594m,
85 1577m, 1473m, 1427m, 1361s, 1097m.
of AgX (X
{[Ag2L1(NO3)2]n·2nH2O}
{[AgL2]n·nNO3} (3),
= NO3 and ClO4 ) and L1-L3, namely,
(1),
{[AgL1]n·nClO4}
(2),
(4),
{[AgL2]n·nClO4}
30 [Ag2(H2L2)2]·6ClO4·9H2O (5), {[AgL3]n·nNO3·nH2O} (6),
{[AgL3]n·nClO4·nH2O} (7), and {[Ag3(L3)2(ClO4)]n·2nClO4}
(8). Structure analyses indicate that these eight complexes exhibit
diverse macrocyclic dinuclear, helical, layer and 3ꢀD svi-x
networks induced by the coordination modes and conformations
35 of L1-L3. It should be noted that the protonation of –NH– groups
in the chelating spacer effectively modulated the target complex
and results in macrocyclic dinuclear motif in complex 5.
Moreover, the elemental analysis, powder Xꢀray diffraction,
infrared spectra, thermal stability, UVꢀVis diffuse reflectance
40 spectra and photoluminescent property of these eight complexes
were also performed.
Complex 4 (68% yield based on Ag). Anal. Calcd for
C15H20N4O4ClAg: C 38.86, H 4.35, N 12.08%; Found: C 38.88,
H 4.39, N 12.06%. IR (ν/cmꢀ1): 3280m, 2927m, 2843m, 1596m,
1572m, 1473m, 1428m, 1089s, 1002m.
90
Complex 6 (78% yield based on Ag). Anal. Calcd for
C15H22N5O4Ag: C 40.56, H 4.99, N 15.76%; Found: C 40.54, H
4.94, N 15.74%. IR (ν/cmꢀ1): 3407m, 3241m, 2935m, 2844m,
1602s, 1560m, 1469m, 1382s, 1202m.
Complex 7 (63% yield based on Ag). Anal. Calcd for
95 C15H22N4O5ClAg: C 37.40, H 4.60, N 11.63%; Found: C 37.42,
H 4.64, N 11.60%. IR (ν/cmꢀ1): 3490m, 3245m, 2933m, 2848m,
1601s, 1556m, 1473m, 1108s, 1004m.
Complex 8 (70% yield based on Ag). Anal. Calcd for
C30H40N8O12Cl3Ag3: C 31.76, H 3.55, N 9.88%; Found: C 31.79,
100 H 3.58, N 9.90%. IR (ν/cmꢀ1): 3276m, 2928m, 2849m, 1602m,
1562m, 1473m, 1433m, 1085s, 1036m.
Experimental
Materials and methods
All chemicals and solvents were of A. R. grade and used without
45 further purification in the syntheses. L1, L2 and L3 were
synthesized according to the previous method19,23. Elemental
analyses were carried out with a Vario MICRO from Elementar
Analysensysteme GmbH, and the infrared spectra (IR) were
recorded from KBr pellets in the range of 4000ꢀ400 cmꢀ1 on a
50 Bruker Equinox 55 FTꢀIR spectrometer. Powder Xꢀray
diffraction (PXRD) patterns were measured at 293 K on a Bruker
D8 diffractometer (Cu Kα, λ = 1.54059 Å). The TG analysis were
carried out on a Perkin Elmer TG/DTA 6300 thermal analyzer
under flowing N2 atmosphere, with a heating rate of 10 ℃/min.
55 UVꢀVis DRS (diffuse reflectance spectra) were measured on a
Perkin Elmer Lambda 900 ultravioletꢀvisible spectrometer with
Synthesis of complex 5. 2 mmol of HClO4 [70% wt, the amount
of acid is calculated from their mass fraction, volume, density and
molecular weight] was added to the aqueous solution of 1mmol
105 of L2, and then 1mmol of AgClO4 was added to this system. The
mixture was stirred at room temperature for 5 min followed by
filtration. Colorless crystals of complex 5 suitable for Xꢀray
diffraction were isolated from the filtrate after avoiding
illumination for several days. Yield: 70% (based on Ag). Anal.
110 Calcd for C30H64N8O33Cl6Ag2: C 24.13, H 4.32, N 7.50%; Found:
C 24.16, H 4.38, N 7.52%. IR (ν/cmꢀ1): 3451m, 3074m, 2935m,
2834s, 1596m, 1537m, 1474m, 1430m, 1089s, 1008m.
2
| Dalton Trans., [2015], [44], 00–00
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CAUTION! Although not encountered in our experiments, metal
perchlorates are potentially explosive. They should be handled
carefully.
in singleꢀcrystal form. Instead, powder samples of these
complexes are isolated from the filtrate, which have been proved
to be new phase. The stretching bands around 3490~3205 cmꢀ1 in
60 the IR spectra of complexes 1-8 can be attributed to the existence
of water molecules, ν(NꢀH) vibrations, and the hydrogenꢀbonding
interactions. The bands appearing in the range of 1602~1427 cmꢀ1
in complexes 1-8 are ascribed to the skeletal vibration of aromatic
rings. The characteristic vibrations of nitrate anions in complexes
65 1, 3 and 6 are at 1380, 1361 and 1382 cmꢀ1, whereas the
characteristic vibrations of perchlorate anions in complexes 2, 4,
5, 7 and 8 are 1091, 1089, 1108, 1085 and 1089 cmꢀ1,
respectively.21
X-ray Crystallographic Measurements
5
Table 1 provides a summary of the crystal data, data collection
and refinement parameters for complexes 1ꢀ8. All diffraction data
were collected at 295
diffractometer with graphite monochromatized MoꢀKα (λ =
0.71073 Å) radiation in scan mode. All structures were solved
K on a RIGAKU RAXISꢀRAPID
ω
10 by direct method and difference Fourier syntheses. All nonꢀ
hydrogen atoms were refined by fullꢀmatrix leastꢀsquares
techniques on F2 with anisotropic thermal parameters. The
hydrogen atoms attached to carbons were placed in calculated
Structure description of complexes 1 and 2
ꢀ
ꢀ
positions with C–H = 0.93 (aromatic) or 0.97 Å (methylene), and 70 Reaction of L1 and AgX (X = NO3 and ClO4 ) leads to the
15 U (H) = 1.2Ueq (C) in the riding model approximation. The
hydrogen atoms of O2w in complex 5 and the hydrogen atoms
attached to nitrogens in complexes 1-5, 7 and 8 were located in
difference Fourier maps and were also refined in the riding model
formation of two different complexes. As illustrated in Fig. 1, the
asymmetric unit of complex 1 consists of two Ag(I) cations, one
L1 molecule, two nitrate anions and two lattice water molecules.
In contrast, the asymmetric unit of complex 2 contains one Ag(I)
approximation, with OꢀH distance restraint 0.85(1), 0.86(1) Å and 75 cation, one L1 molecule and one free perchlorate anion. Owing to
20 U (H) =1.5Ueq(O, N). The left hydrogen atoms of water
molecules in complexes 1, 5ꢀ7 and the hydrogen atoms attached
to nitrogens in complex 6 were fixed by WINGX with O–H
distance restraint (0.85 and 0.88 Å) and U(H) = 1.5Ueq (O, N).
the different coordination mode of L1 molecule and different
coordination ability of nitrate and perchlorate anion, the two
complexes exhibit diverse architectures.
For complex 1, the two Ag(I) cations present different
The perchlorate anions in complex 4 was disordered over two 80 coordination geometry with Ag1 locating in a tetrahedral N2O2
25 positions with the ratio 0.64 : 0.36. All calculations were carried
out with the SHELXL97 program.24 The CCDC reference
numbers are 1037042ꢀ1037049 for complexes 1ꢀ8. Selected bond
distances and selected hydrogen bond parameters for all
sphere and Ag2 locating in a Tꢀshaped N2O sphere (Fig. 1). The
L1 molecules connect adjacent Ag1 and Ag2 cations in ꢀ4 (κ1N1 :
κ1N2 : κ1N3 : κ1N4) mode (Scheme 2) to generate chain motif
along the bꢀaxis (Fig. 2). The shortest separation between two
complexes are presented in Table S1 and Table S2, respectively 85 adjacent Ag1 and Ag2 cations of 3.016(1) Å indicates the
30 (Supporting Information).
argentophilic interaction,14,25ꢀ27 owing to the distance being
slightly shorter than the summed van der Waals radii of two
silver atoms (3.44 Å).28 Meanwhile, the coordinated nitrate
anions bridge adjacent chains in ꢀ2 (κ1O4 : κ1O6) mode, thus
90 generating (4,4) layer motif with the Ag2 cations being regarded
as fourꢀconnected nodes (Fig. 2). Moreover, the lattice O1w
molecules, acting as both donors and acceptors, extend adjacent
layers into 3ꢀD supramolecular network through intermolecular
hydrogenꢀbonding interactions (Fig. S1, Table S2†).
Results and discussion
Syntheses and IR spectroscopy
As stated above, in order to investigate the influence of chelating
spacers between two terminal pyridyl pendants on the structures
35 and properties of Ag(I)ꢀbis(pyridyl) coordination complexes, we
designed and synthesized three flexible bis(pyridyl) molecules
with long aliphatic –CH2–NH–CH2–CH2–CH2–NH–CH2– spacer
based on our previous work. The experimental conditions are also
95
In comparison with the coordinated nitrate anions in complex 1,
the perchlorate anions in complex 2 form hydrogenꢀbonding
interaction with the aliphatic –NH groups instead of coordinating
to Ag(I) cations due to its weak coordination ability. Therefore,
the Ag(I) cation in complex 2 locates in a tetrahedral N4 sphere
ꢀ
ꢀ
similar to former ones by adding AgX (X = NO3 and ClO4 ) and
40 the three flexible bis(pyridyl) ligands into mixed H2O/MeCN (v/v
= 1 : 1) solution. Therefore, eight complexes with diverse
structures are obtained, in which the three flexible bis(pyridyl) 100 (Fig. 1). The L1 molecules adopt different ꢀ2 (κ1N1 : κ1N2 : κ1N3
molecules exhibit different linear, ‘L’ shaped, ‘W’ shaped, as
well as ‘V’ shaped conformations and the spacers adopt
45 monodentate and chelate modes to form fiveꢀ and sixꢀmembered
rings. Meanwhile, the long aliphatic spacers here lead to the
: κ1N4) mode (Scheme 2) with each pair of pyridyl and aliphatic
N atoms chelating to one Ag(I) cation and connect adjacent Ag(I)
cations to generate helical chain along the bꢀaxis (Fig. 3). Such
connection also increases the distance between two nearest Ag(I)
formation of microporous networks which are not observed in 105 cations. The shortest Ag···Ag separation of 5.784(2) Å here is far
previous work.20ꢀ22 Moreover, small amount of inorganic acids
are also introduced to the reaction system to confirm our original
50 idea that prevents the coordination of the propane diamine units
to Ag(I) cations and further induce different structures through
more than the summed van der Waals radii of two silver atoms
(3.44 Å).28 Meanwhile, the N1ꢀ and N4ꢀcontaining pyridyl rings
in adjacent rightꢀ or leftꢀhelical chains are nearly parallel to each
other, which can provide the chance for the formation of π···π
the protonation of spacer. Subsequently, a new complex 5 is 110 interactions with the centroidꢀtoꢀcentroid distance being 3.953(2)
obtained with the protonated propane diamine units forming
hydrogenꢀbonding interactions with inorganic anions.
Å. All these π···π interactions extend adjacent helices into layer
structure as shown in Fig. 3. Furthermore, the perchlorate anions
join adjacent helical layers through the hydrogenꢀbonding
interactions (Table S2†) between atoms O3 and aliphatic –
55 Unfortunately, complexes containing other protonated L1-L3
ꢀ
under the existence of HX (X = NO3ꢀ and ClO4 ) are not obtained
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N3H3N groups, giving rise to 3ꢀD supramolecular network (Fig.
S2†).
giving rise to 3ꢀD hostꢀguest supramolecular network (Fig. S4†).
60 Structure description of complexes 6-8
Structure description of complexes 3-5
As the case above, complexes 6 and 7 are also isomorphous and
Different from the above two complexes, complexes 3 and 4 are
isomorphous and possess the same helical structure under the
identical reaction condition with the reactants of L2 and AgX (X
possess the same 3ꢀD framework under the identical reaction
ꢀ
5
condition with the reactants of L3 and AgX (X = NO3ꢀ and ClO4 ).
Therefore, the structures of complex 6 and 7 will be discussed as
ꢀ
ꢀ
= NO3 and ClO4 ), hence the structures of complex 3 and 4 will 65 a whole. As shown in Fig. 1, the asymmetric units of complexes 6
be discussed as a whole. As shown in Fig. 1, both the asymmetric
units of complexes 3 and 4 consist of one Ag(I) cation, one L2
and 7 consist of one Ag(I) cation, one L3 molecule, one counterꢀ
anion (nitrate for complex 6 and perchlorate for complex 7) and
one lattice water molecule, all of which locate at different special
positions. The Ag(I) cations exhibit tetrahedral N4 sphere (Fig. 1).
10 molecule and one counterꢀanion (nitrate for complex 3 and
perchlorate for complex 4), in which the Ag(I) cations exhibit
tetrahedral N4 sphere (Fig. 1). The L2 molecules in the two 70 The L3 molecules in the two complexes adopt the same ꢀ4 (κ1N1
complexes adopt the same ꢀ3 (κ1N1 : κ1N2 : κ1N3 : κ1N4) mode
(Scheme 2) with the two aliphatic N atoms chelating to one Ag(I)
15 cation and connect adjacent Ag(I) cations to generate helical
chain along the bꢀaxis (Fig. 4). The shortest Ag···Ag separation
: κ1N2 : κ1N3 : κ1N4) mode (Scheme 2) and connect adjacent
Ag(I) cations to generate 3ꢀD positively charged host framework
with the counterꢀanions and lattice water molecules being
encapsulated in the 1ꢀD channels along aꢀ (complex 6) or bꢀaxis
and helical pitch in complex 3 (5.966(3) and 10.314(7) Å) are 75 (complex 7) through hydrogenꢀbonding interactions (Fig. 6,
slightly shorter than those in complex 4 (6.220(2) and 11.068(4)
Å), which is probably ascribed to the larger volume of
20 perchlorate anion than nitrate anion. Different from the
arrangement of helices in complex 2, adjacent helical chains in
Table S2†). Actually, these two complexes also have another type
of 1ꢀD small channels along bꢀ (complex 6) or aꢀaxis (complex 7)
as illustrated in Fig. S5†, which also encapsulates the counterꢀ
anions and lattice water molecules as guests. From the
the two complexes arrange in an inverse order, i.e. ꢀrightꢀleftꢀ 80 topological viewpoint, the Ag(I) cations can be regarded as 9ꢀ
rightꢀ, and are further joined by the counterꢀanions through the
hydrogenꢀbonding interactions (Table S2†) between oxygen
25 atoms and aliphatic –NH groups, forming layer structure in the bc
plane (Fig. 4). Moreover, the counterꢀanions join adjacent helical
connect nodes, and each L3 molecule can be regarded as linker.
Therefore, an analysis by TOPOS430 reveals that the network can
thus be represented to a svi-x net as displayed in Fig. 7 with the
Schläfli symbol of (312.416.58).
layers through the hydrogenꢀbonding interactions between 85 Complex 8 is obtained from the same reaction system of
oxygen atoms and aliphatic or pyridyl –CH groups (C10ꢀ
complex 7. Its asymmetric unit comprise of four Ag(I) cations,
two L3 molecules, one coordinated and two free perchlorate
anions (Fig. 1), in which Ag1 and Ag4 locate at different special
positions. The four Ag(I) cations exhibit three types of
o
H10B···O2, 3.458(2) Å, ∠C10ꢀH10BꢀO2 = 167.2 and C5ꢀ
30 H5A···O3, 2.970(1) Å, ∠C5ꢀH5AꢀO3 = 148.5 o), giving rise to
3ꢀD supramolecular network (Fig. S3†).
By adding a small amount of HClO4 into the reaction system of 90 coordination geometries with different chemical environments
complex 4, a new complex 5 is obtained with the asymmetric unit
containing one Ag(I) cation, one H2L22+ cation, three perchlorate
35 anions and five lattice water molecules (Fig. 1), in which O2w
locates on an inversion center. The Ag(I) cation exhibits linear
(Fig. 1). Ag1 and Ag4 exhibit linear geometry comprised of two
nitrogen atoms, and even longer contact to O12 for Ag4
(Ag4···O12 3.119(5) Å). Ag2 presents trigonal geometry (Fig. 1)
comprised of three nitrogen atoms, and even longer contact to O1
geometry (Fig. 1) comprised of two nitrogen atoms, and even 95 (Ag2···O1 2.919(3) Å). Ag3 exists in a tetrahedral N3O sphere.
longer contact to O3w (Ag1···O3w 2.998(2) Å). Owing to the
two aliphatic –NH groups being protonated, only the two pyridyl
40 N atoms of the H2L22+ cation coordinate to two Ag(I) cations,
which further generate macrocyclic dinuclear unit with another
The two different L3 molecules in the present complex adopt the
same ꢀ3 (κ1N : κ1N’ : κ1N’’ : κ1N’’’) mode (Scheme 2) with the
two aliphatic N atoms chelating to one Ag(I) cation and connect
adjacent Ag(I) cations to generate snakeꢀshaped chain which
symmetryꢀrelated H2L22+ cation. The two protonated aliphatic – 100 contains two types of π···π interactions among adjacent N4, N5
NH groups effectively capture the perchlorate anions and lattice
water molecules through hydrogenꢀbonding interactions. The N1ꢀ
45 and N4ꢀcontaining pyridyl rings in adjacent dinuclear units are
nearly parallel to each other, which can provide the chance for the
and N8ꢀcontaining pyridyl rings (Fig. 8). The centroidꢀtoꢀcentroid
distances are 3.901(5) and 3.938(5) Å, respectively. Meanwhile,
it is interesting to note that the Ag···Ag separations between
adjacent two Ag(I) cations are nearly equal to each other
formation of π···π interactions with the centroidꢀtoꢀcentroid 105 (Ag1···Ag2, 6.577(1) Å; Ag2···Ag3, 6.276(7) Å; Ag3···Ag4,
distance being 3.698(2) Å. All these π···π interactions extend
adjacent dinuclear units into chain structure as shown in Fig. 5.
50 Meanwhile, anion···π interaction between O12 and the centroid
of the N1ꢀcontaining pyridyl ring is observed with the oxygenꢀtoꢀ
6.287(1) Å) owing to the same coordination mode of bridging L3
molecules. Moreover, adjacent snakeꢀshaped chain arrange along
two different directions with the intersection angle of 42.3 o and
are further extended by the hydrogenꢀbonding interactions
centroid distance of 3.212(2) Å (the planeꢀcentroidꢀanion angles 110 between perchlorate anions and aliphatic –NH groups (Table S2†)
α = 84.0 o) being obviously below the maximum bonding
interaction distance of 3.82 Å as calculated from Pythagoras’
55 theorem.29 Such anion···π interactions join adjacent chains into
layer structure (Fig. S4†) Furthermore, pairs of atoms O3 of the
perchlorate anions extend adjacent layers through the hydrogenꢀ
bonding interactions (Table S2†) between atoms O3 and H3N1,
into 3ꢀD supramolecular network (Fig. S6†)
Influence of three flexible bis(pyridyl) ligands on the
structures
From above discussion, owing to the weaker coordination ability
115 of O than N, most of the nitrate and perchlorate anions are not
4
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coordination to the Ag(I) cations except for those in complex 1.
attribute to the π*ꢀπ transitions. In contrast, the blue luminescent
Therefore, the structural diversities of the eight complexes are 60 emission band at 455 nm for complex 1 (exmax = 349 nm), 457
mainly determined by the three flexible bis(pyridyl) ligands in
view of their coordination modes and conformations. As shown
in Table 2, the L1 molecules in complexes 1 and 2 exhibit
different ꢀ4 and ꢀ2 modes as well as different distorted ‘W’
nm for complex 2 (exmax = 353 nm), and 462 nm for complex 5
(exmax = 343 nm) can probably be assigned to the intraligand (IL)
πꢀπ* transitions because of their resemblance of the emission
spectra with those of L1-L3 (Fig. 10).34,35 Menwhile, the weak
5
shaped and linear conformations (Scheme 2). Such differences 65 emission of the three complexes can be attributed to the heavy
lead to the formation of (4,4) layer for complex 1 and helical
chain structure for complex 2. In contrast, the L2 molecules in
10 complexes 3 and 4 present the same ꢀ3 mode and ‘V’ shaped
conformation (Scheme 2). Hence, complexes 3 and 4 show
atom effect of Ag atom.12,13,33 Heavy atoms, such as Ag atom
here, in the fluorophore or in close contact to it increase the rate
of intersystem crossing (ISC) by strengthening spinꢀorbit
coupling.36,37 Thus, the decrease of fluorescence yield (radiative
similar helical chain structure. Likewise, the L3 molecules in 70 transition S1→S0) is in most cases explained by an increase in the
complexes 6 and 7 present the same ꢀ4 mode as well as the same
‘W’ shaped conformation (Scheme 2) and connect adjacent N4Ag
15 tetrahedra into similar 3ꢀD microporous framework. Instead, the
L3 molecules in complex 8 show the similar ꢀ3 mode and ‘V’
shaped conformation with those in complexes 3 and 4, which join
adjacent N3OAg tetrahedra, N3Ag triangles and N2Ag lines into
snakeꢀshaped chain. The H2L22+ cations in complex 5 only
20 present the simple ‘L’ shaped ꢀ2 mode and coordinate to two
Ag(I) cations to form macrocyclic dinuclear unit. As stated, the
probability of the competing S1→Tn radiationless transition of the
fluorophore. In view of such heavy atom effect, the other five
complexes exhibit no emission at room temperature in the solid
state.
The emission spectra of the three complexes show various
degree of redꢀshift towards their corresponding ligands, which
could be ascribed to the structure diversities arising from the
diverse conformation and the different positions of the pyridyl N
atoms in the three positional isomeric unsymmetrical bis(pyridyl)
75
structures of reported Ag(I)ꢀbis(pyridyl) coordination complexes 80 ligands. Then, such structure diversities further changes the
were only modulated by the degrees of freedom of diverse
spacers in flexible bis(pyridyl) ligands and variable position of
25 pyridyl N atoms. In contrast, this work not only retains the above
modes for tuning the target structures, but also adds extra mode
that modulates the structures through the coordination of
designed spacers to Ag(I) cations. Therefore, the construction of
these eight complexes provides a new idea for building Ag(I)ꢀ
30 bis(pyridyl) complexes containing flexible bis(pyridyl) ligands
with chelating spacers.
charge transition energy between lowest excited state and ground
state.
Conclusions
ꢀ
ꢀ
In conclusion, selfꢀassembly of AgX (X = NO3 and ClO4 ) and
85 three flexible bis(pyridyl) ligands with the chelating spacers
results in eight new complexes, which exhibit diverse
macrocyclic dinuclear, helical, layer and 3ꢀD microporous
networks. In contrast to the bis(pyridyl) ligands with reported
spacers, the ones with long flexible spacers are more inclined to
90 form diverse linear, ‘L’ shaped, ‘W’ shaped, ‘V’ shaped and even
more interesting conformations. Meanwhile, the flexible 2,6ꢀ
diazaheptane spacer here presents monodentate and chelate
modes. With two such features, abundant architectures could be
definitely obtained. Furthermore, the different alkalinity between
95 spacer and pyridine unit can be easily utilized to prevent the
coordination of spacer N atoms to Ag(I) cations and further
construct different structures through the protonation of spacer.
Complexes 1, 2 and 5 present violet emissions in the solid state at
room temperature. The present work provides a good example for
100 crystal engineering that the structures and properties of metalꢀ
organic complexes could be modulated through the coordination
of chelating spacers in flexible bis(pyridyl) ligands.
UV-Vis DRS spectra and luminescent property
In order to investigate the electronic structure of these complexes,
the UVꢀVis diffuse reflectance spectroscopy (DRS) of complexes
35 1-8 in the solid state has been studied, which is converted into
absorbance spectra. As shown in Fig. 9, these complexes show
two broad bands at 282 and 445 nm for complex 1, 288 and 438
nm for complex 2, 270 and 436 nm for complex 3, 269 and 433
nm for complex 4, 264 and 424 nm for complex 5, 267 and 459
40 nm for complex 6, 262 and 439 nm for complex 7, as well as 266
and 438 nm for complex 8. The bands at higher emergy can be
assigned to the intralignad πꢀπ* transitions, whereas the bands at
lower emergy can be assigned to LMCT transition from filled
orbital of the three ligands to the low lined vacant dꢀorbital of the
45 Ag(I) cations.31 Moreover, the spectra of these complexes
indicate different absorption edges reflecting their different colors
observed in the solid state32 (Fig. 9). It should be noted that the
two absorption bands for complexes 1, 2 and 5 are different from
their excitation band in their own excitation spectra (Fig. S9†).
50 For other five complexes, although they exhibit two similar
absorption bands, no excitation spectra can be obtained at room
temperature in the solid state.
Acknowledgments
This work is financial supported by the National Natural Science
105 Foundation of China (51302067), Specialized Research Fund for
the Doctoral Program of Higher Education of China
(20132301120002), Key Project of Natural Science Foundation
of Heilongjiang Province (No. ZD200903), Key Project of
Education bureau of Heilongjiang Province (No. 12511z023, No.
110 2011CJHB006), and the Innovation team of Education bureau of
Heilongjiang Province (No. 2013td002). We thank the University
of Heilongjiang and University of Malaya for supporting this
study. Special thanks are offered to Prof. Seik Weng Ng of
Although most of the Ag(I) complexes have no obvious
emission at room temperature in the solid state,12,13,33 we still
55 measured the photoluminescent properties of L1-L3 and
complexes 1-8 at room temperature in the solid state. As shown
in Fig. 10, upon excitation at 348 nm, L1-L3 exhibit strong violet
emission maximum at 440, 436 and 438 nm which is probably
This journal is © The Royal Society of Chemistry [2015]
Dalton Trans., [2015], [44], 00–00 | 5

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32 A. Dey, S. Bera and K. Biradha, Cryst. Growth Des., 2015, 15, 318.
70 33 M. C. Aragoni, M. Arca, F. Demartin, F. A. Devillanova, F. Isaia, A.
Garau, V. Lippolis, F. Jalali, U. Papke, M. Shamsipur, L. Tei, A. Yari
and G. Verani, Inorg. Chem., 2002, 41, 6623.
University of Malaya for refining the structure of complex 6.
Notes and references
34 J. P. Collin, I. M. Dixon, J. P. Sauvage, J. A. G. Williams, F.
Barigelletti and L. Flamigni, J. Am. Chem. Soc., 1999, 121, 5009.
75 35 R. G. Xiong, J. L. Zuo, X. Z. You, H. K. Fun and S. S. S. Raj,
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36 D. S. McClure, J. Chem. Phys., 1949, 17, 905.
37 M. Kasha, J. Chem. Phys., 1952, 20, 71.
a Key Laboratory of Functional Inorganic Material Chemistry, Ministry of
Education, School of Chemistry and Materials Science, Heilongjiang
University, Harbin 150080, People's Republic of China. Eꢁmail address:
lhhuo68@yahoo.com, shangao67@yahoo.com; Tel.: (+86) 0451ꢁ
86608426; Fax: (+86) 0451ꢁ86608040
5
b College of Pharmacy Harbin Medical University, Harbin 150081,
People's Republic of China.
80
10 † Electronic Supplementary Information (ESI) available: Additional
figures, PXRD patterns, TG curves, selected bond distances and selected
hydrogen bond parameters for complex 1ꢀ8. CCDC reference number
1037042ꢀ1037049. For crystallographic data in CIF or other electronic
format see DOI: 10.1039/b000000x/
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| Dalton Trans., [2015], [44], 00–00
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Table 1. Crystal data and structure refinement parameters of complexes 1ꢀ8
Complex
1
2
3
4
Empirical formula
C15H24N6O8Ag2
632.14
Orthorhombic
Pbca
C15H20N4O4ClAg C15H20N5O3Ag
C15H20N4O4ClAg
463.67
Monoclinic
P 21/n
Mr
463.67
Monoclinic
P 21/n
426.23
Monoclinic
P 21/n
Crystal system
Space group
a/Å
16.0866(9)
12.8688(7)
20.3039(2)
90
9.7157(5)
10.1084(4)
19.1032(8)
90
10.1494(8)
10.3138(7)
17.0067(1)
90
9.8204(5)
11.0676(4)
17.5147(4)
90
b/Å
c/Å
α o
β o
/
90
94.253(4)
90
95.884(6)
90
93.162(3)
90
/
γ/o
90
V/Å3
4203.2(5)
8
1870.9 (1)
4
1770.8(2)
4
1900.7(1)
4
Z
Dc/g cm–3
ꢀ /mm–1
1.998
1.646
1.599
1.620
1.920
1.247
1.161
1.227
Reflections collected
Unique reflections
F(000)
9777
6438
6426
7159
4810
4281
4057
4352
2512
936
864
936
R1, wR2 [I > 2σ(I)]
GOF on F2
0.0400, 0.0889
1.063
0.0567, 0.1267
1.009
0.0482, 0.0884
1.069
0.0519, 0.1190
1.021

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Complex
6
7
8
5
Empirical formula
C15H22N4O5ClAg
481.69
Orthorhombic
Fddd
C30H40N8O12Cl3Ag3
1134.66
Monoclinic
P21/c
C30H64N8O33Cl6Ag2 C15H22N5O4Ag
Mr
444.25
1493.33
Crystal system
Space group
a/Å
Orthorhombic
Triclinic
Fddd
P
1
8.6068(3)
24.6534(1)
35.7404(2)
90
24.3650(2)
8.6123(7)
36.092(3)
90
14.966(2)
13.205(2)
23.389(3)
90
8.0338(5)
13.8229(8)
14.0580(1)
70.665(6)
81.349(6)
73.418(6)
1409.1(2)
1
b/Å
c/Å
α o
β o
/
90
90
118.964(9)
90
/
γ/o
90
90
V/Å3
7583.6(5)
16
7573.5(1)
16
4044.1(1)
4
Z
Dc/g cm–3
ꢀ /mm–1
1.556
1.690
1.864
1.760
1.092
1.239
1.704
1.079
Reflections collected
Unique reflections
F(000)
4484
4521
19937
8415
2173
2174
9296
6439
3616
3904
2256
760
R1, wR2 [I > 2σ(I)]
GOF on F2
0.0764, 0.2179
1.028
0.0521, 0.1283
1.020
0.0609, 0.1340
1.030
0.0582, 0.1541
1.031

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Graphical Abstract:
Macrocyclic dinuclear, helical, layer and 3-D Ag(I) complexes
-
-
constructed from AgX (X = NO3 and ClO4 ) and flexible bis(pyridyl)
ligands with chelating spacer: syntheses, structures and
photoluminescent properties †
Jing Huang, Zhao-Peng Deng, Ying-Hui Xiao, Li-Hua Huo*, Shu-Nan Zhao, Fa-Yuan Ge and
Shan Gao*
-
-
Reaction of AgX (X = NO3 and ClO4 ) and flexible bis(pyridyl) ligands with chelating spacer
leads to the formation of eight novel Ag(I)-bis(pyridyl) coordination complexes, which exhibit
diverse macrocyclic dinuclear, helical, layer and 3-D networks induced by the coordination modes
and conformations of the bis(pyridyl) ligands.

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Figure caption:
Scheme 1 Three flexible bis(pyridyl) molecules used in this work.
Scheme 2 Versatile coordination modes of L1, L2, H2L22+ and L3 in complexes 1-8.
Fig. 1 The asymmetric units of complexes 1-8.
Fig. 2 (4,4) Layer motif (top) of complex 1 formed by the connection of nitrate anions
and ꢀAgꢀL1ꢀ chains (down)
Fig. 3 π···π extended layer motif of complex 2 involving the same helical chains.
Righꢀhelical chains were illustrated here for instance.
Fig. 4 Hydrogenꢀbonding interactions extended layer motif of complexes 3 (a) and 4
(b) involving the alternant rightꢀ and leftꢀhelical chains.
Fig. 5 Chain motif (down) in complex 5 extended by π···π interactions (green dashed
lines) with the channels filled by the lattice water molecules (top).
Fig. 6 3ꢀD microporous host framework (spaceꢀfilling mode) of complexes 6 (a) and 7
(b) with the counterꢀanions and lattice water molecules being encapsulated in the
1ꢀD channels.
Fig. 7 svi-x net topology of complexes 6 and 7.
Fig. 8 Snakeꢀshaped chain structure of complex 8 with the two types of π···π
interactions being denoted as green and pink dashed lines.
Fig. 9 UVꢀVis absorbance spectra (converted from diffuse DSR) for complexes 1ꢀ8.
Fig. 10 Emission spectra of L1 and complexes 1ꢀ2 (a), L2 and complex 5 (b), as well
as L3 (c) in solid state at room temperature (inset: images of L1-L3 and
complexes 1, 2 and 5).

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Fig. 1 The asymmetric units of complexes 1-8.
750x319mm (96 x 96 DPI)

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Fig. 2 (4,4) Layer motif (top) of complex 1 formed by the connection of nitrate anions and -Ag-L1- chains
(down)
350x479mm (96 x 96 DPI)

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Fig. 3 π•••π extended layer motif of complex 2 involving the same helical chains. Righꢀhelical chains were
illustrated here for instance.
661x495mm (96 x 96 DPI)

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Fig. 4 Hydrogen-bonding interactions extended layer motif of complexes 3 (a) and 4 (b) involving the
alternant right- and left-helical chains.
450x300mm (96 x 96 DPI)

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Fig. 5 Chain motif (down) in complex 5 extended by π•••π interactions (green dashed lines) with the
channels filled by the lattice water molecules (top).
250x198mm (96 x 96 DPI)

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Fig. 6 3-D microporous host framework (space-filling mode) of complexes 6 (a) and 7 (b) with the counter-
anions and lattice water molecules being encapsulated in the 1-D channels.
460x219mm (96 x 96 DPI)

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Fig. 7 svi-x net topology of complexes 6 and 7.
661x495mm (96 x 96 DPI)

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Fig. 8 Snakeꢀshaped chain structure of complex 8 with the two types of π•••π interactions being denoted as
green and pink dashed lines.
661x495mm (96 x 96 DPI)

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Fig. 9 UV-Vis absorbance spectra (converted from diffuse DSR) for complexes 1-8.

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DOI: 10.1039/C5DT00265F
Fig. 10 Emission spectra of L1 and complexes 1-2 (a), L2 and complex 5 (b), as well as L3 (c) in solid state
at room temperature (inset: images of L1-L3 and complexes 1, 2 and 5).
440x349mm (150 x 150 DPI)

Page 21 of 24
Dalton Transactions
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DOI: 10.1039/C5DT00265F
Fig. 10 Emission spectra of L1 and complexes 1-2 (a), L2 and complex 5 (b), as well as L3 (c) in solid state
at room temperature (inset: images of L1-L3 and complexes 1, 2 and 5).
433x350mm (150 x 150 DPI)

Dalton Transactions
Page 22 of 24
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DOI: 10.1039/C5DT00265F
Fig. 10 Emission spectra of L1 and complexes 1-2 (a), L2 and complex 5 (b), as well as L3 (c) in solid state
at room temperature (inset: images of L1-L3 and complexes 1, 2 and 5).
430x345mm (150 x 150 DPI)

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Dalton Transactions
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DOI: 10.1039/C5DT00265F
Scheme 1 Three flexible bis(pyridyl) molecules used in this work.
115x137mm (300 x 300 DPI)

Dalton Transactions
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DOI: 10.1039/C5DT00265F
Scheme 2 Versatile coordination modes of L1, L2, H2L22+ and L3 in complexes 1-8.
419x419mm (96 x 96 DPI)