Synthesis, spectroscopic characterization, fluorescence properties of new silver(I) complexes with optically active Schiff bases and their application in thin layers deposition

Article abstract of DOI:10.1016/j.poly.2017.07.005

Ag(I) complexes with a series of optically active Schiff bases derived from (1R,2R)(-)cyclohexanediamine and different aldehydes were obtained and characterized by ¹H, ¹³C, NMR in a solution and in the solid state, UV–Vis, fluorescen

Full text of DOI:10.1016/j.poly.2017.07.005

Accepted Manuscript
Synthesis, spectroscopic characterization, fluorescence properties of new sil-
ver(I) complexes with optically active Schiff bases and their application in thin
layers deposition
Magdalena Barwiolek, Julia Sawicka, Magdalena Babinska, Andrzej Wojtczak,
Andrzej Surdykowski, Robert Szczesny, Edward Szlyk
PII:
S0277-5387(17)30488-6
DOI:
http://dx.doi.org/10.1016/j.poly.2017.07.005
POLY 12741
Reference:
To appear in:
Polyhedron
Received Date:
Accepted Date:
22 May 2017
6 July 2017
Please cite this article as: M. Barwiolek, J. Sawicka, M. Babinska, A. Wojtczak, A. Surdykowski, R. Szczesny, E.
Szlyk, Synthesis, spectroscopic characterization, fluorescence properties of new silver(I) complexes with optically
active Schiff bases and their application in thin layers deposition, Polyhedron (2017), doi: http://dx.doi.org/10.1016/
j.poly.2017.07.005
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Synthesis, spectroscopic characterization, fluorescence properties of new silver(I)
complexes with optically active Schiff bases and their application in thin layers
deposition
Magdalena Barwiolek*, Julia Sawicka, Magdalena Babinska, Andrzej Wojtczak, Andrzej Surdykowski, Robert
Szczesny, Edward Szlyk
Faculty of Chemistry, Nicholas Copernicus University in Torun, 87-100 Torun, Poland. E-mail:
*
mbarwiolek@umk.pl, Fax: +48 (56) 654 24 77; Tel: + 48 (56) 611 45 16
Abstract
Ag(I) complexes with a series of optically active Schiff bases derived from (1R,2R)(-
1
13
)
cyclohexanediamine and different aldehydes were obtained and characterized by H, C,
NMR in a solution and in the solid state, UV-VIS, fluorescence, and IR spectroscopy. X-ray
crystal structure of (1R,2R)(-)chxn(5-Br-3OCH baH)2 (4) was solved. Moreover,
3
intermolecular interactions in the crystal structure of (1R,2R)(-)chxn(5-Br-3OCH baH) were
3
2
analyzed using 3D Hirshfeld surfaces and the related 2D fingerprint plots. The obtained
complexes have been used for preparation of thin layers on Si(111) to test the possibility of
their use as the fluorescent materials. Thin layers of silver(I) complexes were deposited on
Si(111) using the spin coating method and characterized by scanning electron microscopy
(
SEM/EDS), atomic force microscopy (AFM), and fluorescence spectroscopy. [Ag(1R,2R)(-
chxn(5-Br-3OCH baH) NO ] (4a) complex exhibited significantly increase of the
)
3
2
3
fluorescence intensity in comparison with ligand (4). The fluorescence of silver complexes
solutions was observed between 395-470 nm. For silver(I) layers, from intraligand transitions
(depending on the exciton wavelengths), the most intensive bands were observed between 390
and 560 nm. The intensity of the fluorescence bands registered for the layers obtained at 1100
rpm or 2000 rpm/min and 30 s time was highest.
Keywords silver, spin coating, Schiff base, thin layer, fluorescence, AFM
1
. Introduction
The application of metal complexes such as CVD, ALD, and spin coating precursors to the
deposition of pure and conformal thin silver films has been reported.[1-3] A spin-coating
technique was successfully used to obtain thin films of a copper(I) [(nBu P) CuO CHxCH O]
3
2
2
2
complex [4], unsubstituted phthalocyanine copper compounds [5], tetra (tricarbethoxy)-
1

substituted metallophthalocyanines (M=Co(II), Cu(II), Pd(II)) or silver complexes with Schiff
bases derived from 2- thiopheneethylamine.[7] Moreover, the spin coating was applied as an
alternative technique for chemical vapour deposition (CVD) in the case of [(nBu P) Ag-
3
2
O C(CH ) CO -Ag(PnBu ) ] and [(nBu P)Ag-O C(CH ) CO -Ag(PnBu )].[8] The film
2
2 2
2
3 2
3
2
2 2
2
3
thickness obtained equaled ca. 2.5 µm. Additionally, metal complexes (Ag, Cu, Ni, Pd) with
Schiff base ligands (derived from pirazine, piperazine, thiazole) were studied as a functional
material in second order nonlinear optics (NLO), as magnetic materials; the luminescent,
photochemical properties and electrical conductivity of these compounds were also
studied.[9-13] Furthermore, Ag(I) complexes with imidazole derivatives, e.g.
[
Ag (L) ](NO ) ], [Ag (L) ](BF )], and [Ag (L) ](CF CO ) ], where L was 1-(imidazol-4-yl)-
2 2 3 2 2 2 4 2 2 3 2 2
5
-(imidazol-1-yl)-2-azapent-1-ene, exhibited phosphorescence in the solid state at room
temperature.[14] The Schiff bases and their silver(I) complexes are known from their
luminescence properties.[13, 15-16] In the case of silver(I) compounds with N,N’-bis-pyridin-
2
-ylmethylene-hydrazine, the luminescence in the solid state from intraligand transitions in
the range 469-494 nm were observed.
Moreover, the Schiff base ligands derived from the reaction of cyclohexanediamine with
silver salts revealed different conformations and unusual structures.[17] Other studies
suggested that the type of silver salt could influence the structural and spectroscopic
properties of silver compounds.[14,17-18]
Additionally, chiral molecules e.g. porphyrins play an important role in biochemical systems
such as the photoreaction centers (chlorophylls) in photosynthesis,[19-20] biomolecular redox
catalysts (cytochrome) and vitamin B12, [21-23], and oxygen transport agents
(hemoglobin).[24-26] Optically active Schiff bases exhibit antimicrobial and antifungal
activity.[27] They show highly specific interlocking properties, what provides an essential
motif in the architecture of biomachinery and biochemical cycles. [28] Chiral transition metal
coordination complexes have attracted substantial research attention because of their wide
range of applications in asymmetric catalysis.[29-31]
The fact mentioned above prompted us to synthesis and the structural and
spectroscopic characterization of Ag(I) complexes with Schiff base ligands derived from
(1R,2R)(-)cyclohexanediamine. Additionally the intermolecular interactions in the crystal
structure of (1R,2R)(-)chxn(5-Br-3OCH baH) were analyzed.
3
2
The obtained silver(I) Schiff base complexes were used as precursors of new materials in the
spin coating method. The morphology, topography and photoluminescence properties of the
compounds and layers were studied and are reported herein.
2

2
. Materials and methods
2
-thiophenecarboxaldehyde (98%) (thca), pyrrole-2-carboxaldehyde (98%) (pyrca), 2-
pyridinecarboxaldehyde (99%) (pyca), 5-bromo-2-hydroxy-3-methoxybenzaldehyde (97%)
5-Br-3OCH baH) , silver nitrate (99%), and pivalic acid (99%) were purchased from Aldrich
(
3
2
and used without further purification. (1R,2R)(-)chxn was isolated from the 1,2-
diaminocyclohexane, 99% mixture of cis and trans using the Galsbol’s method.[32] Silver
pivalate was synthesized in the way described elsewhere.[33]
2
.1 Methods and instrumentation
UV-Vis absorption spectra were recorded on a Milton Roy Spectronic 1201 in CH CN or
3
-5
chloroform ((1) and (1a)) solution (1 x 10 M). IR spectra were performed on a Spectrum
-1
2
000 Perkin/Elmer FT IR using KBr discs in the range from 400 to 4000 cm and
-1
1
13
1
13
polyethylene IR sample cards in the range 400-70 cm . H, C, H C HMQC, HMBC NMR
spectra were collected with a Bruker AMX -300 spectrometer (300 MHz) in CDCl or
3
CD CN against TMS. The fluorescence spectra were recorded on a spectrofluorometer F-
3
7
000 HITACHI and spectrofluorometer Gilden pλotonics in the range from 900 to 180 nm (5
−
4
3
×
10 mol/dm MeCN solution or layers on silicon slides). An elemental analysis was carried
out using an Elementar Gmbh Vario Macro CHN analyzer, and silver was determined
argentometrically (after complex mineralization). The films were deposited on Si(111) wafers
(
10\10 mm) ~500 mm thick or glass slides using the spin coating technique. The precursors
were dissolved in tetrahydrofuran or MeCN and deposited on Si using a spin coater (Laurell
50SZ). Both, the morphology and composition of the obtained materials were analyzed with
6
a scanning electron microscopy (SEM) LEO Electron Microscopy Ltd, England, 1430 VP
model equipped with a secondary electrons (SE) detector and an energy dispersive X-ray
spectrometer (EDS) Quantax with an XFlash 4010 detector (Bruker AXS microanalysis
GmbH). The atomic force microscopy (AFM) studies in the tapping mode of the layers were
performed on a Multi Mode Nano Scope IIIa on Veeco (Digital Instrument).
2
.2 X-ray crystallography
Crystals of (1R,2R)(-)chxn(5-Br-3OCH baH) (4) were grown from the ethanol
3
2
solution. The X-ray diffraction data were collected with an Oxford Sapphire CCD
diffractometer using MoKα radiation λ =0.71073 Å, at 293(2) K, by ω-2θ method. Structure
2
was solved by the direct methods and refined with the full-matrix least-squares method on F
3

with the use of SHELX97 and SHELX2014 program packages[34]. Analytical absorption
corrections were applied (RED171 package of programs[35] Oxford Diffraction, 2000), the
maximum and minimum transmission of 0.8233 and 0.2933. Configuration of the chiral
centers was determined with the Flack method[36] with the Flack x = 0.002(13). Hydrogen
atoms were located from the electron density maps and their positions were constrained in the
refinement. The structural data of (4) have been deposited with Cambridge Crystallographic
Data Centre, the CCDC number 1485462. Hirshfeld surfaces[37-39] and 2D-fingerprint plots
were generated using Crystal Explorer 3.1.[40]
Table 1. Crystal data and structure refinement for (1R,2R)(-)chxn(5-Br-3OCH baH) (4).
3
2
Empirical formula
Formula weight
Temperature; K
Wavelength; Å
Crystal system
C22 H24 Br2 N2 O4
540.25
293(2)
0.71073
Monoclinic
P21
Space group
Unit cell dimensions; Å, °
a = 12.2377(6)
b = 6.3843(3)
c = 14.5403(8)
β= 99.689(5)
1119.82(10)
3
Volume; Å
Z
2
3
1.602
Density (calculated); Mg/m
-1
3.650
Absorption coefficient; mm
F(000)
544
Crystal size; mm
0.533 x 0.225 x 0.067
2.383 to 28.338°.
-15<=h<=14, -8<=k<=6, -17<=l<=19
7422
Theta range for data collection
Index ranges
Reflections collected
Independent reflections
Completeness to theta =
4174 [R(int) = 0.0323]
99.7 %
2
5.000°
4

Absorption correction
Max. and min. transmission
Refinement method
Analytical
0.8233 and 0.2933
2
Full-matrix least-squares on F
4174 / 1 / 271
Data / restraints / parameters
2
0.907
Goodness-of-fit on F
Final R indices [I>2sigma(I)]
R indices (all data)
R1 = 0.0431, wR2 = 0.0920
R1 = 0.0803, wR2 = 0.1036
0.002(13)
Absolute structure parameter
Extinction coefficient
n/a
-3 0.721 and -0.474
Largest diff. peak and hole; e.Å
2
2
.3 Syntheses
.3.1 Syntheses of ligands
Synthesis of (1R,2R)(-)chxn(thca) (1)
2
(
1R,2R)(-)chxn (0.0661 g, 0.58 mmol) in EtOH was mixed with anhydrous MgSO (0.2090 g,
4
1
.74 mmol) and added to 2-thiophenecarboxaldehyde (thca) (108 µl, 1.16 mmol). The mixture
was stirred at r.t. for 16 h. The yellow precipitate was recrystallized from ethanol and yellow
crystals of (1R,2R)(-)chxn(thca) suitable for X-ray crystallography were obtained (70 %
2
1
yield). H NMR [ppm]: δ 8.30 (s, 1H, CH=N), 7.17 (d, 3H, arom.), 3.36 (m, 1H, CH-N), 1.58
1
3
-
chxn. C NMR [ppm]: δ 154.3 C(4)H=N, 142.5 C(5), 130.1 C(7), 128.2 C(6), 127.2 C(8),
-1
7
1
3.4 C(3), 32.8 C(2), 24.4 C(1). IR (KBr, cm ): 1633 ν(C=N), 2926 ν(H-Ar), 1342 ν(C-N),
447 ν(C=C).[41] (Figure 1) UV-vis 259, 276 nm.
Synthesis of (1R,2R)(-)chxn(pyrca) (2)
2
(0.114 g, 1 mmol) (1R,2R)(-)chxn was added to a stirred solution of pyrrole-2-
carboxaldehyde (0.1902 g, 2 mmol) in EtOH. The reaction mixture was stirred under reflux
for 3 h, filtered, and filtrate was kept for 12 h in a refrigerator. The brown crystals of
1
(
1R,2R)(-)chxn(pyrca) ·H O were suitable for X-ray crystallography. (Yield 61 %). H NMR
2
2
CD CN [ppm]: δ 9.5 (s, 1H, NH), 7.93 (s, 1H, CH=N), 6.84 (s, 1H, arom.) H, 6.32 (t, J = 1.4
3
13
Hz, 1H, arom), 6.09 (m, 1H, arom), 3.14 (m, 1H, CH-N), 1.95 -chxn. C NMR [ppm]: δ
1
50.4 C(4)H=N, 129.9 C(5), 121.0 C(8), 116.9 C(6), 112.7 C(7), 72.9 (C(3)H-N), 32.8 C(2),
5

-1
2
3.9 C(1). IR [cm ]: 3232 ν(N-Hpyrca), 1631 ν(C=N), 2950 ν(H-Ar), 1378 ν(C-N), 1445, 1419
ν(C=C). UV-vis 203, 246, 359 nm.
(
1R,2R)(-)chxn(pyca) (3) were obtained as reported.[42-43]
2
1
(
1R,2R )(-)chxn(pyca) (3) H NMR [ppm]: δ 8.31 (CH=N), 7.87 (d, 4H, arom.), 3.54 (m, 1H,
2
1
3
CH-N), 2.31 CH , 1.87-1.21 -chxn. C NMR [ppm]: δ 161.4 C(4)H=N, 154.6 C(5), 149.2
3
13
C(9), 136.4 C(7), 124.4 C(8), 121.3 C(6), 73.5, 58.2, 32.7, 24.3. C CP MAS [ppm]: 172.9,
-1
1
2
59.1, 153.5, 148.2, 136.7, 125.4 122.2, 31.3, 23.8. IR [cm ]: 3232 ν(N-Hpyca), 1647 ν(C=N),
954, 2862 ν(H-Ar), 1445, 1418 ν(C=C)pyca, 1378 ν(C-N).[42-44] UV-vis 201, 234, 270 nm.
The synthesis of ligand (4) was performed similarly to ligand (2).
1
(
1R,2R)(-)chxn(5-Br-3OCH baH) (4) H NMR [ppm]: CDCl , δ 13.83 (OH), 8.16 (CH=N),
3
2
3
6
.95 (d, 2H, J = 2.1 Hz), 6.92 (d, 2H, J = 2.1 Hz), 3.88 (OCH ), 3.33 (m, 1H, CH-N), 2.31
3
13
CH , 1.87-1.21 -chxn. C NMR [ppm]: δ 164.73 C(4)H=N, 152.1 C(6), 150.3 C(8), 125.9
3
-1
C(10), 119.9 C(5), 117.9 C(7), 110.3 C(9), 73.3 (C3), 57.2 (OCH ), 33.8, 24.9. IR [cm ]:
3
3
000 ν(OH), 1626 ν(C=N), 2929 ν(H-Ar), νCH chxn, 1572, 1468 ν(C=C) , 971 δ(O-H). [44]
2
ar
3
UV-vis 242, 270, 359 nm, c.mol. 8,6 mg/100cm .[45-46]
1
1
3
2
2
3
4
4
N
N
N
N
5
6
5
6
7
S
S
7
NH
HN
8
8
(
1)
(2)
6

1
1
2
2
3
3
4
4
HO
N
N
OH
N
N
6
5
6
5
10
7
O
O
8
9
7
N
N
8
9
Br
Br
(3)
(4)
Figure 1. Structural formula and atoms numbering scheme of: (1R,2R)(-)chxn(thca) (1), (1R,2R)(-)chxn(pyrca)2
2
(
2), (1R,2R)(-)chxn(pyca) (3), (1R,2R)(-)chxn(5-Br-3OCH baH) (4).
2
3
2
2
.3.2 Syntheses of complexes
[
Ag(1R,2R)(-)chxn(pyrca)(NO )] (2a)
3
AgNO (0.0237 g, 0.14 mmol) suspended in EtOH was added dropwise to a solution
3
of (2) (0.0382 g, 0.14 mmol) in EtOH, and the mixture was stirred upon reflux for 5 h. The
obtained solution was filtered and the solvent evaporated under argon stream. After
recrystallization from diethyl ether, a brown precipitate was obtained (Yield 63 %). Anal.
Calc. for C H N O Ag: C 42.9, H 5.85, N 9.38, Ag 24.07, Found: C 43.08, H 6.38, N 9.86,
1
1
6
26
3
5
Ag 23.62. H NMR CD CN [ppm]: δ 9.49 (s, 1H, NH), 8.14 (s, 1H, CH=N), 7.14 (s, 1H,
3
arom.) H, 6.97 (t, J = 1.4 Hz, 1H, arom), 6.23 (m, 1H, arom), 3.42 (m, 1H, CH-N), 1.93 -
13
chxn. C NMR [ppm]: δ 154.8 C(4)H=N, 124.4 C(8), 120.2 C(6), 110.6 C(7), 70.9 (C(3)H-
-1
N), 33.2 C(2), 24.2 C(1). IR [cm ]: 3234 ν(N-Hpyrca), 1627 ν(C=N), 2930 ν(H-Ar), 1443,
-
1
419 ν(C=C), 1379, 1316, 1088, 879, 863 νNO .[44] UV-vis 247, 283, 403 nm.
3
Complexes (1a), (3a) and (4a) were obtained in the same way as (2a).
[
Ag(1R,2R)(-)chxn(thca) (NO )] (1a) Yield 42%. Anal. Calc. for C H N O S Ag: C 40.86,
2 3 3 3 2
16 18
1
H 3.44, N 8.94, Ag 22.84, Found: C 40.59, H 3.76, N 9.37, Ag 22.45. H NMR [ppm]: δ 8.59
(s, 1H, CH=N), 7.40-7.02 (d, 3H, arom.), 3.67 (m, 1H, cyclohexane-1,2-diyl-CH-N), 1.24-
1
3
2
.19 amine. C NMR [ppm]: δ 158.2 C(4)H=N, 144.1 C(5), 136.2 C(7), 135.1 C(8), 73.6
7

-1
C(3), 33.3 C(2), 24.3 C(1). IR [cm ]: ν(Ag-O) 280, ν(Ag-S) 473, 1654 ν(C=N), 2927 ν(H-
-
Ar), 1427 ν(C=C), 1370, 1322, 1081, 854, 835 νNO .[44] UV-vis 253, 347, 364, 383 nm.
3
[
Ag(1R,2R)(-)chxn(pyca) (NO )] (3a) Yield 71%. Anal. Calc. for C H N O Ag: C 46.76, H
2 3 18 20 5 3
1
3
4
.36, N 15.15, Ag 23.33. Found: C 46.59, H 4.46, N 14.87, Ag 22.88. C CP MAS NMR
[
ppm]: δ 163.0 C(4)H=N, 160.8 C(5), 151.6 C(9), 140.5 C(7), 128.7 C(6), 72.8 C(3), 31.6
-1
C(2), 23.2 C(1). IR [cm ]: ν(Ag-N) 446, 1645 ν(C=N), 2930 ν(H-Ar), 1568, 1589 ν(C=C)pyca,
-
1
383, 1003, 879, 848 νNO .[44] UV-vis 244, 282 nm.
3
[
(
Ag(1R,2R)(-)chxn(pyca) (C(CH ) COO)] (3b)
2 3 3
0
.1142g (0.39 mmol) of (1R,2R)(-)chxn(pyca) (3) in EtOH was mixed with 0.1659g
2
0.79 mmol) silver(I) pivalate dissolved previously in EtOH. The mixture was stirred at r.t. for
h. The brown precipitate of [Ag(1R,2R)(-)chxn(pyca) (C(CH ) COO)] (3b) was obtained
3
2
3 3
after solvent evaporation. Yield 78%. Anal. Calc. for C H N O Ag: C 55.09, H 5.83, N
2
3
29
4
2
1
1
1.17, Ag 21.51, Found: C 55.20, H 5.46, N 10.37, Ag 21.59. H NMR [ppm]: δ 8.59 (s, 1H,
1
3
CH=N), 7.40-7.02 (d, 3H, arom.), 3.67 (m, 1H, cyclohexane-1,2-diyl-CH-N). C NMR
[
ppm]: δ 184.9 , 168.0 C(4)H=N, 161.9 C(5), 151.6 C(9), 138.3 C(7), 125.2 C(6), 126.9
acid
-1
C(8), 72.6 C(3), 39.3acid, 33.7 C(2), 28.6acid, 23.8 C(1). IR [cm ]: 280 ν(Ag-O) 446 ν(Ag-N),
306, 1356 ν(C-N), 1644 ν(C=N), 2927 ν(H-Ar), 1480, 1590, 1409 ν(C=C)pyca, 1305, 1544
ν(COO).[44] UV-vis 229, 272 nm.
1
[
Ag(1R,2R)(-)chxn(5-Br-3OCH ba) (NO )] (4a) Yield
56%. Anal.
Calc. for
3
2
3
1
C H Br N O Ag: C 37.21, H 3.41, N 5.91, Found: C 37.54, H 3.46, N 5.41. H NMR [ppm]:
22
24
2
3
7
δ 11.06 (s, 1H, OH) 8.17 (CH=N), 7.35 (d, 2H, J= 2.1 Hz), 7.21 (d, 2H, J= 2.1 Hz), 3.95
1
3
(
OCH ), 3.15 (m, 1H, CH-N), 1.65-1.27 -chxn. C NMR [ppm]: δ 164.1 (C=N), 152.2 C(7),
3
1
2
50.2 C(6), 125.9 C(10), 119.8 C(5), 118.0 C(8), 110.2 C(9), 71.4 (C3), 57.2 (OCH ), 33.8,
3
-1
4.9. IR [cm ]: 3317 ν(OH), 1649 ν(C=N), 2957, 2859 ν(H-Ar), ν CH chxn, 1579, 1512
2
ν(C=C) , 956 δ(O-H), 440, ν(Ag-N).[44]. UV-vis: 213, 252, 266, 339, 352 nm.
ar
3
3
. Results and discussion
.1 X-ray crystal structure of (1R,2R)(-)chxn(5-Br-3OCH baH) (4)
3
2
The diffraction experiment and structure refinement are summarized in Table 1. The
8

asymmetric part of the structure consists of a single (1R,2R)(-)chxn(5-Br-3OCH baH)
3
2
molecule (Figure 2). The configuration on C8 and C13 was determined as R,R with the Flack
method.[36] With such configuration, the torsion angle N1-C8-C13-N2 is -61.8(6)º, similar to
values found in complexes with the Schiff base ligands derived from the cycloxexanediamine
with the R,R configuration.[47-48]
Figure 2. ORTEP diagram and atom labeling scheme for (1R,2R)(-)chxn(5-Br-3OCH baH) (4).
3
2
Ellipsoids are plotted at 30% probability level.
Comparison revealed no statistically significant differences between the valence
geometry of two aromatic moieties in (1R,2R)(-)chxn(5-Br-3OCH baH) . The only exceptions
3
2
are the angles on the methoxy O atoms, with values for C2-O2-C21 and C19-O3-C22 being
16.4(6) and 118.9(8)°, respectively (Table 2). Also the valence angles on the imine C atoms
1
differ slightly, with the values for N1-C7-C6 and N2-C14-C15 of 124.3(6) and 122.3(6)°,
respectively. The imine N-C bond distances are C7-N1 1.264(9) Å and N2-C14 1.278(8) Å.
These values are significantly shorter that those of 1.298(4) and 1.286(4) Å reported for
complexes of Schiff bases derived from (1R,2R)(-)cyclohexanediamine.[47-48]
9

Table 2. Selected bond lengths [Å] and angles [°] for (1R,2R)(-)chxn(5-Br-3OCH baH) (4).
3
2
Selected bond lengths
1.352(8) C20-O4
1.396(9) C15-C20
1.373(8) C19-O3
1.436(9) O3-C22
1.892(7) C17-Br2
1.444(9) C14-C15
1.264(9) N2-C14
1.456(8) C13-N2
1.534(8)
O1-C1
C1-C6
C2-O2
O2-C21
C4-Br1
C6-C7
C7-N1
N1-C8
C8-C13
1.353(8)
1.402(10)
1.359(9)
1.408(10)
1.908(7)
1.451(9)
1.278(8)
1.460(8)
Selected angles
O1-C1-C6
O1-C1-C2
C3-C2-O2
O2-C2-C1
C2-O2-C21
C5-C4-Br1
C3-C4-Br1
N1-C7-C6
C7-N1-C8
N1-C8-C9
N1-C8-C13
N2-C13-C12
N2-C13-C8
C12-C13-C8
122.2(5) O4-C20-C15
118.1(6) O4-C20-C19
124.5(6) O3-C19-C18
115.1(6) O3-C19-C20
116.4(6) C19-O3-C22
119.8(5) C16-C17-Br2
118.5(5) C18-C17-Br2
124.3(6) N2-C14-C15
118.0(6) C14-N2-C13
109.8(5)
121.6(7)
118.0(7)
124.2(7)
115.5(7)
118.9(8)
119.5(6)
118.7(6)
122.3(6)
118.1(5)
110.7(5)
108.9(5)
110.5(5)
111.4(5)
The central cyclohexyl ring has a chair conformation. The imine moieties are almost
co-planar with the adjacent phenyl rings, with the C1-C6-C7-N1 and C20-C15-C14-N2
torsion angles being 1.5(11) and -1.4(9)º, respectively. Consequently, orientation of the
aromatic ring relative to the cyclohexyl moiety can be described with the torsion angles C7-
10

N1-C8-C9 and C14-N2-C13-C12 being -100.5(7)º and -99.5(6)º, respectively. In the detected
conformation, the dihedral angle between two phenyl rings is 84.6(3)º.
Electron density maps revealed the presence of protons bound to both phenolic O
atoms. Both groups are donors in the O-H…N intramolecular H-bonds involving the
neighboring imine N atoms, with O1…N1 and O4…N2 distances being 2.652 and 2.608 Å,
respectively.
Analysis of the crystal packing revealed C-H…A intermolecular interactions C21-
H21B…O2[-x,y-1/2,-z+2], C7-H7A…Br1[-x+1,y+1/2,-z+2 ], C13-H13A…Br2[-x,y+1/2,-
z+1] and C22-H22B…Br2[x,y-1,z], with the respective C…A distances being 3.483, 3.742,
3
.996 and 3.982 Å. The C-H…π interaction is found between C16-H16A and C15--C20[-
x,1/2+y,1-z] phenyl ring, with the H…Cg distance to the ring gravity center of 2.97 Å. Also,
C17-Br2…π interactions are found to the C1--C6[-x,1/2+y,1-z] phenyl, with Br…Cg distance
of 3.869(3) Å.
3
.2 Hirshfeld surface analysis of (1R,2R)(-)chxn(5-Br-3OCH baH) (4)
3 2
Hirshfeld surface analysis is a powerful tool which allow to visualize and analyze
different types of intermolecular interactions in crystals. The Hirshfeld surfaces of the ligand
1R,2R)(-)chxn(5-Br-3OCH baH) (4) are illustrated in Figure 3. These surfaces have been
(
3
2
generated using a standard (high) surface resolution (-0.12 to 1.55 Å) with 3D dnorm surfaces
mapped over a red-white-blue color scheme. The red areas indicates short intermolecular
contacts, white indicates contacts close to van der Waals separation distances, and the blue
color designates longer contacts.
.
11

Figure 3. 3D Hirshfeld surface dnorm maps of (4): (a) rear view, (b) face view, (c) bottom
view. Red spots and dotted red lines indicate close contacts.
The intermolecular interactions involved within the structure of title ligand are clearly visible
on the 2D fingerprint plot (Figure 4), which allow to quantify individual contributions of the
particular atoms involved in the close contact. The fingerprint plots for Hirshfeld surfaces
exhibit characteristic wings of the d and d diagonal, where d is distance from a point on the
e
i
e
surface to the nearest nucleus outside the surface and d is distance from a point on the surface
i
to the nearest nucleus inside the surface.
Figure 4. 2D Fingerprint plots of Schiff base (4), broken down into contribution from specific
pairs of atom types: a) H⋅⋅⋅H, b) Br⋅⋅⋅H/H⋅⋅⋅Br, c) C⋅⋅⋅H/H⋅⋅⋅C, d) H⋅⋅⋅O/O⋅⋅⋅H.
The H….H contacts appear in the middle of the scattered points and cover most of area in the
two-dimensional fingerprints maps. They comprise 39.9% of the entire Hirshfeld surface. The
round single peak at d + d ~ 2.1 A (Figure 4a) results from a medium interatomic H…H
e
i
contact. The Br...H/H…Br and C...H/H…C interactions appear as two wings in the fingerprint
plot (Figure 4 b,c) also show a relatively large contribution of 18.2% and 17.9% respectively.
The O…H/H…O hydrogen bonding intermolecular interactions appears as two spikes in the
plot contributes 14.9% to the total areas is shown in Figure 4d. This is followed by
C…Br/Br…C 4.9% as well as other minor interactions including O…Br/Br…O, C…O/O…C,
12

N…H/H…N, N…Br/Br…N which constitute less than 5% of the total area. From the
Hirshfeld surface it is also evident that the aromatic rings are not related to one another
through π-π stacking interaction (C…C interactions comprise 0% of the total surface). In
addition the surface contact data are used to derive enrichment ratios which relate to the
propensity of pairs of chemical species to form crystal packing interactions.[49] The
enrichment ratio (ER) of a pair of elements is defined as the ratio between the proportion of
actual contacts in the crystal and the calculated proportion of random contacts. (Table 3)
Table 3. Enrichment ratio of different inter-contact and percentage of each atom on the
Hirshfeld surface in (4).
enrichment
H
C
O
Br
H
C
0.92
1.14
1.26
1.09
65.7
O
Br
0.5
1.63
12.0
0.9
9.0
%
surface
12.7
The list of enrichment ratios highlights the C…Br/Br…C and O…H/H…C contacts (ECBr
=
1
.63, EOH = 1.26). In π stacking the Br atoms interact with positively charged C atoms which
are themselves covalently bonded to O and Br atoms. However their contribution to the total
surface is small and should be analyzed cautiously. H...O/O…H contacts are, as expected,
quite enriched due to the formation of energetically favorable hydrogen bonds. On the other
hand there is a very clear depletion of H….H contacts presumably due to involvement of H
atom in C-H….O and C-H….Br hydrogen bonds. Nitrogen atoms are rarely present at the
molecular surface (0.5%) as they generally form intra-molecular hydrogen bonds with OH
group. The ER relates to the contacts O…Br/Br…O and C…O/O…C are of low meaning as
they are derived from less important interactions with small contributions to the Hirshfeld
surface.
3
.3 NMR studies
13

1
1
Results of H NMR spectra analysis are listed in Table 4. In the H NMR spectra of ligands
the azomethine signals appeared in the region 7.93-8.31 ppm. After the coordination of Schiff
bases with silver(I) ion, the signal of the azomethine group H(4) (Figure 1) was shifted 0.29
ppm (1a), 0.21 ppm (2a), 0.28 ppm (3b) and 0.01 ppm (4a) downfield. Additionally, a
downfield shift of the H(3)-N signal (Δcoord= Δcomplex - Δligand = 0.31 ppm (1a) and 0.28 ppm
(2a)) was observed.
13
Table 4. Selected signals in C NMR data of ligands and complexes.
C1
C2
C3
C4
Δcoord C5
Δcoord C6
C9
1
1
2
2
3
3
24.4
24.3
23.9
24.2
24.3
23.8
32.8 73.4
33.3 73.6
32.8 72.9
33.2 70.9
32.7 73.5
33.7 72.6
154.3
142.5
128.2
128.6
116.9
117.3
-
-
-
-
a
a
b
158.2 +3.9 144.1 -1.6
150.4 129.9
154.8 +4.4 124.4 -5.5
161.4 154.6
168.0 +6.6 161.9 +7.3 125.29 151.6
121.3 149.2
3
24.6
32.3 73.0
172.9
159.1
125.4 153.5
CPMAS
3a
23.2
31.6 72.8
163.0 -9.9
160.8 +1.7 128.7 151.6
CPMAS
4
24.9
24.9
33.8 73.3
33.8 71.4
164.7
164.1 -0.6
119.9
152.1 110.3
4a
119.8 -0.01 150.2 110.2
1
3
The C NMR spectrum of ligands exhibited signals of azomethine carbons between
1
50.4 and 172.9 ppm. In the case of complexes these signals were shifted downfield ((1a),
(2a) and (3b)) and upfield ((3a) and (4a)) and appeared in the region 154.8 – 168 ppm.
To summarize, the NMR results indicated the coordination of the silver ion via azomethine
nitrogen in all complexes. Moreover, coordination via sulphur in [Ag(1R,2R)(-
1
3
)
chxn(thca) NO ] (1a) was also noted.[50] Furthermore, in the C NMR spectrum of
2 3
-
complex (3b), the signals of the CH group, the tertbutyl group and the COO group were
3
registered at 28.6 ppm, 39.3 ppm, and 184.9 ppm, respectively, confirming the presence of
pivalic acid in the complex.
3
.5 UV-Vis spectra
The UV-Vis spectra of all the isolated compounds have been registered. In the spectra of the
free ligands in the 200-283 nm region, bands from π-π* transitions in the phenyl group (3)
and (4), imidazole (2) and thiophene (1) rings were observed.[51] The higher bands situated
above 300 nm are related to π-π* transitions in the -C=N- group.[52] In the spectra of silver
14

complexes, these bands are shifted towards longer wavelengths. The bands detected above
00 nm are connected to LMCT.
For insoluble [Ag(1R,2R)(-)chxn(pyca) (NO )] (3a), the UV-Vis spectrum was not registered.
3
2
3
3
.6 Thin materials analysis
Silver(I) organic-inorganic layers were deposited on a silicon substrate by the spin-coating
technique. The parameters of the layers depend on the spin speed and time of coating.
Therefore, for all the experiments, the time was set at 30 s and the spin speed at 900, 1000,
1
100, and 2000 rpm (rotation per minute). The layer topography was studied using
SEM/EDX. Because of the low solubility in the common solvents of [Ag(1R,2R)(-
chxn(pyca) (NO )] (3a), this complex was not used in the spin coating process. The SEM
)
2
3
images of the Ag(I) complex layers showed the compound to be uniformly spread on the
surfaces of the substrates. The layers were amorphous, but small crystallities appeared in
some places due to incomplete solidification of the complex solution during the spin coating
process, as previously observed.[8, 53-55] The SEM/EDX analysis of [Ag(1R,2R)(-
)
chxn(thca) (NO )] (1a)/Si layers (7.7 mg/5 ml THF) showed that the complex was spread
2 3
evenly on the silicon surface. The silver content was 1.55%, indicating the presence of the
complex on the Si surface.
A similar situation (regular layout of compounds) was observed for [Ag(1R,2R)(-
)
chxn(pyca) (C(CH ) COO)] (3b) layers obtained at 2000 rpm. The average Ag content was
2
3 3
4
.77%.
The
SEM/EDX
analysis
confirmed
that
new
[Ag(1R,2R)(-
)
chxn(pyca) (C(CH ) COO)] (3b)/Si material was obtained. The AFM images registered in
2 3 3
the tapping mode are shown in Figures 5 and 6. For this type of layer, AFM seems more
informative in terms of morphology than SEM microscopy because AFM provides data on the
roughness and homogeneity of the obtained layers. The surface roughness R (the root mean
q
square roughness) of the [Ag(1R,2R)(-)chxn(thca) (NO )] (1a)/Si was highest when the
2
3
applied speed was set at 2000 rpm. Reducing the spin speed to 1100 rpm resulted in a lower
surface roughness (Figure 5), meaning a flatter material (R = 11.2 nm).
q
15

3
Figure 5. AFM of [Ag(1R,2R)(-)chxn(thca) (NO )] (1a)/Si: 7.7 mg/ 5 cm THF; 1100 rmp; 30s; 2000 rmp; 30s.
2
3
The results of the AFM analysis indicate a uniform distribution of the complex on Si
substrates for the layers achieved at the spin speed at 2000 rpm (EDX: Ag = 3.72%).
Reducing the rotation speed gave a layer with some structures sticking out of the surface (Rq
=
22.8 nm). However, despite the higher R value, better spreading of the compound on the
q
silicon wafer at 2000 rpm was observed.
3
Figure 6. AFM (3b)/Si(111): 8,8 mg/ 8 cm chloroform; 2000 rmp; 30 s.
a)
b)
c)
3
Figure 7. SEM image of (4a)/Si(111): 8.8 mg/ 8 cm chloroform; 2000 rpm; 30 s, magn. 2kxx., AFM a) phase,
b) amplitude, c) height, 800 rpm x5, 5s.
The highest roughness of [Ag(1R,2R)(-)chxn(pyca) (C(CH ) COO)] (3b)/Si was observed at
2
3 3
the applied spin speed of 2000 rpm. Lowering the spin speed did not cause important changes
in the surface roughness. However, the type of a substrate is meaningful because covering a
glass slide with (3b) instead of a silicon slide resulted in a rougher material. Nevertheless,
[
Ag(1R,2R)(-)chxn(pyca) (C(CH ) COO)] (3b) was evenly spread on both the glass and
2 3 3
Si(111) substrates (Figure 6). In some places, the compound stuck out of the surface, i.e., R =
q
8
.89 nm and 21.6 nm for Si(111) and glass, respectively. Spin coating at 2000 rpm for 30 s
time led to materials of the highest roughness. In summary, the best parameters for the spin
coating process to provide new smooth hybrid organic-inorganic silver(I) materials were
found to be a spin speed of 1100 or 2000 rpm and a time of 30 s. The spin coating of the (3a)
on Si(111) substrate lead to the formation of new thin layer, with compound evenly
16

distributed on the silicon surface. The deposition of the complex (4a) on the silicon surface
covered with PMMA resulted in regularly arrangement compound. (Figure 7) SEM/EDX
analysis pointed the presence of silver and nitrogen in the layer indicating presence of the
complex film on the Si/PMMA surface. AFM analysis showed the layer with the spherical
structures. The parameters of roughness of the layer equaled R = 18.3 nm and R = 8.39 nm.
q
a
The layers is relatively thick about 250 nm. Again the best cover parameters were achieved in
multistep spin coating process (800 rpm x5, 5 s) The lowering the spin speed lead to rarely
covered silicon surface by the complex and significant number of crystallities.
3
.7 Fluorescence analysis
The fluorescence properties of the obtained compounds in MeCN, and their layers
were studied. Because of the low solubility in common solvents of [Ag(1R,2R)(-
chxn(pyca) (NO )] (3a), its fluorescence properties were not measured.
)
2
3
The Schiff bases (1) – (3) exhibit relatively low intensity of the fluorescence in solution. The
excitation was done at 385 nm for (1) and (3), and 370 nm for (2). The emission from intra-
ligand π
π* transitions at 460 nm for (1) and (3) and 470 nm for (2) was observed.
Whereas, in the case of (1R,2R)(-)chxn(5-Br-3OCH baH) (4) solution the intensive
3
2
fluorescence band at 489 nm (λ = 406 nm) was noted. Again, the emission is connected with
ex
π
π* intra-ligand transitions. After coordination the shift of the fluorescence bands was
observed. The complexes (1a) and (2a) exhibited significant increase of the fluorescence band
intensity at 470 nm (λ =375 nm). But, in the case of complex (2a) the intensity of the
ex
fluorescence is relatively low when compared with other obtained in this work silver
compounds (Figure 8). The increase of the fluorescence intensity of the complexes (1a) and
(2a) is presumably due to the conformational rigidity of the ligand upon complexation or
strong coordination with Ag(I) metal center.[56] Similar effect of fluorescence intensity in
comparison to ligand was reported for naphthalene complexes.[57] It was suggested, that all
these fluorescent emissions may be assigned to the intra-ligand fluorescence since the free
ligands exhibited a similar emission as complexes under the same condition. Whereas, in the
case of (3b) and (4a) complexes decrease of the intensity of the fluorescence band was
observed (λ = 320 nm, λ =395 nm (3b) and λ = 406 nm, λ =469 nm (4a)) (Figure 8). The
ex
em
ex
em
decreasing and hypsochromic shift of the fluorescence can be a results of silver electron
density. This was already observed in the case of other complexes and can be related to
reduction of the ligand conformational rigidity and enhancement of the non-radiative energy
17

losses in solution. It is known that the mechanism of fluorescence based sensing may result an
electron transfer or energy transfer process, or a combination of the two, which may lead to a
alteration in emission intensity or a shift in emission wavelength, or a combination of both. A
short-ranged electron transfer can lead to fluorescence quench or enhancement of the host
framework.[58]
Because the (1a), (3b) and (4a) complexes exhibited the relatively high intensity of the
fluorescence in solution, they have been used to obtain thin fluorescent materials. In the case
of (1a)/Si materials the excitation was done at 348 nm and observed emission at 394 nm was
noted. Studies of the fluorescence properties of the (3b)/Si and (3b)/glass layers the highest
fluorescence intensity (λ =350 nm, λ =390 nm) was registered for the (3b)/Si(111) layer
ex
em
obtained at the spin speed of 1000 rpm. The best spin speed for the (3b)/glass layer (highest
intensity of fluorescence band, λ =350 nm, λ =390 nm) was at 1100 rpm. In both cases,
ex
em
these properties result from compounds evenly spread on the substrate surfaces. Average
silver content was 6.39% and 9% for (3b)/Si(111) and (3b)/glass, respectively. In comparison
to the solution of (1a) and (3b) the hypsochromic shift of the fluorescence band was noted.
The layers of (4a)/Si exhibited fluorescence at 570 nm, after irradiation at 360 nm. There is an
example of batochromic shift of the fluorescence. In general, the intensity of the layers
fluorescence was weaker than intensity of the corresponding solutions. The highest intensity
band was registered for the layer obtained at multistage spin speeds, time 5 s for each applied
speed. All these layers displayed even distribution of complexes over the silicon surface.
10000000
9000000
8000000
7000000
6000000
5000000
4000000
3000000
2000000
1000000
0
complex(2a)
complex(3b)
complex(1a)
complex(4a)
300
400
500
600
700
800
18

Figure 8. Fluorescence spectra of complexes.
The above results indicate that the silver layers exhibit emission and that uniformly
distributed substrate increases the emission band intensity.
Conclusions
New silver(I) complexes with Schiff bases obtained from (1R,2R)(-)cyclohexanediamine and
various aldehydes were synthesized. The silver(I) complexes with Schiff bases exhibit
different types of coordination depending on the type of aldehyde at cyclohexanediamine
(chxn). In the coordination sphere of the silver ion, nitrogen or pivalate groups appear. The
Hirschfield surface and fingerprint plot analysis of (1R,2R)(-)chxn(5-Br-3OCH baH) (4)
3
2
show that the H…H interactions play the most important role on the stabilization of the
crystal. The solutions of silver complexes exhibited luminescence stronger than in thin layers.
The strongest luminescence was detected for solution of complex (1a). The increase of the
fluorescence intensity after coordination was observed in the case of (1a). In the case of other
silver complexes the decrease of the luminescence was noted. All the Ag(I) compound layers
exhibit luminescence at λ between 250 and 334 nm. The emission bands were observed in
ex
the range between 390 and 560 nm. The fluorescence properties depend on the results of the
compound deposition on a substrate surface. The highest intensity of the emission bands was
observed for the layers with more uniformly placed compounds, which were obtained in the
multistage spin coated process. The increase in spin speed leads to a decrease in the surface
density and intensity of the fluorescence layers. Studies of the material properties and the
emission of the layer reveal that the complex can be used as a potentially optically active
material.
Acknowledgement
Authors would like to thank the National Science Centre (NCN), Poland for financial support
(grant no. 2013/09/B/ST5/03509).
19

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21

New silver(I) complexes with optically active Schiff bases were synthesized and structurally and
spectroscopically characterized. Silver complexes exhibit fluorescence in solution. The new silver
complexes were used in wet methods to obtain thin layers. The layers were amorphous and some of
them exhibited fluorescence.
22