Structural and spectroscopic study of novel Ag(I) metal-organic complexes with dyes - Experimental vs. theoretical methods

Article abstract of DOI:10.1016/j.ica.2011.10.015

Sixteen new metal-organic Ag^I-compounds of organic dyes are synthesized, isolated spectroscopic and structurally elucidated by means of single crystal and powder X-ray diffraction, high resolution ESI mass spectrometry (MS), electronic absorption (EAs) and vibrational spectroscopy, diffuse reflectance (Ds) and fluorescence (Fs) spectroscopy in condense phases, nuclear-magnetic resonance, ICP, and thermal methods. Quantum chemical DFT calculations, as well as NBO analysis are performed of the novel complexes and ligands. Structurally related model metal-organic chromophores are also studied. The obtained correlation between the theoretical and experimental data marked the studied complexes as promising novel nonlinear optical (NLO) materials.

Full text of DOI:10.1016/j.ica.2011.10.015

Inorganica Chimica Acta 382 (2012) 96–104
Contents lists available at SciVerse ScienceDirect
Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Structural and spectroscopic study of novel Ag(I) metal–organic complexes
with dyes – Experimental vs. theoretical methods
⇑
M. Lamshöft, C. Stolle, J. Storp, B. Ivanova , M. Spiteller
Institute of Environmental Research of the Faculty of Chemistry, Dortmund University of Technology, Otto-Hahn-Str. 6, D-44227 Dortmund, Germany
a r t i c l e i n f o
a b s t r a c t
I
Article history:
Sixteen new metal–organic Ag -compounds of organic dyes are synthesized, isolated spectroscopic and
structurally elucidated by means of single crystal and powder X-ray diffraction, high resolution ESI mass
spectrometry (MS), electronic absorption (EAs) and vibrational spectroscopy, diffuse reflectance (Ds) and
fluorescence (Fs) spectroscopy in condense phases, nuclear-magnetic resonance, ICP, and thermal meth-
ods. Quantum chemical DFT calculations, as well as NBO analysis are performed of the novel complexes
and ligands. Structurally related model metal–organic chromophores are also studied. The obtained cor-
relation between the theoretical and experimental data marked the studied complexes as promising
novel nonlinear optical (NLO) materials.
Received 13 July 2011
Received in revised form 29 September
2
011
Accepted 5 October 2011
Available online 14 October 2011
Keywords:
I
Ag -complexes
Ó 2011 Elsevier B.V. All rights reserved.
Organic dyes
Structures
Physical properties
Quantum chemistry
1
. Introduction
The design of metal–organic NLO materials includes strategy for
avoidance of unwanted optical losses from d ? d transitions with-
1
0
II
Recent studies on design of novel NLO materials have been
in the visible region. Metal ions with configuration d such as Zn ,
II
II
I
focused on metal organic compounds [1]. The success here encour-
ages the utilization of the strong and highly directional coordination
metal–ligand bonds, and tuning the noncentrosymmetric networks
in the crystals. The noncentrosymmetric networks can be designed
by taking advantage of the well-defined geometry of the metal ions
and bridging coordination ability of the ligands. The successful
developments in the field divided the dimensionality of coordina-
tion networks into 1D–3D systems [1]. The large molecular first
hyperpolarizabilities b, governing second order NLO effects, are gen-
erally required for the ligands. Thus, molecules with strong electron-
donating group (D), connected to an electron-accepting unit (A) via a
Cd , Hg and/or Ag are especially attractive [1]. Rigid conjugated
bridging ligands of organic dyes have been chosen to minimize
the potential packing complexity. The asymmetrical group as sub-
stituents (Scheme 1) also introduces electronic asymmetry with
good conjugation between the electron donors and acceptors. Thus
obtained novel optical limiters (OL) materials have the property of
limiting the transmitted light intensity to a maximum value, play-
ing an important role as protecting sensitive photo detectors, opti-
cal sensors, and more [1]. An ideal OL material should exhibit a
high, linear transmission below a certain ‘‘limiting’’ threshold with
the transmission becoming highly NLO above this threshold [3]. In
I
p-conjugated bridge, exhibiting intramolecular charge-transfer
this respect Ag -coordination compounds are attractive templates
(
ICT) excitations are characterized with especially large b-responses
for generating metal–organic crystals, as a result of the remarkable
photochemical and photo physical properties [4]. Several Ag -
I
[
2]. Organic dyes are attractive for modeling of the molecular archi-
tecture find are widely used as second and third order materials, EO
polymers and/and thin films in the NLO technologies. The 4-styryl-
complexes and clusters have been reported as OLs. Although there
have a large number of Ag -bridged coordination compounds with
infinite 1D network, the OL properties are poorly explored as yet
and they present a large field for investigation [5].
I
0
0
pyridinium type systems, such as 4-N,N-dimethylamino-4 -N -
methyl-stilbazolium tosylate (DAST), exhibit a very large second
order NLO susceptibility b, allowing an optimization of bulk and thin
film growth properties. THz-waves generation properties of organic
dyes have been found [2h], allowing an application in the field of the
THz-technologies as well [3].
2. Experimental
2.1. Physical methods
⇑
Corresponding author. Tel.: +49 231 755 40 89; fax: +49 231 755 40 85.
E-mail addresses: B.Ivanova@infu.uni-dortmund.de, B.Ivanova@web.de
B. Ivanova).
The X-ray diffraction intensities were measured on a Bruker
Smart X2S diffractometer, using micro source Mo Ka radiation
(
0
020-1693/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2011.10.015

M. Lamshöft et al. / Inorganica Chimica Acta 382 (2012) 96–104
97
R4
R4
R3
R1
N
R3
R3
R1
N
R1
N
x I
x I
x I
R2
R1
N
N
(
I)
(II)
(III)
(IV)
R
1
R
2
R
3
R
1
R
3
R
4
R
1
R
3
R
4
R
1
I-(1)
I-(2)
I-(3)
I-(4)
2-pyrimidine -OH
F
II-(1)
II-(2)
II-(3)
II-(4)
H
H
H
H
F
OH
III-(1)
III-(2)
III-(3)
III-(4)
H
H
H
H
F
OH
IV-(1)
IV-(2)
IV-(3)
IV-(4)
-N(CH
Pyrrole
-N(Ph)
9H-carbazole
2 3 2
CH )
H
H
H
-CH
-CH
-CH
3
3
3
Pyrrole
Pyrrole
-CH
-CH
-CH
3
Pyrrole
-CH
-CH
-CH
3
-N(Ph)
2
-N(Ph)
2
3
3
-N(Ph)
2
3
3
2
9H-carbazole
9H-carbazole
9H-carbazole
R4
L
N
N
F
R3
OH2
Ag(I)
O
Ag(I)
O
N
N
O
O
R3
N
N
O
O
N
R1
N
N
Ag(I)
O
O
O
Ag(I)
N
O
O
O
N
O
I
I
I
I
[
Ag (I-(1))(NO
3
)]
[Ag (I-(i))
2 3
(NO )], i = 2-4
[Ag (X-(i))(NO
3
)(H
2
O)], i = 1-4, X = II or III
[Ag (IV-(i))(NO
3
)], i = 1-4
Scheme 1. Chemical diagrams and labeling of the studied novel organic ligands and the corresponding metal–organic compounds.
and employing the
on multiple scanned reflections. The crystal structures were solved
x
scan mode. An absorption correction based
HPLC–ESI-MS/MS measurements are made, using TSQ Quantum
AM ULTRA (Thermo Electron Corporation) instrument. Two eluents
by direct methods using SHELXS-97 [6]. The crystal structures were
refined by full-matrix least-squares method against F . Anisotropic
2 3
will be used A – H O with 0.1% HCOOH and B – CH CN with 0.1%
2
HCOOH. ESI mass spectrometry: a triple quadruple mass spectrom-
eter (TSQ 7000 Thermo Electron, Dreieich, Germany) equipped with
an ESI 2 source is used for detection and operated under the follow-
ing conditions: capillary temperature 120 °C; sheath gas 60 psi and
spray voltage 4.5 kV. The samples are injected into the ion source
by an auto sampler (Surveyor) with a flow rate of 0.2 ml/min pure
acetonitrile. 1 mg/ml of the sample are dissolved in acetonitrile.
The data obtained are processed using Xcalibur 1.3 software. Solu-
tions and solid-state phases of the metal complexes are examined
by electro spray, since the uncompleted ligands survive the electro
spray process intact and can be detected simultaneously by mass
spectrometry. Best sensitivity is achieved in the positive ion mode,
when species present in solution as anions are detected in the pro-
tonated form with a single positive charge. Except for the proton-
ation, the aqueous complexes are preserved and neither
fragmentation of complexes nor formation of clusters with more
than one metal or ligand is observed in the mass spectra. The HPLC
ESI MSMS method is applied for the separation of the complex mix-
tures, possibly formed on account of the polydentatecharacter of the
ligands and possibility to formation of more than one complex
species.
displacement parameters were introduced for all non-hydrogen
atoms. The hydrogen atoms attached to carbon were placed at cal-
culated positions and refined allowing them to ride on the parent
carbon atom. The hydrogen atoms bound to nitrogen and the oxy-
gen were constrained to the positions which were confirmed from
the difference map and refined with the appropriate riding model.
Structures were procedure by PLATON [6]. The powder X-day dif-
fraction measurements were carried out on polycrystalline and/
or glass samples. The XRD patterns were obtained using a Rigaku
MiniFlex powder diffraction system, equipped with a horizontal
goniometer in the h/2 ꢀ h mode. The X-ray source was nickel-
filtered K-a emission of copper (1.54056 Å). Samples were packed
into an aluminum holder using a back-fill procedure and will be
scanned over the range of 50–6° 2 ꢀ h, at a scan rate of 0.5°
2
ꢀ h/min. Using a data acquisition rate of 1 point per second,
the scanning parameters equate to a step size of 0.0084° 2 ꢀ h.
Calibration of each powder pattern will be effected using the char-
acteristic scattering peaks of aluminum at 44.738° and 38.472°
2
ꢀ h.
The UV–VIS–NIR spectra between 190 and 1190 nm, using sol-
vent acetonitrile (Uvasol, Merck product) at a concentration of
ꢀ
5
2
.5 ꢁ 10 M in 0.921 cm quartz cells were recorded on Tecan
Safire Absorbance/Fluorescence XFluor 4 V 4.40 spectrophotometer.
Solid-state diffuse-reflectance and fluorescence spectra were mea-
sured on a PerkinElmer Lambda 750 in reflectance mode. The reflec-
tion spectra were automatically converted to absorbance spectra
using Kubelka–Munk theory. Conventional IR and Raman spectros-
copy in solid-state were performed on a Thermo Nicolet 6700 FTIR
2.2. Statistical and mathematical methods
The experimental and theoretical spectroscopic patterns were
processed by R4Cal OpenOffice STATISTICs for Windows 7 program
package [7]. Baseline corrections and curve-fitting procedures
were applied. The baseline correction performs operations on a
spectra by multi-point level or function fitting, using the standard
linear equation. The curve-fitting nonlinear procedure was applied.
ꢀ
1
ꢀ1
spectrometer (4000–400 cm
00 scans), and a NXR FT-Raman module within the 4000–50 cm
region, resolution 0.5 cm
and
ꢀ1
1
region. The thermo gravimetric study was carried out using a
Perkin-Elmer TGS2 instrument. The calorimetric measurements
were performed on a DSC-2C Perkin Elmer apparatus under argon.
The content of the metal ions are obtained by the ICP measurements
on the ICP–OES Thermo Elemental spectrometer with abominator
Argon–plasma. The detection is obtained by the following lines for
In the case of the Levenberg–Marquardt method, the merit equa-
2
tion used is
minimum in the reduced
v
the equation. The final solution is found when a
2
v equation is reached. The interpreta-
tion of the CD and fluorescence spectra is performed, using the
Gaussian function, best fitting the experimental data set. The sta-
tistical significance of each regression coefficient was checked by
the use of t-test (calculation of the number of significance using
data from the experimental error, usually higher than 0.100). The
1
13
Ag (328.0 and 338.2 nm). H and C NMR spectra were obtained at
Bruker 400 XC spectrometer, using TMS as standard in CD OD.
3

9
8
M. Lamshöft et al. / Inorganica Chimica Acta 382 (2012) 96–104
model fit was determined by F-test (comparison of calculated by
the model and experimentally obtained signal values).
22.5, 22.6, 28.0, 28.4, 29.7, 29.9, 34.6, 44.4, 44.8, 45.2, 45.8, 50.7–
73.1, 111.2, 113.9, 114.7, 118.5, 121.1, 124.8, 127.4, 148.9, 151.9.
I-(4): Anal. Calc. for C26
H
21
N
2
I: C, 69.9
4 3 4
; H, 4.3 . Found: C, 63.7 ;
1
2.3. Quantum chemical methods
4.3
H), 6.64 (d, 2H, J = 9.3), 6.70 (s, 1H), 7.45 (d, 2H, J = 9.3).
NMR: d 19.7, 22.5, 28.2, 28.3, 34.5, 44.4, 45.2, 45.8, 73.3, 111.2–
124.9, 127.4, 148.9. II-(1): Anal. Calc. for C17 13NOFI: C, 51.9 ; H,
%. H NMR: d 2.22–4.13 (m, 5H), 3.17 –
3
%. H NMR: d 1.40–3.00 (m, 7H), 3.39 (q, 4H, J = 6.9), 5.58 (s,
13
1
C
Quantum chemical calculations are performed with GAUSSIAN 98
and DALTON 2.0 program packages [8], visualizing by GAUSVIEW03
program. The geometries of the studied species were optimized by
density functional theory (DFT), employing B3LYP, CAM-B3PW91
and M06–2X functionals. Molecular geometries were fully opti-
mized by the force gradient method using Bernys’ algorithm. For
every structure the stationary points found on the molecule poten-
tial energy hypersurfaces were characterized using standard analyt-
ical harmonic vibrational analysis. The absence of the imaginary
frequencies, as well as of negative eigenvalues of the second-deriv-
ative matrix, confirmed that the stationary points correspond to
minima of the potential energy hypersurfaces. The EAs and Fs in
gas phase and methanol are obtained by TD-DFT calculations, utiliz-
ing the polarizable continuum model (PCM). The calculations are
performed by triple-f quality TZVP, triple-f plus double polarization
TZ2P, Los Alamos National Laboratory’s 2 double-f as well as quasi-
relativistic effective core pseudopotentials from Stuttgart-Dresden.
The large ‘‘correlation consistent’’ basis sets aug-cc-pVDZ and
aug-cc-pVTZ (augmented correlation-consistent polarized valence
double and triple zeta levels) are also applied.
H
1
1
3 2 7
3.3 . Found: C, 51.9 ; 3.4
1
3
3.44 (m, 7H), 6.72 (d, 2H, J = 9.3). C NMR: d 22.3, 22.6, 28.2,
28.3, 29.5, 29.9, 34.6, 44.3, 44.8, 45.2, 45.8, 50.7–73.1, 111.2,
113.9, 114.7, 118.5, 148.6, 169.2. II-(2): Anal. Calc. for C22
H
23
N
2
I:
1
C, 59.7 ; H, 5.2 . Found: C, 59.7 ; 5.2 %. H NMR: d 2.22–4.13 (m,
6 4 7 0
1
3
5H), 3.02–3.22 (m, 7H), 6.72 (d, 2H, J = 9.3). C NMR: d 22.3, 22.6,
28.2, 28.3, 29.5, 29.9, 30.3, 32.7, 34.6, 44.3, 44.8, 45.2, 45.8, 50.7–
73.1, 111.2, 113.9, 114.7, 118.5, 148.6, 155.9. II-(3): Anal. Calc. for
1
C H
30 25
N
2
I: C, 66.6
7
; H, 4.6
6
. Found: C, 66.8
9
; 4.9
1
%. H NMR: d
13
2.22–4.15 (m, 5H), 3.02–3.25 (m, 7H), 6.73 (d, 2H, J = 9.3).
C
NMR: d 22.2, 22.7, 28.1, 28.2, 29.4, 29.8, 30.3, 32.7, 34.5, 44.2,
44.7, 45.1, 45.9, 50.7–73.1, 111.1, 113.8, 114.5, 118.6, 148.7,
155.8. II-(4): Anal. Calc. for C30
H
24
N
2
I: C, 66.8
0 8
; H, 4.4 . Found: C,
1
66.2 ; 4.4 %. H NMR: d 2.22–4.14 (m, 5H), 3.02–3.25 (m, 7H),
3 7
1
3
6.71 (d, 2H, J = 9.2). C NMR: d 22.2, 22.5, 28.1, 28.2, 29.4, 29.8,
30.2, 32.5, 34.5, 44.2, 44.7, 45.1, 45.7, 50.7–73.2, 111.1, 113.8,
114.5, 118.3, 148.5, 166.1. III-(1): Anal. Calc. for C21
H
15NOFI: C,
1
56.9
H), 3.02–3.22 (m, 7H), 6.72 (d, 2H, J = 9.3). C NMR: d 22.3, 22.6,
28.2, 28.3, 29.4, 30.2, 30.3, 32.7, 34.6, 44.3, 44.8, 45.2, 45.8, 50.7–
3.1, 112.7, 113.8, 114.7, 118.2, 148.4, 153.0. III-(2): Anal. Calc.
0 1 7 2
; H, 3.4 . Found: C, 58.1 ; 3.4 %. H NMR: d 2.27–4.19 (m,
1
3
5
2.4. Synthesis
7
1
The ligands are obtained according the classical scheme for syn-
for C26
25 2 2 2 1 7
H N I: C, 63.4 ; H, 5.1 . Found: C, 63.7 ; 4.7 %. H NMR: d
13
thesis of stilbazolium salts [1]. The iodide salt, methyl-substituted
benzene and aldehydes were mixed in 50.0 ml toluene at molar ra-
tio 1:1:1. To the reaction mixture are added 5.00 ml acetic acid and
2.22–4.13 (m, 5H), 3.02–3.22 (m, 7H), 6.72 (d, 2H, J = 9.3).
C
NMR: d 22.3, 22.6, 28.2, 28.3, 29.5, 29.9, 30.3, 32.7, 34.6, 44.3,
44.8, 45.2, 45.8, 50.7–73.1, 111.2, 113.5, 114.7, 118.5, 148.6,
0
.77 g (10.00 mmol) ammonium acetate. The obtained suspensions
155.9. III-(3): Anal. Calc. for C34
H
27
N
2
I: C, 69.1
6 4
; H, 4.7 . Found: C,
1
are stirring during 24 h at r.t. The 0.50 ml k. HI acid and 10.00 ml
ethanol are added. The obtained reaction mixtures stay 16 h at r.t.
69.2 ; 4.4 %. H NMR: d 2.22–4.10 (m, 5H), 3.10–3.20 (m, 7H),
5 3
1
3
6.71 (d, 2H, J = 9.3). C NMR: d 22.2, 22.5, 28.1, 28.5, 29.5, 29.7,
The precipitates were filtered off, washed with C
2
5
H OH and dried
30.3, 32.7, 34.6, 44.2, 44.2, 45.1, 45.7, 50.7–73.0, 111.0, 113.2,
on P at 298 K. The high resolution MS data were in a good agree-
ment with the proposed elemental composition of the singly
2
O
5
114.5, 118.3, 148.5, 155.7. III-(4): Anal. Calc. for C34
H
25
N
2
I: C,
1
69.3 ; H, 4.7 . Found: C, 69.7 ; 4.2 %. H NMR: d 3.11–4.13 (m,
9 6 5 6
+
+
13
charged cations [(C17
H
14
N
3
OF)] (I-(1)), [(C17
H
18
N
2
)] (I-(2)),
5H), 3.15–3.43 (m, 7H), 6.70 (d, 2H, J = 9.2). C NMR: d 22.3–30.0,
+
+
+
[
[
[
(
(
(C26
(C22
(C22
3)), [(C36
IV-(2)), [(C30
H
H
H
23
N
N
2
)] (I-(3)), [(C26
H
21
N
2
)] (I-(4)), [(C18
H
15NOF)] (II-(1)),
30.2, 32.4, 34.5, 44.2, 44.8, 45.2, 45.8, 50.7–73.1, 111.1, 113.8,
+
)]+ (II-(3)), [(C30
+
24
2
)] (II-(2)), [(C30
H
26
N
2
H
24
N
H
2
)] (II-(4)),
114.5, 118.1, 148.5, 155.3. IV-(1): Anal. Calc. for C22
H
23
N
3
: C,
+
+
+
1
17NOF)] (III-(1)), [(C26
H
25
N
2
)] (III-(2)), [(C36
27
N
2
)] (III-
80.2
10H), 3.18–3.34 (m, 4H), 6.92 (s, 1H). C NMR: d 44.4–50.7,
111.2–118.5. IV-(2): Anal. Calc. for C22 : C, 80.7 ; H, 6.4
%. H NMR: d 2.22–3.20 (m, 9H), 3.18–3.34
1
; H, 7.0
4
. Found: C, 80.2
4
; 7.0
7
%. H NMR: d 2.22–3.15 (m,
+
+
+
13
21
H
25
N
2
)] (III-(4)), [(C22
H
23
N
3
)] (IV-(1)), [(C22
H
21
N
3
)]
+
+
H
23
N
3
)] (IV-(3)), and [(C30
H
21
N
3
)] (II-(4)) as well
H
N
3
0
5
.
1
as the elemental analysis. The MS peaks are at m/z 295.221
2
,
Found: C, 80.3
(m, 4H), 6.93 (s, 1H). C NMR: d 44.4–50.5, 111.2–118.3. IV-(3):
Anal. Calc. for C30 : C, 84.4 ; H, 5.6 . Found: C, 84.7 ; 5.5 %.
H NMR: d 2.22–3.23 (m, 9H), 3.20–3.30 (m, 4H), 6.92 (s, 1H).
NMR: d 44.4–50.5, 111.2–118.5 and IV-(4): Anal. Calc. for
2 6
; 6.4
1
3
2
2
3
50.131
18 , 330.386
24.175 , 327.323
6
, 363.444
, 365.189
, 424.181
2
, 361.101
0
, 280.333
3
, 316.487
9
, 414.544
4
, 412.
2
2
5
, 513.227
6
, 538.877 , 487.619
5
1
, 485.334
3
,
H
24
N
3
8
7
9
5
1
13
5
3
1
and 423.545
2
, respectively. Common
C
1
signals of the substituents in the H NMR: d = 2.95 (t, 2H, N-
1
CH
2H), 6.55 (1H), 7.40 (1H), 7.55 (2H) and 8.15 ppm (2H), respec-
tively. Elemental analysis: I-(1): Anal. Calc. for C17 OF: C,
%. H NMR: d, ppm, 9.71 (d,
N), 9.04 (d, 2H, J = 5.2 Hz, C ), 8.10 (d, 2H,
N), 7.80 (t, 1H, J = 4.3 Hz, C
q, 4H, J = 6.8), 6.64 (d, 2H, J = 9.3), 6.69–6.73 (d, 2H), 7.45 (d, 2H,
2
CH
3
), 1.55 (m, 4H, CH
2
CH
2
), 2.13 (t, 3H, CH
3
), 6.55 (2H), 7.18
30 22 3 8 2 1 9
C H N : C, 84.8 ; H, 5.2 . Found: C, 84.9 ; 5.3 %. H NMR: d
1
3
(
2.22–3.21 (m, 9H), 3.20–3.35 (m, 4H), 6.95 (s, 1H). C NMR: d
44.4–51.3, 111.2–120.1. The recrystallization of the ligand IV-(1)
from the solvent mixture methanol to water at ratio 1:1 results to
formation of thin polycrystalline fraction with crystal size 0.02–
13 3
H N
1
6
8 5 2 7
9.3 ; H, 4.4 . Found: C, 69.2 ; 4.4
2
H, J = 6.0 Hz, C
H
5 3
4 3 2
H N
1
J = 6.2 Hz, C
5
H
4
4
H
3
N
2
); H NMR: 3.39
1
0.04 Å. The crystallographic data result to high R -factor of 23%.
The obtained parameters unit cell parameters are a = 10.880(2),
b = 13.483(3) and c = 25.250(5) Å, b = 93.00(3)°, Z = 8, V = 3698.97
(
13
J = 9.3). C NMR: d 12.5, 19.6, 22.5, 28.3, 28.3, 34.5, 44.1, 45.2,
5.9, 73.2, 111.1, 113.4, 114.2, 118.9, 121.2, 124.1, 127.4, 168.8. I-
2): Anal. Calc. for C18 I: C, 55.1 ; H, 5.4 . Found: C, 55.1
%. H NMR: d 1.40–3.00 (m, 7H), 3.40 (q, 4H, J = 6.9), 5.59 (s,
4
Å, monoclinic space system and space group P2
are obtained from (1) and (2) derivatives of ligand type II, where R
is pentyl (or ethyl) substituents, and R = OH, using the labeling in
Scheme 1. The structural parameters are: a = 9.302(2),
b = 12.068(3), c = 12.230(5) Å, = 77.73(3), b = 74.858(10), = 73.7
13(5)°, Z = 1 (1) and a = 9.3087(17), b = 12.032(2), c = 12.216(2) Å,
= 77.751(6), b = 74.627(6), = 73.578(6)°, Z = 2 (2), triclinic space
system and P space group. The crystallographic parameters for the
positions of the heavy atoms are used as input parameters for the
1
/n. Thin 2D crystals
(
5
1
H
21
N
2
1
0
4
;
1
1
.4
H), 6.64 (d, 2H, J = 9.3), 6.72 (s, 1H), 7.46 (d, 2H, J = 9.3).
3
4
1
3
C
NMR: d 19.7, 22.5, 28.0, 28.4, 34.6, 44.4, 45.2, 45.8, 73.2, 111.0,
14.2, 114.3, 118.8, 121.3, 124.9, 148.9, 151.9, 157.2. I-(3): Anal.
a
c
1
1
Calc. C26
H
23
N
2
I: C, 63.6
8
; H, 4.7
3
. Found: C, 63.7
7
; 4.7
2
%. H NMR:
a
c
d 1.42–3.00 (m, 7H), 3.39 (q, 4H, J = 6.8), 5.58 (s, 1H), 6.65 (d, 2H,
1
J = 9.3), 6.68 (s, 1H), 7.47 (d, 2H, J = 9.3). 13C NMR: d 12.5, 19.7,

M. Lamshöft et al. / Inorganica Chimica Acta 382 (2012) 96–104
99
I
quantum chemical calculations of the EAs. Since the
p-electronic
N
py-atom. The Ag -complexes with dyes of type IV are mononu-
transitions are localized within the frame of the molecular skeleton
of the conjugated aromatic systems, the good correlation between
the theoretical and experimental optical properties are found. The
usage of the crystallographic data set give possibility to predict rea-
sonably well the optical phenomena in solid-state [1l]. On our study
these model systems allow to evaluate theoretically the possibility
for the interlayered CT in the frame of the crystals, which could
have contributions in the corresponding optical Ds and Fs spectra.
The metal–organic complexes were obtained during the interaction
clear. The ligands act bidentately, by the N-atoms, forming stable
-
5-membered rings. The bidentately coordinated NO
3
ions are
I
found as terminal ligands, similar to other Ag -metal–organic
NLO materials [1,9]. The thermogravimetric and calorimetric data
(I)
3 2
for the [Ag (X-(i))(NO )(H O)] (i = 1–4, X = II or III) complexes
show an inclusion of the solvent water molecule. The coordination
to the metal ion is assumed (below). The obtained geometry
I
I
parameters for the Ag –O and Ag –N bond lengths within
2.215(1)–2.235(2) and 2.185(6)–2.433(1) Å, correlated well to the
I
of the ligands with Ag(NO
3
)
2
at molar ratio metal-to-ligands 1:1
crystallographic data for Ag complexes [l]. The corresponding
I
I
and 1:2 in acidic medium. The solvent water is used. The complex
formation in methanol (or at pH higher than 4), leads to red-ox pro-
O–Ag –O and O–Ag –N angles are within 105.0(1)–98.6(8)° and
I
88.7(7)–120.7(3)°, respectively. The symmetry of the Ag ON
mophore in [Ag (I-(1))(NO
X = II or III), as well as the Ag O
3
chro-
III
I
I
cess of the metal ion to Ag or Ag(0) ions/colloid suspension,
3
)] and [Ag (X-(i))(NO
3
)(H
2
O)] (i = 1–4,
I
I
I
respectively. Elemental analysis: [Ag (I-(1))(NO
3
)]: Anal. Calc. for
2
N
2
chromophore in the [Ag (I-
)], i = 1–4 is evaluated,
I
I
C
17
H
12
N
4
O
4
FAg: C, 44.0
8
; H, 2.6
1
. Found: C, 45.1
Ag: C, 61.8 ; H, 5.7
)]: Anal. Calc. for C26
8
; 2.7
2
%; [Ag (I-
. Found:
Ag: C,
)]: Anal. Calc.
(1))
studying the models systems Ag (H
with square planar and T geometry (symmetry respectively). Sim-
2
(NO
3
)], i = 2–4 and [Ag (IV-(i))(NO
3
I
I
(
2))
C, 61.9
9.8 ; H, 4.9
for C26
1))(NO
Found: C, 45.8
Ag: C, 52.6
)(H O)]: Anal. Calc. for C30
Found: C, 60.4
Ag: C, 60.1
)(H O)]: Anal. Calc. for C21
Found: C, 50.2
Ag: C, 56.5
)(H O)]: Anal. Calc. for C34
Found: C, 62.9
Ag: C, 62.6
)]: Anal. Calc. for C22
2
(NO
3
)]: Anal. Calc. for C18
H
20
N
3
O
3
9
7
2 2 3 2 2 3 3
O) (NH ) and Ag (H O) (NH )
I
2
; 5.8
9
%; [Ag (I-(3))
. Found: C, 69.7
Ag: C, 66.5 ; H, 4.2
O)]: Anal. Calc. for C17
2
(NO
3
H
33
N
3
O
3
d
I
I
II
6
0
6
3
; 4.9
6
%; [Ag (I-(4))
. Found: C, 66.6
FAg: C, 45.0
)(H O)]: Anal. Calc. for
. Found: C, 52.7
Ag: C, 60.0
)(H O)]: Anal. Calc. for
. Found: C, 60.7
FAg: C, 50.1
)(H O)]: Anal. Calc. for
. Found: C, 56.8
Ag: C, 69.3
)(H O)]: Anal. Calc. for
. Found: C, 62.9
Ag: C, 52.9
)]: Anal. Calc. for C22
2
(NO
3
ilar to the data for other Ag and Zn complexes [1l] the obtained
NEC values (Table 1), show typical configurations for coordination
compounds with removed degeneracy of the d-states. The obtained
NEC values for PO of N- and O-atoms of the CT stabilized systems,
show configurations, attributed to a Jahn–Teller (JT) effects both in
the ligands as well as in the metal ion. If we describe the obtained
I
H
20
N
3
O
3
3
9
3
; 4.2
8
%; [Ag (II-
; H, 3.1
(
3
)(H
2
H
14
N
2
O
5
6
1
.
I
9
; 3.1
4
. [Ag (II-(2))(NO
; H, 8.3
3
2
I
C
22
H
24
N
3
O
4
0
7
1
; 8.9
7
. [Ag (II-
; H, 4.3
(3))(NO
3
2
H
26
N
3
O
4
1
6
.
I
7
; 4.8
9
%; [Ag (II-(4))(NO
; H, 4.2
3
2
data by an induced JT effect of the distorted T
d
geometry of the
I
C
30
H
25
N
3
O
4
1
0
1
; 4.7
7
%; [Ag (III-
; H, 3.2
chromophores, than we could expect a photon emission in the rest
2ꢀ
(1))(NO
3
2
H
16
N
2
O
5
2
0
.
part of the crystal medium similar to the ZnCl
4
complexes [1l].
I
2
; 3.0
3
%; [Ag (III-(2))(NO
; H, 4.7
3
2
Since, the crystal structures contain more than one organic mole-
cule (and ions) characterizing with strong optical emission both
in solution as well as in solid-state, the further excitation is diffi-
cult to be located. The observed data, however, could explain our
MS data in gas-phase. The stabilized quasi metal–organic species
could assign as a result of the CT effect and the chelating properties
of the ligands I-(1) and IV.
I
C
26
H
26
N
3
O
4
3
4
1
; 4.7
9
%; [Ag (III-
; H, 4.4
(3))(NO
3
2
H
29
N
3
O
4
8
5
.
I
1
; 4.9
1
%; [Ag (III-(4))(NO
; H, 4.0
3
2
I
C
34
H
26
N
3
O
4
9
4
1
; 4.0
; H, 4.6
1
%; [Ag (IV-
. Found:
Ag:
)]: Anal.
; 4.0 .%;
Ag: C, 60.6 ; H,
(
1))(NO
C, 53.2
C, 53.1
Calc. for C30
3
H
23
N
4
O
3
2
4
I
9
; 4.9
6
%; [Ag (IV-(2))(NO
. Found: C, 53.1
Ag: C, 60.4
)]: Anal. Calc. for C30
; 3.3 %, respectively.
3
21 4 3
H N O
I
4
; H, 4.2
4
8
; 4.2
9
%; [Ag (IV-(3))(NO
. Found: C, 60.8
3
H
24
N
4
O
3
2
; H, 4.0
6
2
8
I
3.2. Spectroscopic data in condense phase
and [Ag (IV-(4))(NO
3
H
22
N
4
O
3
2
3
.7
3
. Found: C, 60.7
1
9
The experimental and theoretical EAs of the ligands are shown
in Table 1, and Fig. 1. The data for the coordination compounds are
I
3
. Results and discussion
summarized in Table 2. The coordination with the Ag ion leads to a
bathochromic shifting of the ICT band within 15–25 nm as well as
I
ꢀ1
ꢀ1
Since, the Ag -containing complexes always exhibit large and
the hypochromic effect of 650–700 l mol cm . This result is an
additional evidence for the metal-to-ligand CT effect in the com-
plexes. The solvatoschromic effect of 120–235 nm, depending of
the solvent polarity is found. The observed untypical for the ligand
interesting OL capabilities; the impact of the ligands on OL perfor-
mance in the novel Ag -complexes is small. An insignificant contri-
bution to delocalization of
I
p-electron cloud or the relatively poor
orbital overlap between the metal ions and the ligands is found.
The physical optical properties of the ligands in corresponding
coordination compounds, however, are discussed below. The novel
ligands belong to four main classes of organic dyes. The 4-
styryl-pyridinium type (I), 4-styryl-quinolinium type (II), 4-(2-
naphthalen-1-yl-vinyl)-quinolinium type (III) and phenyl-
Table 1
Otimized geometries of the AgI complexes at B3PW91/SDD levels of theory; The
coordination centers are calculated as solvent H O molecules; Theoretical values of
the atomic charges, natural electron configuration and total energy are obtained in
gas-phase and polar solvent (methanol).
2
(
phenyl-pyridin-2-yl-methylene)-amine type (IV) of organic
molecules are depicted and labeled in Scheme 1. The main reason
for the tuning of the molecular skeletal of these derivatives is based
on the already found NLO properties of analogous systems [1,9].
The substituents chose according their impact on the (b) in series
of different classes of organic dyes [1,2]. Their coordination ability
to form different self-assembly in the 1D, 2D, and 3D crystals, and
thin films is also evaluated.
Charges
Natural electron configuration (NEC)
Non-polar
Polar
Non-polar
Polar
I
Ag (H
2
O)
3
(NH
0.965
3
)
Ag
O
2
ꢀ4.699
7
. . .5s(0.22)4d(9.79)
. . .2s(1.79)2p(4.70)
. . .2s(1.73)2p(5.26)
. . .2s(1.74)2p(5.25)
. . .2s(1.44)2p(4.50)
. . .5s(0.49)4d(1.20)
. . .2s(0.03)2p(0.23)
. . .2s(1.00)2p(3.00)
. . .2s(0.91)2p(2.84)
. . .2s(0.02)2p(0.27)
ꢀ0.5013
ꢀ0.998
ꢀ1.001
ꢀ0.962
3.4922
O
O
N
8
ꢀ5.731
ꢀ5.620
3.024
1
6
4
1
0
I
Ag (H
2
2
O) (NH
3
)
2
3.1. Molecular geometry
Ag
O
0.482
0.206
ꢀ0.495
ꢀ0.498
ꢀ0.498
4
1
0
9
1
ꢀ6.042
9
4
. . .5s(0.12)4d(4.87)
. . .2s(0.89)2p(1.89)
. . .2s(0.86)2p(2.63)
. . .2s(0.87)2p(2.62)
. . .2s(0.72)2p(2.27)
. . .4d(2.25)5p(1.56)
. . .2s(0.03)2p(0.20)
. . .2p(2.97)3s(1.00)
. . .2s(0.96)2p(2.98)
. . .2s(0.02)2p(0.21)
3.534
I
O
N
N
ꢀ5.8112
The ligand type I-(1) act bidentately to the Ag -ion through the
py-atom and the deprotonated OH-group at R -position. Similar
3.458
3.1028
2
N
2
4
to ligand-types II and III, I act monodentately as well by the

1
00
M. Lamshöft et al. / Inorganica Chimica Acta 382 (2012) 96–104
3
Fig. 1. Non mathematically procedured spectroscopic curves of the EAs of the ligands and corresponding metal complexes in solutions (CH OH, ACN, THF or water depending
ꢀ
4
ꢀ5
of the solubility of the complexes); nonlinear curve-fitted spectroscopic pattern of II-(2) in methanol; concentration range 10 –10 mol/l (a), diffuse reflectance (D) and
fluorescence (F) spectra in solud state; nonlinear curve-fitted spectroscopic patterns by multipeak GAUSSIAN function after applied baseline correction method; A – total area
2
under the curve from the baseline center of the peak; w ‘‘sigma’’, approximately 0.869 the FWHM; w/2 – is the standard deviation (b).
series of bands within 300–400 and 600–800 nm in the spectrum
The solid-state IR-spectra of the ligands type I are characterized
I
ꢀ1
of [Ag (I-(4))
2 3
(NO )], could be associated to an existence of both
with most intensive IR-band about 1600 cm of the aromatic in-
⁄
aromatic and quinoide like forms of the ligands, similar to the opti-
cal properties of merocyanine 2,4-dihydroxybenzaldehyde mono-
hydrate dye [9]. The ICT bands of ligands I-VI are batochromic
plane (i.p.) vibration, 8a with local C 2v symmetry. The data for
the ligands II-IV are assigned using the statement for C
s
symmetry
)] is characterized with pairs
of bands at 1600 and 1565 cm corresponding to the C=C and i.p.
I
2 3
of the molecules. The [Ag (I-(4)) (NO
ꢀ1
shifted ca. 10 nm in solid-state. A splitting effect is also found
m
⁄
[
8l,m]. About 5 nm is shifted the band belonging the n ?
p
transi-
vibrations of the quinoide molecules. These characteristics are
strongly influenced by the tautomerism of such ligands, depending
of the solvent polarity. The quinoide forms are characterized with
tion. These results are in accordance with the assumed NHꢂ ꢂ ꢂO
and/or CHꢂ ꢂ ꢂO bonding type in solid-state [2,10]. The Ds of the
complexes are characterized with the highest wavelength band
at ca. 720 nm, assigned to ICT band within the frame of the mole-
cule skeleta of the dyes. The complex spectroscopic patters within
ꢀ1
the
band of
system about 1440 cm . The first maximum is significantly
mC=O stretching vibrations about 1500 cm and complex IR-
m
C=C stretching vibrations of the conjugated double bonds
ꢀ
1
I
4
40–490 nm are also observed. Their assignment, however is diffi-
2 3
shifted at lower frequencies. The spectrum of [Ag (I-(4)) (NO )]
cult as a result of the splitting of the bands under the crystal field
as well as the metal-to-ligand CT effects [1q,r]. For such complex
molecular species is difficult the unambiguously assignment of
the discussed maxima. The theoretical calculations of the EAs of
could be described in terms of a superposition of the spectroscopic
patterns of aromatic and quinoide forms of the ligand (Fig. 2).
3.3. Powder X-ray diffraction data
(
1) and IV-(1) and the HOMO–LUMO gaps predict an intermolecu-
lar CT band character of the maxima as result of a -stacking effect.
So, the interlayer CT phenomenon is also typical for such systems.
p
The powder XRD data for the complexes are shown in Fig. 3. The
obtained reflections, i.e. one strong peak at (100) and two with low

M. Lamshöft et al. / Inorganica Chimica Acta 382 (2012) 96–104
101
Table 2
The calculated total dipole moments (
electronic absorption data (k, nm (f – oscillator strength)) of the ligands and corresponding coordination compounds.
l
tot), dynamic polarizability (
a
),
a
= (a
xx
+
a
yy
+
a
zz)/3 (a.u.), hyperpolarizability (btot), ||b|| = (b2
x
+ b2
y
+ b2
z
)1/2; (ꢁ10ꢀ30 cm5 esuꢀ1
)
I-(1)
I-(2)
I-(3)
I-(4)
II-(1)
II-(2)
II-(3)
II-(4)
III-(1)
III-(2)
III-(3)
III-(4)
l
a
tot
10.22
ꢀ79.62
600.2
447
12.13
ꢀ51.48
712.3
533
(0.980)
421
(0.003)
367
(0.002)
20.94
ꢀ72.6
1605.3
759
(0.641)
507
(0.001)
456
(0.005)
ABILEC
[2]
24.25
ꢀ68.51
1833.8
843
(0.000)
790
(0.514)
488
(0.008)
DASJEN
[2]
10.22
ꢀ71.14
326.45
487
(0.360)
412
(0.220)
332
(0.031)
9.09
24.42
ꢀ97.34
470.4
731
(0.000)
680
(0.002)
679
(0.001)
26.5853
ꢀ110.16
1605.4
768
(0.003)
675
(0.000)
673
(0.000)
12.20
ꢀ80.33
610.2
455
(0.888)
390
(0.010)
350
(0.010)
IVꢀ (1)
12.13
ꢀ51.48
712.3
531
(0.080)
420
(0.011)
366
(0.010)
IVꢀ (2)
20.94
ꢀ72.6
1322.1
670
(0.641)
545
(0.010)
525
(0.015)
IVꢀ (3)
24.25
ꢀ68.51
1611.7
650
(0.010)
595
(0.500)
477
(0.011)
IVꢀ (4)
ꢀ128.92
368.0
617
(0.748)
392
(0.006)
382
(0.001)
b
tot
k (nm)
f)
(
(0.884)
3
94
0.007)
52
0.001)
XAFTAA
2]
(
3
(
[
l
a
tot
9.88
11.33
ꢀ103.22
622.1
500
(0.001)
412
14.23
ꢀ68.22
677.2
508
(0.077)
395
11.44
ꢀ100.02
489.13
468
(0.621)
385
14.13
ꢀ70.89
522.2
530
(0.070)
425
10.30
ꢀ94.41
465.7
666
(0.650)
550
10.03
ꢀ125.00
440.2
585
(0.010)
590
ꢀ80.22
862.2
422
b
tot
k (nm)
f)
(
(0.931)
3
95
0.055)
50
(
3
(0.010)
355
(0.010)
351
(0.011)
348
(0.010)
365
(0.015)
520
(0.700)
468
(0.011)
(0.011)
(0.010)
(0.019)
(0.015)
(0.018)
(0.310)
I
I
I
I
I
I
I
I
k (nm)
f)
[Ag (I-(1))(NO
3
)]
[Ag (I-
(2)) (NO
[Ag (I-
[Ag (I-
(4)) (NO
[Ag (II-
[Ag (II-
(2))(NO
[Ag (II-
[Ag (II-
(4))(NO
(
2
3
)]
(3))
2
(NO
3
)]
2
3
)]
(1))(NO
3
)(H
2
O)]
3
)(H
2
O)]
(3))(NO
3
)(H
2
O)]
3
)(H
2
O)]
Theor.
10
0.231)
11
0.033)
00
Exp. Theor.
Exp. Theor.
Exp. Theor.
756 743
(0.012)
Exp. Theor.
734 466
(0.900)
Exp. Theor.
Exp. Theor.
Exp. Theor.
693 722
(0.043)
675 660
(0.034)
Exp.
700
5
(
4
(
508
540
540
760
470
596
600
693
(0.312)
445
(0.552)
(0.800)
(0.012)
410
448 517
(0.033)
375 460
(0.007)
520
766
760
435
435 388
(0.011)
375
391 675
(0.011)
377 630
(0.015)
654
570
(0.012)
397 377
(0.015)
(0.500)
457
(0.210)
455 330
(0.060)
4
460
330
630
572
(0.010)
(0.039)
(0.044)
(0.011)
I
I
I
I
I
I
I
I
k (nm)
f)
[Ag (III-
(1))(NO
[Ag (III-
[Ag (III-
[Ag (III-
[Ag (IV-
(1))(NO
[Ag (IV-
[Ag (IV-
(3))(NO
[Ag (IV-
(
3
)(H
2
O)]
(2))(NO
3
)(H
2
O)]
(3))(NO
3
)(H
2
O)]
(4))(NO
3
)(H
2
O)]
3
)]
(2))(NO
3
)]
3
)]
3
(4))(NO )]
4
(
3
(
3
(
80
0.972)
92
0.000)
51
0.015)
477 530
(0.060)
410
(0.010)
351 350
(0.065)
528 675
(0.666)
555
667 650
(0.000)
552 595
(0.505)
480
(0.001)
647 445
(0.545)
598 396
(0.041)
479 350
(0.088)
450
400
530
(0.070)
435
533 670
(0.800)
438 555
(0.025)
372 525
(0.029)
590
550
380
590
(0.030)
495
(0.921)
473
(0.010)
587
496
465
390
400
350
(0.025)
515
(0.025)
(0.050)
510
362 370
(0.025)
Fig. 3. XRD data – radial distribution vs. the distance in Å.
I
Fig. 2. Solid-state IR-spectra of IV-(1) and the metal complex [Ag (I-(4))(NO
3
)].
different to those of the starting (1) and (2) as well as to those of
the ligands isolated and studied themselves.
intensity at (110) and (200) planes in the range 2h = 0.8–2°, indi-
cates a significant degree of long-range ordering, typical for 1D
self-assembly. The relative intensities of the prominent diffraction
peak (100) decreased after the introduction of bulky substituents
in the dye skeletal of corresponding coordination compounds with
ligands X-(2), where X = I–IV. This result could be associated with a
formation of the metal–organic glasses at the temperatures near to
the melting points, i.e. 346–423 °C, respectively (procedure for
formation of oriented solid-films). The obtained reflections are
3.4. Thermal methods
I
The TG/DSC analysis result of the complexes of type [Ag (X-
(i))(NO )(H O)], where i = 1–4, and X = II or III, need a discussion.
3
2
Quantification of weight loss at various steps is possible because
of their no overlapping patterns. Weight loss below 100 °C could
be associated with the phase transition or to the physically

1
02
M. Lamshöft et al. / Inorganica Chimica Acta 382 (2012) 96–104
adsorbed water. The 7.8–9.13% weight loss at 123–135 °C is mainly
related to the solvent water molecule, joined to the metal center.
Larger loss of 13.7% in the temperature range from 343 to 400 °C
is probably attributed to the decomposition of the organic ligands.
The loading of organic dyes is 0.21 mmol/g based on the 9.8% of
weight loss, and silver content is 0.35 mmol/g estimated by ICP-
AES. The molar ratio of metal to ligand is approximately 1:1. The
DSC curve agrees with the TG result. An intense exothermal peak
at 295 °C gives an evidence for the existence of a transition of
the metal-complexes, which could be associated with the change
of the geometry of the chromophore as well.
7.30 and 7.46 ppm (Fig. 4) [2]. The 13C NMR signals of I-(4) are
weakly affect and are observed about 132.0, 122.1, 152.2, 118.1
and 131.3 ppm, respectively. In the quinoide structure stabilization
leads to a shifting of the proton chemical of the first group of about
D
d 1.24, 0.80, 0.79 and 1.10 ppm, respectively. The aromatic proton
chemical signals are shifted as well and are observed within
0.55–1.05 ppm.
3.7. Nonlinear-optical properties
The obtained data of the molecular dipole moments, static
polarizabilities and nonlinear optical first hyperpolarizabilities
for the ligands are shown in Table 2. The btot values of the novel li-
gands I–IV are within 1.2–1.51 times larger than the corresponding
one of the DAST, using as standard [1,2]. The performed theoretical
analysis of the NLO properties are taking into account the molecu-
lar architecture of the studied organic dyes. Since, the effect of the
counterions is significant for the crystallographic packing, in the
calculations of the isolated molecules of organic dyes, it is ne-
glected. In the analysis of the crystals, however, depending of the
packing, it is important to note that it has been found large scale
of the effect of the anions on the NLO properties of the crystals
of organic dyes in the bulk. The minor modification of the substit-
uents on the anions would basically change the crystal structure
and NLO response of stilbazolium salts [2]. Other reports have been
show that medium size counter anions like tosylate are advanta-
geous in achieving large second order nonlinearities [2]. Studies
on N-aryl pyridinium salts have shown that in some instances
smaller anions like hexafluorophosphate are better than tosylate
for generating non-centrosymmetric crystal structures. As has
been shown the bulky anions tends to decrease the intermolecular
interaction and to a negative influence on the nonlinearity of the
molecules. Promising for further NLO measurements are appeared
the complexes with the ligands of type X-(3) and X-(4), where X =
3
.5. Mass spectrometric study
The analysis of the complexes exhibits quasi-molecular ions
indicating a CT bound metal ion to the organic moiety. These
results supported by the characteristic isotopic pattern of the
observed mass peaks, which exhibited the natural distribution of
silver 107 and 109 in a ratio of 52/48. The ESI-MS spectrum of
the complexes of types [Ag (I-(1))(NO
I
3
)], also indicate the gas-
I
3 2
phase stabilized CT complexes. The [Ag (III-(2))(NO )(H O)] is
characterized with peak at 357.4. The correlation between the data
for the ligands of type II and III, and the corresponding metal com-
plexes assumes a dominant role of the CT stabilized gas phase spe-
cies. The stabilizing chelating effect of the ligands types I-(1) and
IV, is also taking into account. In the metal complexes with mono-
dentately coordinated ligands only peaks for cationic organic moi-
eties are found [1q,r].
3
.6. Nuclear-magnetic resonance data
Additional confirmation about the existence of both aromatic
and quinoide like forms of the ligands as a result of the CT effects
in the complex [Ag (I-(4)) (NO )] is obtained, studying the corre-
2 3
sponding H and C NMR spectra. The H- chemical signals are
shifted within 8.44–9.12, 8.00, 7.37 and 7.82 ppm, respectively.
The aromatic protons are characterized with signals at 7.00, 6.80,
I
1
13
1
2 3
I–V with the –N(Ph) and 9H-carbazole substituents at R -position.
The obtained btot values are within 3.8–4.4 times larger than the
DAST, respectively. It is important to note for the further design
I
Fig. 4. 2D-NMR spectra in solution of the IV-(2) and [Ag (IV-(2))(NO
3
)], respectively.

M. Lamshöft et al. / Inorganica Chimica Acta 382 (2012) 96–104
103
of the molecular skeletal of the ligands I–IV in respect their appli-
cation as organic NLO materials as well as ligands for correspond-
ing metal–organic derivatives, that the large conjugation systems
from 4-styryl-pyridinium type to 4-(2-naphthalen-1-yl-vinyl)-
quinolinium one leads to decreasing of the btot values ca. 1.7 times.
chaft (DFG) for Grants SPP 255/21-1 and SPP/22-1. The authors also
thank the central instrumental laboratories for structural analysis
at Dortmund University of Technology (TUD, Germany) and the
analytical and computational laboratories at the Institute of
Environmental Research (INFU) at the TUD.
3
Thus important are appears the type of the substituent at R -posi-
tion in the DAST analogous with 4-styryl-pyridinium type of the
molecular architecture. Moreover, the relatively bulky substituents
at the end of the chromophore of the dye molecule, decrease the
inter-chromophore interactions in the corresponding crystals by
the site-isolation effect. As has been shown [2] this may be benefi-
cial for enhancing (or not reducing) the hyperpolarizability of the
chromophores in the solid state. Indeed, for DAST it was shown
that the hyperpolarizabilities in the solid state are reduced by
more than 80% compared to solution because of intermolecular
interactions. The comparison of the obtained theoretical data also
need to attend that the electronic structures of the molecules with
the asymmetric chromophores as the metal–organic species,
where the metal-to-ligand CT effect is observed, thus hyperpolariz-
abilities of these chromophores are in fact substantially 2D in nat-
ure, so in such cases is rather to probe the relative importance of
different tensor components of b. Such for example the chromoph-
ores with C2v symmetry has five nonzero components of the b ten-
sor, moreover these tensor components show no clear dependence
on the nature. Since, formally the hyperpolarizability terms enter
into the expansion of the overall polarization of a molecule of an
applied electric field the obtained btot values appear informatively
about the NLO properties of the molecules. The second-order re-
sponse, the magnitude of which increases as the molecule becomes
less centrosymmetric by the tuning of the substituents and the
manner of the coordination with the metal ion, depending of the
experimental conditions, such as pH and mainly the molar ratio
metal to ligand, is the quantity of interest in the presented study.
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