A novel copper(I) sulfamate π-complex based on the 5-(allylthio)-1-(3,5-dimethylphenyl)-1H-tetrazole ligand: Alternating-current electrochemical crystallization, DFT calculations, structural and NLO properties studies

Article abstract of DOI:10.1016/j.poly.2018.03.015

Using the alternating-current electrochemical technique, the novel π-complex [Cu^I(m-dmphast)NH₂SO₃] (1), based on the 5-(allylthio)-1-(3,5-dimethylphenyl)-1H-tetrazole (m-dmphast) ligand, was obtained and it was studied by single crystal X-ray diffraction as well as IR and UV–Vis spectroscopy. The structure 1 should be considered as the first known example of a metal sulfamate coordination compound with a tetrazole ligand. The copper(I) ion in 1 possesses a trigonal pyramidal environment, arranged from the N4 atom of the tetrazole core, the C[dbnd]C bond from the S-allyl group of the same m-dmphast ligand and O and N atoms of the NH₂SO₃^? anions. The sulfamate anion is coordinated to the two neighboring Cu(I) ions in a bridged mode, occupying a basal plane (through the N atom) and an apical (through an O atom) position of the two neighboring metal trigonal pyramids. The bicolor coherent photoinduced treatment by a nanosecond Nd:YAG laser at a wavelength of 1064 nm caused the occurrence of charge density acentricity, which in turn favours an occurrence of second harmonic generation described by third rank polar tensors, that are usually forbidden for centrosymmerical crystals.

Full text of DOI:10.1016/j.poly.2018.03.015

Accepted Manuscript
A novel copper(I) sulfamate π-complex based on the 5-(allylthio)-1-(3,5-dime-
thylphenyl)-1H-tetrazole ligand: alternating-current electrochemical crystalli-
zation, DFT calculations, structural and NLO properties studies
Yu.I. Slyvka, A.A. Fedorchuk, N.T. Pokhodylo, T. Lis, I.V. Kityk, M.G.
Mys'kiv
PII:
S0277-5387(18)30140-2
https://doi.org/10.1016/j.poly.2018.03.015
POLY 13081
DOI:
Reference:
Polyhedron
To appear in:
Received Date:
Accepted Date:
5 February 2018
13 March 2018
Please cite this article as: Yu.I. Slyvka, A.A. Fedorchuk, N.T. Pokhodylo, T. Lis, I.V. Kityk, M.G. Mys'kiv, A novel
copper(I) sulfamate π-complex based on the 5-(allylthio)-1-(3,5-dimethylphenyl)-1H-tetrazole ligand: alternating-
current electrochemical crystallization, DFT calculations, structural and NLO properties studies, Polyhedron (2018),
doi: https://doi.org/10.1016/j.poly.2018.03.015
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A novel copper(I) sulfamate π-complex based on the 5-(allylthio)-1-(3,5-
dimethylphenyl)-1H-tetrazole ligand: alternating-current electrochemical
crystallization, DFT calculations, structural and NLO properties studies
Yu.I. Slyvkaa,*, A.A. Fedorchuka, N.T. Pokhodyloa, T. Lisb, I.V. Kitykc,d, M.G. Mys’kiva
aFaculty of Chemistry, Ivan Franko National University of Lviv, KyrylaiMefodiya Str., 6,
79005, Lviv, Ukraine
bFaculty of Chemistry, University of Wrocław, Joliot-Curie 14, 50-383 Wrocław, Poland
cInstitute of Optoelectronics and Measuring Systems, Faculty of Electrical Engineering,
Czestochowa University of Technology, 17 ArmiiKrajowej Str., 42-200 Czestochowa, Poland
dDepartment of Physics, Eastern European National University, 13 Voli
Avenue, 43025 Lutsk, Ukraine
*Corresponding author: E-mail address: yurii.slyvka@lnu.edu.ua (Yu.I.Slyvka)
ABSTRACT
Using the alternating-current electrochemical technique, the novel π-complex [CuI(m-
dmphast)NH2SO3] (1), based on the 5-(allylthio)-1-(3,5-dimethylphenyl)-1H-tetrazole (m-
dmphast) ligand, was obtained and it was studied using single crystal X-ray diffraction as well
as IR and UV–Vis spectroscopy. The structure 1 should be considered as the first known
example of a metal sulfamate coordination compound with a tetrazole ligand. The copper(I)
ion in 1 possesses a trigonal pyramidal environment, arranged from the N4 atom of the
tetrazole core, the C=C bond from the S-allyl group of the same m-dmphast ligand and O and
–
N atoms of the NH2SO3 anion. The sulfamate anion is coordinated to the two neighboring
Cu(I) ions in a bridged mode, occupying a basal plane (through the N atom) and an apical
(through an O atom) position of the two neighboring metal trigonal pyramids. The bicolor
coherent photoinduced treatment by a nanosecond Nd:YAG laser at a wavelength of 1064 nm
caused the occurrence of charge density acentricity, which in turn favours an occurrence of
second harmonic generation described by third rank polar tensors, that are usually forbidden
for centrosymmerical crystals.
Keywords: tetrazole; copper(I) π-complex; crystal structure; ac-electrochemical
technique; NLO properties
1. Introduction

Intensive efforts to search for and design compounds with organic molecules
(chromophores) possessing enhanced non-linear optical (NLO) susceptibilities in a wide
spectral range of transparency are of a special interest due to the development of laser
optoelectronic devices [1,2]. Organometallic compounds with a large delocalized π-
conjugated electron system have potential applications in the field of non-linear optics due to
their specific electronic absorptions, allowing them to be applied the typical lasers, facile
preparation, large optical non-linearity (particularly third-order NLO properties) and the
possibility of diverse ligand design and preparation [3-8]. The geometrically defined donor-
metal-acceptor arrangement of an organometallic fragment was found to be crucial for optical
properties such as phosphorescence, quadratic and cubic non-linear optics, photoinduced
effects etc. It was also shown that the photochromic properties could be readily tuned by
varying the metal systems or by incorporating alternative donor centers in the organic ligand
[8]. Among them, copper(I)-olefine complexes with alkenes have received considerable
theoretical and practical interest because of their remarkable catalytic and luminescent
activities, and other useful properties [9-12]. Also, the key role of heterocycles in the crystal
engineering of copper π-compounds with extremely rare occurring inorganic fragments was
found in recent years [13-15]. In contrast to solely σ-donor ligands, the coordination role of
allyl derivatives in the stabilization of unusual Cu(I) compounds is in good accordance with
the hard and soft acids and bases theory [13] (the olefin C=C bond acts as a soft base and the
heterocyclic molecule donor atoms possess border-line basicity); the coordination of an allylic
group as well as heterocyclic donor atoms to copper(I) ions causes specific interaction
conditions between the π,σ-coordinated soft Cu+ acid, on the one hand, and hard bases (O, F),
on the other. These specific coordination conditions are also caused by the contribution of a
directed Cu(I)-olefin interaction (which includes σ-donor (CuI←C=C)σ and π-dative
(CuI→C=C)π components) to the splitting of the copper atom’s localized 3d orbitals
(accompanying by a significant increase of the dz2 orbital energy), which leads to a significant
distortion of the copper(I) tetrahedral coordination. Therefore, the synergy of a flexible allyl
group and a conformationally rigid heterocyclic core plays an exceptionally crucial role in the
stabilization of the unique fragments, resulting in the formation of compounds that exhibit a
range of useful properties. Among the organic ligands possessing 6π-electron aromaticity,
recently 1-allyloxybenzotriazole was found to be a good instrument for the design of a
crystalline π-compound with enhanced non-linear optical susceptibilities [16]. Copper(I)
complexes also have a couple of potential applications in advanced laser operated materials.
For example, such compounds work as acid/base-induced “on–off” luminescence switch

materials or display high photocatalytic activity at ambient temperature [17]. Copper
complexes exhibit considerable biochemical activities, ranging from antibacterial and anti-
inflammatory to cytostatic and enzyme inhibitory. Copper ions may be considered as
multifunctional, participating in a broad spectrum of intracellular processes under normal and
pathologic conditions [18]. Cu(I) complexes have been tested in vitro as potential anticancer
drugs and have been found to be effective against A549 adenocarcinoma cells, which are
resistant to the widely used anticancer drug, cisplatin [19]. Moreover, cancer progression is
accompanied by increased ceruloplasmin and copper levels in various tissues, and the
elevated copper levels and increased oxidative stress in cancer cells provide for the prospect
of selective cancer treatment [20,21]. The exploration of their NLO features may be useful for
the monitoring and clarification of the mentioned biochemical mechanisms.
Taking into account that most studied copper(I) coordination compounds for NLO
properties are based on pyridine ligands [22], an investigation of the tetrazole containing
system should attract enhanced attention. Moreover, an increase in the number of donor atoms
in the heterocyclic ring should significantly contribute to the above conditions, that is why N-
or S-allyl derivatives of tetrazoles (being practically unknown as ligands with respect to Cu(I)
complexes) in this aspect appears to be of particular interest. So far, only five π-compounds
(in accordance with the Cambridge Crystallographic Database (CCD) [23]) of ionic Cu(I)
salts with allyl derivatives of tetrazole have been obtained and studied by X-ray
crystallography [24-27]. In the present work, we have focused on the synthesis, structural
characterization and optical properties of the novel copper(I) π-complex [Cu(m-
dmphast)NH2SO3] (1), based on the 5-(allylthio)-1-(3,5-dimethylphenyl)-1H-tetrazole (m-
dmphast) ligand. At present, the metal sulfamate coordination compound with a tetrazole
ligand is studied for a first time. Particular attention will be devoted to the second non-linear
optical features.
2. Experimental
2.1. Materials and instrumentation
Unless otherwise mentioned, all chemicals were obtained from commercial sources
1
(Sigma Aldrich) and were used without further purification. The H NMR spectrum of m-
dmphast was recorded on a Varian Mercury 400 instrument (400 MHz) with deuterated
solvent as an internal reference. IR spectra for m-C12H14N4S and complex 1 were recorded in
KBr pellets on a FT-IR Spectrum BX-II, PerkinElmer spectrometer in the 4000-400 cm-1
range (see supplementary materials). Measurement of the electronic spectrum of complex 1 in

methanol was performed at 25 °C with a double-beam UV-VIS Spectrophotometer
Spekol 2000 (Analytik Jena) in the wavelength range λ = 190-1100 nm (with a 1 nm step
size). The solution was placed in quartz cuvette with a 10 mm thickness of the absorption
layer and then the UV-Vis spectrum was recorded against methanol. Diffraction data for 1
were collected on a Kuma KM-4-CCD diffractometer with Mo Ka radiation (λ = 0.71073 Å).
2.2. Preparation of 5-(allylthio)-1-(3,5-dimethylphenyl)-1H-tetrazole
The target ligand IV (m-dmphast) was synthesized from the commercially available 3,5-
dimethylaniline I by several procedures (Scheme 1). The appropriate dimethylaniline I was
converted into dimethylisothiocyanatobenzene II by the reaction with methanedithione,
followed by the treatment with ethyl chlorocarbonate and HCl, according to a modified
Kaluza method [28]. By the 1,3-dipolar cycloaddition reaction of the obtained
dimethylisothiocyanatobenzene II with the azide ion, 1-(dimethylphenyl)-1H-tetrazole-5-thiol
III was formed, which was then readily reacted with 3-bromoprop-1-ene in the presence of
KOH, yielding the corresponding ligand IV [29,30]. 5-(Allylthio)-1-(3,5-dimethylphenyl)-1H-
tetrazole (m-dmphast, C12H14N4S): 1Н NMR (400 MHz, DMSO-d6), δ, ppm: 7.21 (s, 1H, HPh-
4), 7.17 (s, 2H, HPh-2,6), 5.98 (dt, J = 16.8, 7.0 Hz, 1H, =CH), 5.37 (d, J = 16.8 Hz, 1H,
CH2=), 5.18 (d, J = 9.8 Hz, 1H, CH2=), 4.00 (d, J = 7.0 Hz, 2H, CH2), 2.40 (s, 6H, CH3); IR
(KBr, cm−1): 3016 (w), 2975 (m), 2924 (m), 2858 (w, Csp3–H), 1844 (w, C-C), 1732 (m, C-C),
1637 (w, C=C), 1614 (s, C–C, phenyl ring), 1595 (s, C–C, phenyl ring), 1475 (s, C=C and
C=N, tetrazole ring), 1383, (vs, C–S), 1271 (s, C–N and N–N, tetrazole ring), 924 (s, Csp2–H,
allyl), 730 (m, Csp2–H, allyl), 687 (s, CPh–H).
CS2
H C
NCS
H C
3
NH
2
3
Et3N
NaN3
H2O
1. ClCOOEt
Et3N
CH
CH
3
3
2. HCl
II
I
N
S
N
N
N
N
N
N
N
H C
3
Br
H C
3
KOH
SH
EtOH
CH
3
CH
3
IV
III
Scheme 1 Synthesis of m-dmphast

2.3 Synthesis of the copper(I) π-complex
For the synthesis of complex 1, an alternating-current electrochemical synthesis [31,32]
was chosen due to the possibility of large anion variety usage [14,33-35], contrary to the
classic direct method.
Crystals of complex 1 were obtained starting from a water-alcohol solution of the
appropriate organic ligand and the corresponding copper(II) salt. To 4.5 mL of a saturated
water-alcohol (0.5mL of H2O, 0.5 mL of C2H5OH and 3.5 mL of CH3OH) solution of
Cu(NH2SO3)2 0.15 g (0.61 mmol) of m-dmphast was added. Afterwards the mixture was
carefully stirred. A copper wire was wrapped into a spiral of 1 cm diameter. A straight copper
wire was placed inside the spiral. These copper electrodes were inserted in cork and immersed
in the above mentioned solutions. The synthesis was performed using alternating current
tension, providing the course of the following reactions:
-
Cu2+
e
m-dmphast
m-dmphast
NH SO
[Cu(m-dmphast)(NH2SO3)]
[Cu(m-dmphast)(NH2SO3)]
K(-):
+
+
+
2
3
Cu0
-
A(+):
NH SO
e
+
+
2
3
After application of an alternating-current tension (frequency 50 Hz) of 0.45 V for 7
days, good quality colorless crystals of 1 appeared on copper electrodes. The yield was about
75%. IR (KBr, cm−1): 3266 (s), 3192 (s); 2972 (m), 2921 (s), 2858 (m, Csp3–H), 1838 (vw, C-
C), 1616 (m, C–C phenyl ring), 1594 (m, C–C phenyl ring), 1477 (m, C=C and C=N,
-
-
tetrazole ring), 1433 (N–O, NO3 ), 1266 (vs), 1211 (vs), 1051 (vs), 1030 (vs, NH2SO3 ), 915
-
(m, Csp2–H, allyl), 772(s, N–S, NH2SO3 ), 714 (m, Csp2–H allyl), 690 (m, CPh–H).
2.4 Single crystal X-ray diffraction studies
The crystallographic parameters and summary of the data collection for 1 are presented
in Table 1. The collected diffraction data for 1 were processed with the CrysAlis PRO
program [36]. The structure was solved by the ShelXT program and refined by the least
squares method on F2 by the ShelXL program with the graphical user interface OLEX2 [37-
39]. Atomic displacements for non-hydrogen atoms were refined using an anisotropic model.
Hydrogen atoms (except N-bonded H atoms) were placed in ideal positions and refined as
riding atoms with their relative isotropic displacement parameters.
Table 1

Selected crystal data and structure refinement parameters of 1
CCDC number
Empirical formula
Formula weight
Temperature, K
Wavelength, Å
Crystal system,
space group
Unit cell dimensions
a, Å
1816413
C12H16CuN5O3S2
405.96 g/mol
150(2)
0.71073
orthorhombic
Pbca
7.737(3)
14.866(4)
27.640(8)
3179.1(17)
8
b, Å
c, Å
V, Å3
Z
Calculated density, g/cm3 1.70
Absorption coeff., mm-1
1.658
F(000)
1664
Crystal size, mm
Color
0.47 × 0.22 × 0.17
Colorless
Diffractometer
θ range, °
Kuma KM-4-CCD
3.01 – 28.74
–10 ≤ h ≤ 5, –19 ≤ k ≤ 18,
–35 ≤ l ≤ 35
Full-matrix least-squares
on F2
Limiting indices
Refinement method
Measured reflections
Used in refinement
Free parameters
15060
3829
218
Goodness-of-fit on F2
1.036
R ( F02 2(F2 )
)
R1 = 0.0457, wR1 = 0.1209
0
R (all)
R1 = 0.0516, wR2 = 0.1269
Largest diff. peak and
hole, e Å−3
0.87 and -0.64

2.5 Theoretical quantum chemical calculations
For the dimer fragment in 1 of the {Cu(m-dmphast)NH2SO3}2 composition (Fig. 6a),
additional quantum chemical calculations of the dipole moment, first order
hyperpolarizabilitiy (β) at 1064 nm as well as simulations of the HOMO and LUMO, and UV-
Vis spectra were performed using the Gaussian W09 package [40]. Calculation of the dipole
moment, average first order hyperpolarizability (β), HOMO and LUMO shape were
performed using the DFT and B3LYP functional methods supplemented with the standard 6-
31G(d) basis set for H, C, N, O and S atoms and LANL2DZ ECP for the Cu atom. The UV-
VIS spectrum was simulated using TD-DFT and B3LYP with 6-31G(d) (H, C, N, O, S) and
LANL2DZ ECP (Cu) basis sets. A primary model derived from the structure obtained by X-
ray diffraction was used.
3. Results and discussion
3.1. Crystal structure
The crystal structure of [Cu(m-dmphast)NH2SO3] (1) demonstrates the only example to
date of a metal sulfamate coordination compound with a tetrazole ligand (Fig. 1). The π-
complex 1 crystallizes in the orthorhombic centrosymmetric space group Pbca, with one
–
copper(I) ion, one NH2SO3 ion and one m-dmphast molecule in the asymmetric unit. In 1, the
Cu(I) ion possesses a trigonal pyramidal environment, coordinated by the N4 atom of the
tetrazole core, a C=C bond from the S-allyl group of the same ligand and O and N atoms of
–
the NH2SO3 anion (Fig. 1). The sulfamate anion is coordinated to the two neighboring Cu(I)
ions in a bridging mode, occupying a basal plane (through the N atom) and an apical position
(through an O atom) of the two neighboring metal trigonal pyramids. Thus, an infinite
coordination {Cu(m-dmphast)NH2SO3}n polymer is formed in 1 (Fig. 2). Two hydrogen
atoms of the sulfamate anion participate in N-H….O hydrogen bonding with two
neighbouring anions and it provides stabilization of the organometallic chain (Table 2).

Fig. 1. Fragment of the crystal structure 1. Symmetry codes: (i) 0.5+x, y, 1.5-z; (ii) -0.5+x, y,
1.5-z. Selected bond length (Å) and angle (deg) values: Cu–N4 1.994(2), Cu–N5 2.015(2),
Cu–O1 2.444(2), C1–C2 1.369(4), Cu–m 1.927(3) (m - middle point of the C1=C2 bond), C1-
Cu-C2 39.1(1), m-Cu-N4 116.7(1), m-Cu-N5 139.7(1), N4-Cu-N5 103.10(9), N4-Cu-O1
94.5(1).
The organic molecule m-dmphast in the structure of 1 adopts N,(C=C)-bidentate and
chelate functions, being attached to the metal centre through the S-allylic C=C bond and the
most nucleophilic N atom of the tetrazole ring. Such a bidentate π,σ-coordination behavior of
1-aryl substituted 5-(allylthio)-1H-tetrazoles with regard to ionic Cu(I) salts is observed for
the first time, while the previously studied 1-phenyl- (phast), 1-(4-chlorophenyl)- (clphast)
and 1-[2-(trifluoromethyl)phenyl]- (trifphast) substituted 5-(allylthio)-1H-tetrazoles showed a
dominant tendency to be bound with copper(I) ions by means of two N3 and N4 tetrazole
atoms, forming stable {Cu2(L)2}2+ dimers [23-25]. The dihedral angle between the planes of
the tetrazole and phenyl rings equals 39.06(7)º.

Fig. 2. The organometallic {Cu(m-dmphast)NH2SO3}n chain in 1.
Table 2
Geometry of selected hydrogen bonds in the crystal structure of 1
Atoms involved
D−H···A
Symmetry
Distances, Å
H···A
Angle, deg
D−H···A
167(3)
D−H
D···A
N5−H5A···O3
N5−H5B···O2
−0.5+x, y, 1.5−z
0.5+x, y, 1.5−z
0.82(3)
0.89(4)
2.13(4)
2.939(3)
3.096(3)
2.26(4)
157(3)
The allylic C=C bond is slightly elongated to 1.369(4) Å (due to a back-donation from
an occupied 3d metal orbital to a low-lying empty π* orbital of the olefin) in contrast to the
values for free ethylene: 1.338(1) Å gas phase [41], 1.3142(3) Å at 85 K [42]. The efficiency
of the Cu(I)(C=C) interaction in 1 is also confirmed by the fact that the Cu(I) ion deviates
from the base of the trigonal pyramid by 0.086(1) Å, as well as by the relatively small angle
between the C=C bond and the polyhedron base plane (14.2(1)°). A rather short Cu–m (m =
mid-point of the C=C bond) bond distance and large C-Cu-C angle also confirm this
conclusion. A comparison of the vibrational spectra of the pure ligand and the corresponding
π-compound shows a significant frequency decrease of the C=C band, caused by the effective
Cu(I)(C=C) interaction. In the IR spectrum of the pure m-dmphast ligand the C=C stretching
mode is observed at 1637 cm-1, while the band arising from the C=C vibrations of the allyl
group coordinated to the copper ion in 1 is bathochromically shifted and disguised by the C-C

stretching bands of the phenyl ring. The deformational vibration C-H band of the –CH=CH2
group, observed at 730 cm-1, is also shifted to lower frequencies by 14 cm-1.
3.2. Non-linear optical effects
It is well known that optical second harmonic generation (SHG) is forbidden in
centrosymmetric media, including crystals. The presence of Cu(I) ions possessing localized
3d-states and an additional absorption in visible light spectra may favor the performance of
bicolor coherent stimulated material treatment. The process of the treatment by two coherent
beams of the fundamental and doubled frequency leads to the occurrence of a long lived
reversible dc-electric field [43]. During the treatment by the two coherent beams, which are
space separated, features similar to single-axis crystals appear [44]. The corresponding
mechanisms are theoretically well described in detail in the literature [45].
Fig. 3. Principal set-up for performance of bicolor coherent laser treatment.
The bicolor treatment and registration of the photoinduced SHG was performed using
the principal set-up shown in Fig. 3. A light beam from a pulsed Nd:YAG nanosecond laser
with a frequency repetition of about 10 Hz was incident on the single non-linear crystals of
BiB3O6 (BiBO) cut under the phase matching angle. After the crystals, two coherent beams at
wavelengths ω=1064 nm and doubled frequency 2ω=532 nm were incident on the set of
mirrors M2 and M3, forming two optical channels. The first channel at 1064 nm was the
fundamental channel and the doubled frequency channel at 2ω formed a writing channel. A
set of polarizers P1/P2 and lenses L1/L2 form two coherent beams with different intensities.
Additionally using a set of polarizers and lenses gives an opportunity to tune the power
densities of the fundamental ω and writing 2ω beams. The photoinduced process contains two

stages. The first one is the bicolor photopolarization, realized using simultaneous illumination
by two bicolor beams. This process has a duration of up to 2-3 mins and its efficiency and
saturation were controlled using continuous wave (CW) low power He-Ne laser diffraction
gratings. During this step, a non-centrosymmetric charge density is created. The second step
(measurements of the photoinduced SHG) requires switching off the writing channels and
only performing registration for the output SHG using a set of green interferometer filters.
The polarizers operate by light polarizations of the angles between the laser beams based on
the ratio between the fundamental and the writing beams. The SHG efficiency was
determined using the photomultiplier with the ratio of the corresponding intensities.
Additionally, for space control of the SHG we analyzed the SHG space distribution using a
CCD camera.
The principal mechanisms of the bicolor coherent treatment are explained by the
occurrence of gratings. Generally, in our case some optically induced electrostatic field occurs
due to photocarrier charge separation, which is more prominent for the 3d-localized Cu states.
The electrostatic field favors an occurrence of second order optical susceptibilities through the
(2)
equations χijk(2)= χijkl E0l , where χijk(2) corresponds to third rank polar tensors requiring charge
density acentricity and χijkl(2) corresponds to fourth rank tensors describing the effects which
do not need space density acentricity. Additionally, the bicolor coherent interaction leads to
the occurrence of birefringence of the nij gratings, which is responsible for the existence of
the SHG [46].
For the non-linear optical studies, the powders were embedded into polyvinyl alcohol
(PVA) photopolymer matrices. Among the different concentrations, 35% was optimal. All the
solidified processes were carried out similarly to that described in the literature [47]. To
evaluate the efficiency of the second order susceptibilities, we have used the reference organic
samples studied earlier [1]. These crystals are among the best for observing photoinduced
second order NLO effects. For example, in many materials [48-52] studied under the same
experimental conditions by us, the effect was less than 15 %.
The effective second order susceptibility, determined by the ratio of the corresponding
maximal SHG intensities, versus the fundamental power density is given in Fig. 4.

1.0
0.8
0.6
0.4
0.2
0.0
parallel
perpendicular
0
5
10
E[MW/cm2]
15
20
Fig. 4. Dependence of the laser induced second order susceptibilities versus the laser induced
power density for the two output polarization of the SHG with respect to the fundamental
ones.
The optical treatment was performed by two bicolor coherent beams at angles varying
within 20-21 degrees for the two polarizations with respect to the fundamental beams. Fig. 4
shows an increase of the second order susceptibility with enhancement of the laser induced
power density up to 20 MW/cm2. To avoid the influence of the parasitic fluorescence
background, two filters at wavelengths of 528 and 535 nm have been used. The further
increase of the SHG was limited by the samples photo-thermal destruction. The effect
disappeared over 2-3 minutes after switching off the two bicolor beams, however some
irreversible SHG remains (up to 10 %).

Fig. 5. The beam profile of the output SHG for the different ratios of the photoinduced ω to 2
ω beam powers. The left (a) corresponds to a ratio of 4:1 and the right one (b), 6:1.
Fig. 5 clearly confirms that some space gratings occur, and the gratings are also directly
related to the SHG efficiency and the laser stimulated gratings absorption. The higher space
frequency favors higher SHG intensities and it is closely connected to the photoinduced
gratings. During the measurements we varied the ratio between the fundamental and the
doubled frequency intensities within the range 3:1 to 10:1. It appeared that the maximal signal
was achieved for the ratio 6:1. This confirms the huge role of the laser induced gratings.
Additionally, it is necessary to empathize that a similar treatment of the optical lead
containing glasses [53-56] gives an effect a least half an order less. This may indicate the
principal role of the Cu-containing bonds to the effect observed. Additionally, disordered
oxide materials, even with Cu, are more stable and are not sensitive to laser induced changes
[57].
3.3. Quantum chemical calculations
HOMO and LUMO space distribution plots for compound 1 are presented in Fig. 6. In
the calculated UV-Vis spectra in the range 250-700 nm, the electronic transitions are
presented mainly by three peaks – a main peak at an approximate wavelength of 255 nm and
two weak absorption maxima at around 279 and 297 nm (Fig 7). The last two mentioned
peaks mainly correspond to the electronic transitions from HOMO-1 (MO 197) to the MOs
which are located near ligand molecules, which is associated with a charge transfer from the
–
NH2SO3 anion and Cu+ cation donor fragments to the rest of the ligand molecule (Tables 3
and S1). One can conclude that we deal with a clear donor-acceptor space separation defining
–
a principal charge transfer from the NH2SO3 anion to the ligand molecule.

Table 3
Selected calculated absorption wavelengths, energies and oscillator strengths of 1
Excitation
CI expansion
coefficient
Excitation
energy (eV)
Calculated
wavelength (nm)
Oscillator
strength (f)
Singlet-A
-0.27001
0.59886
0.15688
Singlet-A
0.51946
-0.23470
-0.11137
0.30556
0.16581
-0.12269
4.1801
296.60
0.0120
197 ->205
197 ->206
197 ->208
4.4434
279.03
0.0102
193 ->200
194 ->200
197 ->204
197 ->205
197 ->206
197 ->208
Since the samples were prepared in the form of microcrystalline powders, characteristic
SHG properties could be described using average first-order hyperpolarizability. First-order
hyperpolarizability (β) is a third order tensor which can be described by a 3 × 3 × 3 matrix
with 27 components, which can be reduced to 10 components due to the Kleinman symmetry.
Using x, y and z components, the hyperpolarizability (β) could be written as follows:
The (β) components of the GAUSSIAN 09 output are reported in atomic units and
therefore the calculated values are converted into esu units (1a.u =8.6393 × 10-33esu). The
computed values of the dipole moment μ and the average hyperpolarizability (β) for 1 equals
20.79 D and 3.92×10–29esu.

Fig. 6. {Cu(m-dmphast)NH2SO3}2 fragment (a) and its HOMO-1 (b),
HOMO (c) and LUMO (d) plots.
Fig. 7. Experimental (a) and theoretically calculated (b) UV-VIS spectra of compound 1.
4. Conclusions
We have synthesized and determined the crystal structure of a novel copper(I) π-
complex, [CuI(m-dmphast)NH2SO3] (1), with the 5-(allylthio)-1-(3,5-dimethylphenyl)-1H-
tetrazole (m-dmphast) ligand. It is the only example to date of a metal sulfamate coordination

compound with a tetrazole ligand. m-Dmphast acts as a chelate π,σ-ligand, being attached to
the Cu(I) ion by means of the allylic C=C bond and one tetrazole N atom. In complex 1, the
sulfamate anion is coordinated to two neighboring Cu(I) ions in the bridged mode, occupying
a basal plane (through the N atom) and an apical position (through an O atom) of two
neighboring metal trigonal pyramids. A high efficiency of the studied material for optical
treatment by an external bicolor laser nanosecond light at 1064 nm was established. The effect
is almost independent of the polarization and is higher than for known non-linear optical lead
containing glasses. The principal role here is played by highly localized 3dCu states.
Appendix A. Supplementary data
CCDC 1816413 contains the supplementary crystallographic data for compound 1. These
data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or
from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ,
UK; fax: (+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
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A novel crystalline π-complex, [CuI(C12H14N4S)NH2SO3], was grown.
The complex was studied by single crystal X-ray diffraction, IR- and UV–VIS spectroscopy.
The structure is considered as the first known example of a metal sulfamate coordination
compound with a tetrazole ligand.
Quantum chemical calculations were performed using DFT and the B3LYP functional
Effective laser operated non-linear optics are found