Optical Materials 35 (2013) 1481–1486

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Optical Materials
journal homepage: www.elsevier.com/locate/optmat

Synthesis of nickel(II) complexes containing modified phenanthroline ligands

for potential nonlinear optical applications
Zhi-Bin Cai a,⇑, Li-Fen Liu a, Mao Zhou b
a
College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310014, PR China
b
Zhejiang Poly Pharmaceutical Co. Ltd., Hangzhou 310009, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Three nickel(II) complexes containing modified phenanthroline ligands were synthesized and character-
Received 30 December 2012 ized by UV–visible, IR, MS and elemental analysis. Their off-resonant third-order nonlinear optical prop-
Received in revised form 25 February 2013 erties were measured using femtosecond laser and degenerate four-wave mixing technique. The third-
Accepted 11 March 2013
order nonlinear optical susceptibilities v(3) were 3.74–4.23  1013 esu. The nonlinear refractive indexes
Available online 6 April 2013
n2 were 6.88–7.77  1012 esu. The second-order hyperpolarizabilities c of the molecules were 3.74–
4.22  1031 esu. The response times were 58–75 fs. The results show that these complexes have poten-
Keywords:
tial nonlinear optical applications.
Nonlinear optics
DFWM technique
Ó 2013 Elsevier B.V. All rights reserved.
Nickel(II) complex
Synthesis

1. Introduction cyclometallated iridium(III) and ruthenium(II) complexes with

Rapid advancements in the field of photonics have greatly in-
creased the demand for high-performance third-order nonlinear
optical (NLO) materials. In recent years, the research for novel
third-order NLO materials has found a new horizon with the devel-
opment of organometallic and coordination materials [1–8]. Com-
pared with purely organic materials, greater design flexibility can
be achieved by varying the metal, its oxidation state, the ligand
environment and the geometry. In addition, the incorporation of
transition metal ions introduces more sublevels into the energy
hierarchy, thus permitting more allowed electronic transitions
and giving larger NLO effects.
Third-order NLO materials typically have delocalized p-conju-
gated electron systems, which are believed to be a potential source
of fast nonlinearity [9–14]. 1,10-Phenanthroline (phen) is an inter-
esting molecule. It possesses a planar p-conjugated electron sys-
tem and can act as an acceptor group due to the deficiency of
electron density on the ring C atoms. Furthermore, it is an impor-
tant bidentate ligand towards a variety of transition metal ions.
Many metal complexes of ruthenium(II), copper(II), cobalt(II) con-
taining phen or phen derivatives have been synthesized and their
valuable applications as DNA structural probes [15–17], DNA
photocleavage reagents [18–20], molecular light switches [21,22]
and dye-sensitized solar cells [23,24], etc. have been found. Re-
cently, Dragonetti and Valore [25–28] have also reported that
⇑ Corresponding author. Tel.: +86 571 88320428.
E-mail address: caizbmail@126.com (Z.-B. Cai).
substituted phen can exhibit strong second-order NLO response.
However, the vast potential of this kind of complexes containing
phen or phen derivatives as third-order NLO materials remains
largely untapped.
The nickel transition metal has an open d-shell, which allows
the possibility of low energy charge transfer transitions. Several
studies indicate that the nickel ion is an excellent template to gath-
er conjugated organic molecules around to form two or three
dimensional third-order NLO materials [29–36].
Herein, we describe in detail the synthesis and the third-order
NLO properties of three nickel(II) complexes a–c (Fig. 1) that fea-
ture different modified phen ligands (IP, PP, DPPZ). Their struc-
tures were characterized by UV–visible, IR, MS and elemental
analysis. By using femtosecond laser, the off-resonant third-order
optical nonlinearities of the complexes were measured with
degenerate four-wave mixing (DFWM) technique. The relation-
ships between molecular structure and optical property were ana-
lyzed. To our knowledge, it is the first study of the NLO properties
for these complexes and the complexes a and c are new.
2. Experimental
2.1. Materials
The compound 1,10-phenanthroline-5,6-dione was prepared
according to the literature method [37]. Other materials were pur-
chased from East China Pharmaceutical Group Co. Ltd., and of re-
agent grade. All of them were used without further purification.

0925-3467/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.optmat.2013.03.009
1482 Z.-B. Cai et al. / Optical Materials 35 (2013) 1481–1486

c
Fig. 1. Structures of the nickel(II) complexes a–c.

2.2. Physical measurements on a Shimadzu UV-2550 UV–visible spectrometer. Elemental

FT-IR spectra were recorded on a Vector 22 spectrometer
using KBr pellets. 1H NMR spectra were collected on a AVANCE
III 500 MHz apparatus, with TMS as internal standard and
DMSO-d6 (or CDCl3) as solvent. UV–visible spectra were recorded
analyses were conducted on a Thermo Finnigan Flash EA 1112
apparatus. Mass spectra were taken on a Therm LCQ TM Deca
XP plus ion trap mass spectrometry instrument. Melting points
were measured on an X-4 micromelting point apparatus without
correction.
 Z.-B. Cai et al. / Optical Materials 35 (2013) 1481–1486
2.3. Synthesis of the ligands
The synthetic route to the ligands is outlined in Scheme 1.
2.3.1. 1H-Imidazo[4,5-f][1,10]phenanthroline (IP)
A mixture of 1,10-phenanthroline-5,6-dione (1.05 g, 5 mmol),
formaldehyde (0.18 g, 6 mmol), ammonium acetate (7.7 g,
100 mmol), and glacial acetic acid (16 mL) was heated under reflux
with stirring for 3 h. The cooled solution was diluted with H2O and
neutralized with concentrated aqueous ammonia. The precipitate
was collected and recrystallized from DMF. A light yellow crystal-
line powder was obtained. Yield: 0.8 g, 72.7%. m.p. > 310 °C (Lit.
m.p. > 310 °C [38]). 1H NMR (500 MHz, DMSO-d6), d (ppm): 13.75
(s, 1H), 9.03 (dd, 2H, J1 = 4.3 Hz, J2 = 1.5 Hz), 8.83 (dd, 2H, J1 = 8 Hz,
J2 = 1.5 Hz), 8.47 (d, 1H), 7.83 (dd, 2H, J1 = 8 Hz, J2 = 4.3 Hz).
2.3.2. Pyrazino[2,3-f][1,10]phenanthroline (PP)
A solution of ethylenediamine (0.45 g, 7.5 mmol) in ethanol was
added dropwise to 1,10-phenanthroline-5,6-dione (1.05 g,
5 mmol) dissolved in ethanol (20 mL). The resulting mixture was
refluxed for 4 h. The solution was concentrated in vacuo, and the
solid was recrystallized from methanol. A light yellow needle crys-
tal was obtained. Yield: 0.91 g, 78.4%. m.p. = 255–256 °C (Lit.
m.p. = 253–255 °C [39]). 1H NMR (500 MHz, CDCl3), d (ppm): 9.52
(dd, 2H, J1 = 8.1 Hz, J2 = 1.8 Hz), 9.31 (dd, 2H, J1 = 4.4 Hz,
J2 = 1.8 Hz), 9.00 (s, 2H), 7.82 (dd, 2H, J1 = 8.1 Hz, J2 = 4.4 Hz).
2.3.3. Dipyrido[3,2-a: 20 ,30 -c]phenazine (DPPZ)
This ligand was synthesized as above using o-diaminobenzene.
The product was a light yellow needle crystal. Yield: 1.15 g, 81.6%.
m.p. = 253–254 °C (Lit. m.p. = 251–252 °C [40]). 1H NMR (500 MHz,
CDCl3), d (ppm): 9.72 (d, 2H, J = 8.0 Hz), 9.36 (d, 2H, J = 4.0 Hz), 8.40
(dd, 2H, J1 = 6.5 Hz, J2 = 3.5 Hz), 7.96 (dd, 2H, J1 = 6.5 Hz,
J2 = 3.5 Hz), 7.86 (dd, 2H, J1 = 8.0 Hz, J2 = 4.0 Hz).
2.4. Synthesis of the complexes
2.4.1. Tris(1H-imidazo[4,5-f][1,10]phenanthroline-jN7,jN8)-
nickel(2+) (a)
A mixture of nickel dichloride hexahydrate (0.24 g, 1 mmol), IP
(0.73 g, 3.3 mmol) and methanol (30 mL) was heated under reflux
Scheme 1. Synthesis of the ligands.
1483
with stirring for 3 h. The resulting reaction mixture was cooled to
room temperature, and a saturated aqueous sodium perchlorate
solution (10 mL) was added. The precipitate was collected and
recrystallized from DMF twice. A pink crystalline powder was ob-
tained. Yield: 0.71 g, 69.8%. FT-IR (KBr), m (cm1): 3390 (mNH, mOH),
3090 (m=CH), 1610, 1538, 1444, 1417, 1117 (mClO4), 813 (d=CH), 734
(d=CH), 625 (dClO4). Anal. Calc. for C39H24Cl2N12NiO85.5H2O: C,
46.04; H, 3.47; N, 16.52. Found: C, 46.09; H, 3.33; N, 16.13%. ESI-
MS (CH3CN): m/z 717.4 ([M2ClO4–H]+), 359.8([M2ClO4]2+).
2.4.2. Tris(pyrazino[2,3-f][1,10]phenanthroline-jN8,jN9)-nickel(2+)
(b)
This complex was synthesized using a procedure similar to that
described for a, with PP instead of IP. The product was a pink crys-
talline powder. Yield: 0.66 g, 64.9%. FT-IR (KBr), m (cm1): 3436
(mOH), 3082 (m=CH), 1612, 1582, 1483, 1405, 1087 (mClO4), 817
(d=CH), 735 (d=CH), 623 (dClO4). Anal. Calc. for C42H24Cl2N12NiO8-
3.5H2O: C, 49.58; H, 3.07; N, 16.52. Found: C, 49.61; H, 3.01; N,
16.15%. ESI-MS (CH3CN): m/z 377.6([M2ClO4]2+).
2.4.3. Tris(dipyrido[3,2-a: 20 ,30 -c]phenazine-jN4,jN5)-nickel(2+) (c)
This complex was synthesized using a procedure similar to that
described for a, with DPPZ instead of IP. The product was a light
pink crystalline powder. Yield: 0.82 g, 71.9%. FT-IR (KBr), m
(cm1): 3428 (mOH), 3072 (m=CH), 1635, 1580, 1495, 1419, 1094
(mClO4), 818 (d=CH), 737 (d=CH), 622 (dClO4). Anal. Calc. for C54H30Cl2-
N12NiO82H2O: C, 56.87; H, 3.00; N, 14.74. Found: C, 56.74; H, 3.21;
N, 14.38%. ESI–MS (CH3CN): m/z 452.8([M2ClO4]2+).
2.5. Nonlinear optical measurements
The third-order NLO properties were measured using femtosec-
ond DFWM technique, with a Ti: Sapphire laser. Fig. 2 shows the
experimental setup. The pulse width was determined to be 80 fs
on a SSA25 autocorrelator. The operating wavelength was centered
at 800 nm. The repetition rate of the pulses was 1 kHz. During the
measurement, the laser was very stable (rms < 0.1%). The input
beam was split into two beams k1 and k2 with nearly equal energy
by using a beam splitter, then focused on the sample. The beam k2
passed through a delay line driven by a stepping motor in order
that the optical path length difference between the k2 and k1
beams could be adjusted during the measurement. The angle be-
tween the beams k1 and k2 was about 5°. When k1 and k2 were
overlapped spatially in the sample, the generated signal beam k3
or k4 passed through an aperture, recorded by a photodiode and
then analyzed by a Lock-in amplifier and computer.
The experiments were performed at 22 °C. The samples dis-
solved in DMF at concentrations of 5  104 mol/L were placed in
a 1 mm thick quartz cell. The solvent DMF has no nonlinear signal
under the light intensity adopted. So the third-order optical non-
linearities measured come from the complexes themselves.
3. Results and discussion
3.1. Synthesis and characterization
The ligands IP, PP and DPPZ were prepared through condensa-
tion of 1,10-phenanthroline-5,6-dione with formaldehyde, ethy-
lenediamine and o-diaminobenzene, respectively. All of them
gave well-defined 1H NMR spectra, which permit their unambigu-
ous identification and assessment of purity. The nickel(II) com-
plexes a-c were synthesized by direct reaction of corresponding
ligands with NiCl26H2O in methanol. They were isolated as the
perchlorates and purified by recrystallization in relatively high
yield. The elemental analyses of these complexes were in
1484 Z.-B. Cai et al. / Optical Materials 35 (2013) 1481–1486
Fig. 2. Experimental setup of DFWM.
agreement with their molecular formulas. The new strong band
around 1100 cm1 in the FT-IR spectra was assigned to the
mðClO4 Þ vibrations. In the ESI–MS spectrum of the complex a, the
signals of [M2ClO4]2+ and [M2ClO4–H]+ were detected. In the
case of the comlexes b and c, the only signal of [M2ClO4]2+ was
observed. Due to their paramagnetic properties, the complexes
a–c could not be further characterized by 1H NMR spectra.
3.2. Absorption spectra
The UV–visible absorption spectra of three nickel(II) complexes
a–c in DMF solutions are displayed in Fig. 3. Their maximum
absorption peaks appear at 255 nm, 258 nm and 278 nm, respec-
tively, which are attributed to intraligand p–p transitions. Most
notably, they do not show absorptions above 450 nm so that signif-
icant off-resonant third-order optical nonlinearities may be ob-
tained without any great cost in transparency, which is a crucial
aspect in the practical applications of NLO materials.
3.3. Third-order NLO properties
The third-order nonlinear optical susceptibility v(3) is measured
via a comparison with that of a reference sample CS2, calculated
from the DFWM signal (I), the linear refractive index (n), the sam-
ple thickness (L) and absorption correction factor using the follow-
ing equation [41]:
Fig. 3. UV–visible absorption spectra of the nickel(II) complexes a–c in DMF.
 1=2  2
Is Lr ns aL exp ðaL=2Þ ð3Þ
vsð3Þ ¼ v ð1Þ
Ir Ls nr 1  exp ðaLÞ r
where the subscripts s and r represent the parameters for the sam-
ple and CS2. And a indicates the linear absorption coefficient. The
fraction a1expð
L expðaL=2Þ
aLÞ comes from the sample absorption and equals to
one approximately while the sample has little absorption around
ð3Þ
the employed laser wavelength. The values of vr and nr for CS2
14
are 6.7  10 esu and 1.632, respectively [42].
The nonlinear refractive index n2 in isotropic media is estimated
through the equation [43]:
n2 ðesuÞ ¼ 12pvð3Þ =n2 ð2Þ
where n is the linear refractive index of solution, measured by 2WAJ
Abbe refractometer.
The second-order hyperpolarizability c of a molecule in isotro-
pic media is related to the solution v(3) by [44]:
c ¼ vð3Þ =Nf 4 ð3Þ
where N is the number density of the solute per milliliter, related to
the molar concentration c by N = NAc with NA being Avogadro’s
number. And f4 is the local field correction factor which is
[(n2 + 2)/3]4 (n is the linear refractive index of solution).
The dependence of DFWM signal intensity on the delay time of
the input beam is shown in Fig. 4. The curves are obtained via fit-
ting the time convolution between autocorrelation function of
pulse and single exponent decline function expðTt 2 Þ. The response
times of the samples can be obtained from Fig. 4.
The values of v(3), n2, c and response times for the samples de-
duced and calculated from the experimental results are listed in
Table 1.
The c values of three nickel(II) complexes a–c with modified
phen (IP, PP, DPPZ) as the chelating ligands are 3.74  1031 esu,
3.86  1031 esu and 4.22  1031 esu, respectively, which are lar-
ger than those of some known NLO organometallic and coordina-
tion materials (for example, 6.5  1032–1.9  1031 esu for 1,3-
dithiole-2-thione-4,5-dithiolate complexes at 1064 nm [45,46],
1.21  1031 esu for a heterometal cluster containing iron at
532 nm [47], 2.6  1034–1.7  1032 esu for alkynylruthenium
complexes at 800 nm [48], 2.8  1033–1.04  1032 esu for fuller-
ene-containing organometallics [49], 1.0  1031 esu for azo-nickel
chelate compound at 830 nm [50]).
Phen is a tricyclic aromatic hydrocarbon composed of three
fused benzene rings and two nitrigen heteroatoms in 1- and
 Z.-B. Cai et al. / Optical Materials 35 (2013) 1481–1486 1485

6 7

5 a 6 b
5

Intensity (a.u.)
Intensity (a.u.)
4
4
3
3
2
2

1 1

0 0
-150 -100 -50 0 50 100 150 -150 -100 -50 0 50 100 150
Time delay (fs) Time delay (fs)

6
c
5
Intensity (a.u.)

0
-150 -100 -50 0 50 100 150
Time delay (fs)

Fig. 4. DFWM signal versus delay time for the nickel(II) complexes a–c in DMF solution.

Table 1
The values of v(3), n2, c and response times for the nickel(II) complexes a–c.

Sample n v(3) (1013 esu) n2 (1012 esu) c (1031 esu) Response time (fs)
a 1.4315 3.74 6.88 3.74 60
b 1.4323 3.87 7.10 3.86 58
c 1.4325 4.23 7.77 4.22 75

10-positions. It possesses a planar and rigid p-conjugated
electron system, which can be polarized in the light induction.
Thus it exhibits a relatively large c value of 1.76  1031 esu
[51].
Compared with phen, the c values of the complexes a–c are
more than twice larger. A reasonable explanation might be two-
fold. On one hand, by fusing phen with imidazole, pyrazine and
quinoxaline, respectively, the p-conjugated electron systems of
the ligands IP, PP and DPPZ are enlarged, which is in favor of high-
er delocalization of electrons. On the other hand, the nickel(II) ion
organizes the ligands (IP, PP, DPPZ) around so that the polarizable
systems are further enlarged. The central nickel(II) ion with d8
electron structure functions mainly as a polarizable bridge. The
overlapping between its d orbitals and p-electron orbitals of li-
gands can allow the three ligands to be in electronic communica-
tion with one another, which makes the complexes have stronger
intramolecular charge transfer.
The c value comparison among a, b and c indicates that pyra-
zine is more effective than imidazole as the conjugate framework
and the increase of the conjugation length always contributes to
the high hyperpolarizability. From the UV–visible absorption spec-
tra, it can also be seen that there is a red shift in the maximum
absorption wavelength for them (c > b > a), which implies a larger
extension of p delocalization, and finally results in the better third-
order optical nonlinearity.
The off-resonant photoelectric field-induced polarization is
mainly produced by four processes. Each process has a specific
time scale. The third-order NLO response time induced by delocal-
ized electrons is believed to be 1014–1015 s. While the response
time induced by molecular reorientation is 1011–1012 s, that in-
duced by electrostriction is 108–109 s and that induced by heat
absorption is 101–107 s. The NLO response times of complexes
a–c are obtained in the range of 58–75 fs, which is commonly re-
garded to be caused by the transient motion of the p-conjugated
electron distribution.
4. Conclusions
Three nickel(II) complexes containing modified phen ligands
were synthesized and characterized. Their off-resonant third-order
NLO properties were investigated by the DFWM technique with
the laser duration of 80 fs at the wavelength of 800 nm. The results
indicate that the extensive electronic delocalization and polariza-
tion have an important effect on the NLO properties of the
complexes.
Acknowledgement
We are grateful to the National Natural Science Foundation of
China for financial support (Grant No. 21103151).
1486 Z.-B. Cai et al. / Optical Materials 35 (2013) 1481–1486

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