Synthesis, characterization, crystal structure and DFT studies on 3-(1H-benzo[d][1,2,3]triazol-1-yl)-1-oxo-1-m-tolylpropan-2-yl-nicotinate

Article abstract of DOI:10.1016/j.saa.2011.02.040

3-(1H-Benzo[d][1,2,3]triazol-1-yl)-1-oxo-1-m-tolylpropan-2-yl-nicotinate (BOTN) has been synthesized and characterized by elemental analysis, IR, UV-vis and fluorescence spectroscopy. Its crystal structure has also been determined by X-ray single crystal

Full text of DOI:10.1016/j.saa.2011.02.040

Spectrochimica Acta Part A 79 (2011) 219–225
Contents lists available at ScienceDirect
Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa
Synthesis, characterization, crystal structure and DFT studies on
3-(1H-benzo[d][1,2,3]triazol-1-yl)-1-oxo-1-m-tolylpropan-2-yl-nicotinate
Pusu Zhaoa,∗, Xiumei Gaob, Jie Songa, Xiaojun Suna, Wu lan Zengc
a Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials, Huaiyin Normal University, Huaian, Jiangsu 223300, PR China
b Department of Computer Science and Technology, Huaiyin Normal University, Huaian, Jiangsu 223300, PR China
c MicroScale Science Institute, Department of Chemistry and Chemical Engineering, Weifang University, Weifang 261061,China
a r t i c l e i n f o
a b s t r a c t
Article history:
3-(1H-Benzo[d][1,2,3]triazol-1-yl)-1-oxo-1-m-tolylpropan-2-yl-nicotinate (BOTN) has been synthesized
and characterized by elemental analysis, IR, UV–vis and fluorescence spectroscopy. Its crystal structure
has also been determined by X-ray single crystal diffraction. For BOTN, density functional theory (DFT)
calculations of the structure and vibrational frequencies have been performed at B3LYP/6-311G** level.
The comparisons between the experimental vibrational frequencies and the predicted data show that
B3LYP/6-311G** method can simulate the IR of BOTN on the whole. Based on the vibration analysis,
thermodynamic properties of BOTN have been calculated. The correlative equations between the ther-
modynamic properties and the temperatures have also been listed. The experimental UV–vis spectra
present two peaks and theoretical UV–vis spectra obtained by TD-DFT method exhibit three peaks. The
comparison between them suggests that the B3LYP/6-311G** method can only approximately simulate
the UV–vis spectra of BOTN. The fluorescence determination reveals two emission bands at 423 and
489 nm, respectively.
Received 20 December 2010
Received in revised form 5 February 2011
Accepted 16 February 2011
Keywords:
N-heterocyclic compound
Synthesis
Crystal structure
UV–vis spectrum
Fluorescence spectrum
DFT calculation
© 2011 Elsevier B.V. All rights reserved.
1. Introduction
tional theory (DFT) calculational results about BOTN are also
reported.
As N-heterocyclic compounds, benzotriazole and its derivatives
have attracted considerable attentions in industry and agricul-
ture because of their significant biological activities including
efficient antifungal, antitumor and antineoplastic activities [1–4].
Also, benzotriazoles are extensively used as synthetic auxiliaries
in organic chemistry [5–7] and versatile ligands in coordination
chemistry [8,9]. For example, the deprotonated benzotriazolate
anion can coordinate up to three metal centres via its three nitro-
gen donors [10,11] and the copper complexes of benzotriazole
drew many attentions due to the importance of benzotria-
zole as a corrosion inhibitor [12,13]. Recently, benzotriazoles
have also been used as luminescent materials and fluorescent
chemical sensor laser dyes [14,15]. However, to the best of
our knowledge, among so many reported benzotriazoles, 1H-
benzotriazole derivatives containing one nicotinato group are very
rare. Herein, we report the four-steps synthesis and character-
ization on the title compound of 3-(1H-benzo[d][1,2,3]triazol-
1-yl)-1-oxo-1-m-tolylpropan-2-yl- nicotinate (BOTN). The crystal
structure, fluorescent spectra along with the density func-
2. Experimental and theoretical methods
2.1. Physical measurements
Elemental analyses for carbon, hydrogen and nitrogen were per-
formed by a Perkin-Elmer 240C elemental instrument. The melting
points were determined on a Yanaco MP-500 melting point appa-
ratus. IR spectra (4000–400 cm−1), as KBr pellets, were recorded
on a Nicolet FT-IR spectrophotometer. Electronic absorption spec-
tra were measured on a Shimadzu UV3100 spectrophotometer in
EtOH solution and solid state fluorescence spectra were measured
on a F96-fluorospectrophotometer.
2.2. Synthesis of BOTN
All chemicals were obtained from a commercial source and used
without further purification.
The synthetic route is shown in Scheme 1.
Firstly, the intermediate II were prepared according to our ear-
lier report [16]. IR ꢀ (KBr disc)/cm−1: 3092(m), 2921(m), 1624(s),
1584(s), 1486(m), 1472(m), 1375(m), 1361(m), 1268(s), 1213(m),
1060(m), 970(m), 914(m), 879(m), 850(m), 610(m). 1H NMR
(DMSO, ı, ppm): 2.35(s, 3H, –CH3), 3.03(m, 2H –CH2), 3.92(m, 2H,
∗
Corresponding author. Tel.: +86 0517 83525083; fax: +86 0517 83525085.
E-mail address: zhaopusu@163.com (P. Zhao).
1386-1425/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2011.02.040

220
P. Zhao et al. / Spectrochimica Acta Part A 79 (2011) 219–225
H
N
O
O
N
HN(CH3)2HCl
N
N(CH3)2HCl
(CH2O)n
CH3
CH3
I
O
O
Br
N
H3C
N
N
N
N
Br2
Na(CH3COO)
H3C
N
II
III
N
O
O
O
O
OH
N
N
N
N
Et3N
H3C
IV
Scheme 1.
–CH2), 7.20–7.98(m, 8H, ArH). 13C NMR (DMSO, ı, ppm): 24.1, 37.7,
43.5, 118.2, 125.8, 127.2, 128.4, 129.3, 133.2, 136.4, 138.2, 145.5,
200.3.
Secondly, the intermediate II (5.31 g, 0.02 mol) and sodium
acetate (1.6 g, 0.02 mol) were dissolved in acetic acid (50 mL).
Then, bromine (3.2 g, 0.02 mol) was added dropwise with stir-
ring at 55–60 ◦C. After the mixture being stirring for 8 h, water
(50 mL) and chloroform (20 mL) were added. The organic layer was
washed successively with saturated sodiumbicarbonate solution.
The washed solution was purified by flash column chromatography
(silica gel, using V petroleum ether:V acetic ether = 4:1 as eluent)
to afford intermediate III. IR ꢀ (KBr disc)/cm−1: 3092(m), 3024(m),
2965(m), 2921(m), 1624(s), 1572(s), 1486(m), 1472(m), 1375(m),
1361(m), 1329(s), 1268(s), 1213(m), 1198(m), 1152(m), 971(m),
915(m), 879(m), 851(m), 610(m). 1H NMR (DMSO, ı, ppm): 2.35(s,
3H, –CH3), 4.26(d, 2H –CH2), 4.92(m, 1H, –CH), 7.20–7.98(m, 8H,
ArH). 13C NMR (DMSO, ı, ppm): 24.1, 50.6, 57.6, 118.3, 125.8, 127.4,
128.4, 129.3, 32.9, 133.5, 136.4, 138.2, 145.5, 191.3
Fig. 1. The molecular structure with the atomic numbering for BOTN.

P. Zhao et al. / Spectrochimica Acta Part A 79 (2011) 219–225
221
Table 1
Table 3
Summary of crystallographic results for BOTN.
Intermolecular hydrogen bonds and C–H· · ·ꢃ supramolecular interactions.a
∠D–H· · ·A (◦)
Empirical formula
C22H18N4O3
D–H· · ·A
Symmetry
D· · ·A (Å)
Formula weight
Temperature, K
Wavelength, Å
Crystal system, space group
Unit cell dimensions
a (Å)
386.40
293(2)
0.71073
Monoclinic, P2(1)/c
C(7)–H(7A)· · ·O(3)
1 − x, −1/2 + y, 1/2 − z
3.0317
2.7640
3.939
3.497
3.924
112.64
100.36
160.92
93.60
C(21)–H(21A)· · ·O(2)
C(5)–H(5A)· · ·Cg(4)
C(18)–H(18A)· · ·Cg(4)
C(22)–H(22B)· · ·Cg(1)
1 − x, −1/2 + y, 1/2 − z
1 − x, 1/2 + y, 1/2 − z
1 − x, −1/2 + y, 1/2 − z
122.22
10.094(3)
9.331(3)
20.682(6)
96.575(5)
1935.2(10)
4, 1.326
0.091
808
a
C(1) ring denotes triazolyl ring N(1)–N(2)–N(3)–C(1)–C(6); C(4) ring denotes
phenyl ring C(10)–C(15).
b (Å)
c (Å)
ˇ (◦)
Volume (Å3)
Table 4
Z, calculated density (Mg m−3
)
)
ꢃ· · ·ꢃ stacking interactions.a
Absorption coefficient (mm−1
F(0 0 0)
Cg(I)· · ·Cg(J)
Symmetry
Distance
between
ring
centroids
(Å)
Perpendicular
distance of
Cg(I) on ring J
(Å)
Perpendicular
distance of
Cg(J) on ring I
(Å)
ꢁ range for data collection (◦)
Limiting indices
2.03–24.99
−12 ≤ h ≤ 11, −11 ≤ k ≤ 10, −18 ≤ l ≤ 24
9829/3398 [Rint = 0.0529]
Full-matrix least-squares on F2
3398/1/263
Reflections collected/unique
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2ꢂ(I)]
R indices (all data)
Cg(1)· · ·Cg(3) 1 − x, −y, 1 − z 3.768
Cg(3)· · ·Cg(1) 1 − x, −y, 1 − z 3.768
3.608
3.610
3.610
3.608
1.085
R1 = 0.0504, wR2 = 0.1240
R1 = 0.0901, wR2 = 0.1472
0.0066(15)
0.216 and −0.160 e A
a
C(1) ring denotes triazolyl ring N(1)–N(2)–N(3)–C(1)–C(6); C(3) ring denotes
phenyl ring C(1)–C(6).
Extinction coefficient
Largest diff. peak and hole
−3
˚
24.1, 53.2, 84.0, 118.2, 122.0, 125.8, 127.2, 128.0, 129.3, 133.2, 136.4,
138.2, 145.5, 151.1, 166.1, 197.0.
Single crystal of BOTN suitable for X-ray measurements was
obtained by recrystallization from ethanol at room tempera-
ture.
Thirdly, in a 100 mL flask, the intermediate III (5.16 g, 0.015 mol)
was dissolved in acetone (20 mL), then nicotinic acid (2.46 g,
0.02 mol) and triethylamine (2.8 mL, 0.0175 mol) were added and
the mixture was stirred at 0–5 ◦C. 5 h later, solid materials were
observed and reaction was stopped. The mixtures were filtered and
the filtrate was concentrated by rotary vacuum evaporation. Then,
the concentrated filtrate was re-dissolved in chloroform (30 mL)
and was washed three times with distilled water (30 mL) by using
extraction method. Finally, the organic layer was rotary vacuum
evaporation to obtain the IV. Yield 50.6%. m.p. 141.3–142.3 ◦C.
Found: C, 68.13; H, 4.56; N, 14.34%. Calc. for C22H18N4O3: C, 68.38;
H, 4.70; N, 14.50%. IR ꢀ (KBr disc)/cm−1: 3068(m), 2980(m), 1720(s),
1690(s), 1590(s), 1567(m), 1499(m), 1466(m), 1388(m), 1337(s),
1254(s), 1224(s), 1088(m), 1050(w), 984(m), 950(w), 853(m),
773(m), 680(w), 620(w), 509(w). 1H NMR (DMSO, ı, ppm): 2.35(s,
3H, –CH3), 4.31(s, 2H, –CH2), 5.54(s, 1H, –CH), 7.20–7.88(m, 8H,
ArH, 1H in pyriding ring), 8.30(d, 1H in pyridyl ring), 8.89(d, 1H in
pyridyl ring), 9.20(s, 1H in pyriding ring). 13C NMR (DMSO, ı, ppm):
2.3. Crystal structure determination
The selected colorless crystal of BOTN was mounted on a CCD
area diffractometer. Reflection data were measured at 293.2 K
˚
using graphite monochromated Mo-K˛ (ꢄ = 0.71073 A) radiation
and a ϕ–ω scan mode. The structure was solved by direct meth-
ods and refined by full-matrix least-squares method on Fo2bs
using the SHELXTL software package [17]. All non-H atoms were
anisotropically refined. The hydrogen atom positions were fixed
geometrically at calculated distances and allowed to ride on
the parent C atoms. The final least-square cycle gave R = 0.0504,
wR2 = 0.1240 for 2064 reflections with I > 2ꢂ(I) using the weight-
ing scheme, w = 1/[ꢂ2(Fo2) + (0.0618P)2], where P = (Fo2 + Fc2)/3.
Atomic scattering factors and anomalous dispersion corrections
Table 2
Selected geometric parameters by X-ray and theoretical calculations for BOTN at B3LYP/6-311G** level.
Bond
Bond lengths (Å)
Exp.
Bond
Bond lengths (Å)
Exp.
Calc.
Calc.
O(1)–C(9)
O(3)–C(16)
N(1)–C(6)
N(1)–C(7)
N(3)–C(1)
C(2)–C(3)
C(7)–C(8)
C(10)–C(15)
N(4)–C(20)
C(17)–C(18)
1.214(3)
1.202(2)
1.352(3)
1.454(3)
1.366(3)
1.345(5)
1.519(3)
1.394(3)
1.343(5)
1.366(3)
1.212
1.206
1.366
1.450
1.378
1.382
1.354
1.403
1.337
1.397
O(2)–C(16)
O(2)–C(8)
N(1)–N(2)
N(2)–N(3)
C(1)–C(6)
C(4)–C(5)
C(8)–C(9)
C(11)–C(12)
N(4)–C(21)
C(12)–C(22)
1.346(3)
1.439(2)
1.359(3)
1.307(3)
1.385(3)
1.357(4)
1.533(3)
1.384(3)
1.343(4)
1.498(3)
1.358
1.431
1.366
1.287
1.408
1.384
1.545
1.394
1.334
1.510
Bond angle
Bond angle (◦)
Exp.
Bond angle
Bond angle (◦)
Exp.
Calc.
Calc.
C(16)–O(2)–C(8)
C(10)–C(9)–C(8)
O(2)–C(8)–C(9)
C(6)–N(1)–N(2)
C(20)–N(4)–C(21)
C(11)–C(10)–C(15)
114.55(16)
119.7(2)
110.47(17)
110.27(19)
116.1(3)
115.92
118.35
110.28
109.97
117.37
119.34
N(1)–C(7)–C(8)
O(3)–C(16)–O(2)
N(3)–N(2)–N(1)
C(2)–C(3)–C(4)
C(18)–C(17)–C(21)
C(13)–C(14)–C(15)
111.87(19)
122.6(2)
108.4(2)
122.3(3)
117.6(2)
120.1(2)
112.51
123.09
109.49
121.33
118.36
120.32
118.67(19)

222
P. Zhao et al. / Spectrochimica Acta Part A 79 (2011) 219–225
Table 5
Comparison of the observed and calculated vibrational spectra of BOTN.a
Assignments
Exp.
B3LYP/6-311G**
3110–3024
Phenyl ring and pyridyl
ring C–H str.
3068
–CH3 and –CH2 C–H str.
2980
1720
1690
3009–2908
1719
1693
C
C
O str.
O str.
Phenyl ring and pyridyl
ring C–C str. + C–N str.
Phenyl ring and pyridyl
ring C–H ip. def.
1590, 1567
1591–1547
1499, 1466
1466–1448
–CH3 C–H rock
1428
Fig. 2. Packing diagram of the unit cell along the a-axial for BOTN. The distances of
C(7)–H(7A)· · ·O(3) and C(21)–H(21A)· · ·O(2) are 3.0317 and 2.7640 A, respectively.
–CH2 C–H rock
Phenyl ring and pyridyl
ring C–H ip. def.
1417
1398–1379
˚
1388
–CH and –CH2 C–H rock
Phenyl ring and pyridyl
ring C–H ip. def.
1337
1254
1346–1337
1306–1259
C–O str.
Phenyl ring and pyridyl
ring C–H ip. def.
1224
1088
1224
1090–1080
3. Results and discussion
3.1. Description for the crystal structure of BOTN
C(8)–C(9) str.
N–N str.
1050
984
1041
984
Phenyl ring and pyridyl
ring C–H opp. def.
Phenyl ring and pyridyl
ring C–H opp. def.
Phenyl ring and pyridyl
ring C–H opp. def.
Phenyl ring and pyridyl
ring C–H opp. def.
Phenyl ring and pyridyl
ring C–C def. + C–N def.
Whole molecular skeleton
def.
950
979–955
For BOTN, the displacement ellipsoid plot with the numbering
scheme is shown in Fig. 1. Fig. 2 shows a perspective view of the
crystal packing in the unit cell. Selected bond lengths and bond
angles by X-ray diffractions are listed in Table 2 along with the
calculated bond parameters.
853
773
680
620
509
894
791–752
700–663
625–607
509
The molecular structure of BOTN consists of discrete
[CH3PhCOCHCH2C5H4NCOOPhN3] entities. All of the bond lengths
and bond angles in the phenyl ring, pyridyl ring and benzotriazole
ring are in the normal range. All of the C–O bond lengths are also in
the normal range. The phenyl ring along with the methyl group and
atoms C(9) and O(1) define a plane P1, with the biggest deviation
a
The atomic numbering scheme is as shown in Fig. 1. str.: stretch; ip: in-plane;
oop: out-of-plane; def.: deformation.
˚
being 0.046 A for C(9) atom. The pyridyl ring along with the atom
C(16) define another plane P2, with the biggest deviation being
˚
−0.015 A for C(18) atom. The benzotriazole ring and the joined
atom of C(7) are also coplanar to P3, with the biggest deviation
were taken from International Table for X-ray Crystallography [18].
The key crystallographic data are given in Table 1.
˚
being 0.007 A for C(7) atom. The dihedral angles between the
P1–P2, P1–P3 and P2–P3 are 82.34(2), 16.20(3) and 83.00(3)◦,
respectively.
In the crystal lattice, there are three potentially weak inter-
molecular interactions (C–H· · ·Y, Y O) [25,26], three C–H· · ·ꢃ
supramolecular interactions and two ꢃ· · ·ꢃ stacking interactions
(see Tables 3 and 4), which make BOTN to be three-dimension (3D)
network and stabilize the crystal structure.
2.4. Computational methods
Initial
molecular
geometry
was
optimized
using
MM + molecular modeling and semi-empirical AM1 methods
[19] (HYPERCHEM 6.0, Hypercube, Ont., Canada). Then, DFT calcu-
lations with a hybrid functional B3LYP at basis set 6-311G** by the
Berny method [20] were performed with the Gaussian 03 software
package [21]. The calculated vibrational frequencies ascertained
that the structure was stable (no imaginary frequencies). Based
on the optimized geometry and by using time-dependent density
functional theory (TD-DFT) [22–24] methods, electronic spectra of
the title compound were predicted.
248 nm
290 nm
245 nm
All calculations were performed on a DELL PE 2850 server and a
Pentium IV computer using the default convergence criteria
Table 6
Predicted
Thermodynamic properties at different temperatures at B3LYP/6-311G** level.
Experiment
T (K)
Cp0,m (J mol−1 K−1
)
Sm0 (J mol−1 K−1
)
Hm0 (kJ mol−1
)
200.0
298.1
300.0
400.0
500.0
600.0
700.0
800.0
285.24
409.79
412.15
533.05
634.14
714.86
779.20
831.17
637.57
774.46
777.00
34.56
68.62
69.38
116.78
175.32
242.92
317.74
398.35
912.51
200
250
300
350
400
1042.71
1165.75
1280.96
1388.51
Wavelength(nm)
Fig. 3. Experimental and theoretical electronic spectra for BOTN.

P. Zhao et al. / Spectrochimica Acta Part A 79 (2011) 219–225
223
Fig. 4. Isodensity surfaces of eight frontier molecular orbitals for BOTN.
3.2. Optimized geometry
As seen in Table 2, most of the predicted geometric param-
eters have higher values than those determined experimentally.
Comparing the predicted values with the experimental ones, it
can be found that the biggest difference in bond angles occurs at
the C(16)–O(2)–C(8) bond angle with the difference being1.37◦.
Considering the bond lengths, the biggest variation between the
The optimized geometry of BOTN has been obtained at B3LYP/6-
311G** level. To make the comparison easy, the calculated
geometric parameters of the title compound are also included in
Table 2.

224
P. Zhao et al. / Spectrochimica Acta Part A 79 (2011) 219–225
Table 7
Experimental and theoretical UV–vis spectra values.
Exp.
Calc. (TD-DFT)
Wave length
(nm)
log ε
Wave length
(nm)
Oscillator strength
Electronic transition modes
101 (HOMO) → 107 (LUMO + 5)
101 (HOMO) → 108 (LUMO + 6)
96 (HOMO-5) → 102 (LUMO)
96 (HOMO-2) → 103 (LUMO + 1)
97 (HOMO-4) → 102 (LUMO)
101 (HOMO) → 102 (LUMO)
245
290
1.95
1.55
200
248
331
0.2945
0.1099
0.0045
experimental and predicted values can be found at bond C(7)–C(8),
with the difference being 0.165 A. This is most likely due to the
3.4. Thermodynamic properties
˚
fact that the experimental data describe BOTN in the solid state,
whereas the calculated data correspond to the molecule in the
gas phase. The geometry of the solid-state structure is subject to
intermolecular forces, such as van der Waals interactions, crys-
tal packing forces, hydrogen-bond forces and the other types of
supramolecular interactions. For example, the bonds of C(7)–H(7A)
and C(8)–H(8A) and the atom O(2) all involve in forming hydrogen
bonds, which make the experimental geometric parameters around
the above three atoms have bigger differences from the calculated
ones. In spite of these differences, the predicted molecular struc-
ture can simulate the crystal structure on the whole. Based on the
optimized structure, thermodynamic properties and the UV spectra
of BOTN are obtained.
For BOTN, on the basis of vibrational analyses and statisti-
cal thermodynamics, the standard thermodynamic functions: heat
capacity (Cp0,m), entropy (Sm0 ) and enthalpy (Hm0 ) were obtained and
listed in Table 6. The scale factor for frequencies is also 0.96 [27].
As observed in Table 6, with the temperature increasing from
200.0 to 800.0 K, all the values of Cp0,m, Sm0 and Hm0 increase, which
is attributed to the enhancement of the molecular vibration while
the temperature increases.
The correlation equations between these thermodynamic prop-
erties and temperature T are as follows:
Cp0,m = −33.647 + 1.746 T − 8.315 × 10−4T2 (R2 = 0.9998)
Sm0 = 332.502 + 1.583T − 3.277 × 10−4T2 (R2 = 0.99998)
3.3. Vibrational frequency
Hm0 = −17.181 + 0.156T + 4.572 × 10−4T2 (R2 = 0.9998)
Vibrational frequencies of BOTN have been calculated and
scaled by 0.96 [27], which is a typical scaled factor for the calcu-
lated method. Some primary calculated harmonic frequencies are
listed in Table 5 and compared with the experimental data. The
descriptions concerning the assignment have also been indicated
in Table 5. Gauss-view program [28] has been used to assign the
calculated harmonic frequencies. Seen from Table 5, by using the
B3LYP/6-311G**method, all of the experimental vibrational bands
can be predicted and the predicted vibrational frequencies are in
good agreement with experimental values except that two C–H
stretch vibrations frequencies of 1428 and 1417 cm−1 for methyl
group and methylene group, which can not be found in experiment.
Namely, on the whole, the B3LYP/6-311G** method can be used to
predict the vibrational frequencies.
These equations will be useful for the further studies on BOTN.
3.5. UV–vis absorption spectra
For BOTN, UV–vis absorption spectra have been measured in
EtOH solution at room temperature. To compare the experimen-
tally obtained spectra with theoretical values, TD-DFT method has
been applied to predict UV–vis spectra based on the B3LYP/6-
311G** level optimized structure. Both the experimental and
predicted UV–vis spectra are shown in Fig. 3. The theoretical UV–vis
spectra are drawn using the SWizard program, revision 4.5 [29,30].
The detailed experimental and theoretical UV–vis spectra values
are listed in Table 7. Seen from Fig. 3, in experiment, there exist
two peaks at 245 and 290 nm, respectively. In theory, there are
three peaks is at 200, 248 and 331 nm, respectively. Therefore, for
the system studied here, TD-DFT-B3LYP/6-311G** level can approx-
imately simulate the experimental electronic spectra. Fig. 4 shows
the isodensity surfaces of eight frontier molecular orbitals for BOTN,
which all are corresponding with the electronic transitions listed
in Table 7. As seen from Fig. 4, in eight frontier molecular orbitals,
the electron clouds are mainly distributed on phenyl ring, pyridyl
ring, benzotriazole ring and three oxygen atoms, respectively,
which suggest that the electronic transitions in UV–vis spectra are
corresponding to the n → ꢃ* and ꢃ → ꢃ* electron transitions. For
example, the electron transitions related with the transition peak
at 331 nm are mainly assigned to two electronic transition modes,
HOMO-4 → LUMO and HOMO → LUMO. In HOMO-4 and HOMO,
electron clouds are mainly distributed on pyridyl ring, benzotria-
zole ring and oxygen atoms, while in LUMO, the electron clouds are
mainly distributed on phenyl ring along with oxygen atoms. Then,
the electron transitions related with the transition peak at 331 nm
are mainly from pyridyl ring, benzotriazole ring and oxygen atoms
to phenyl ring and oxygen atoms, which are corresponding to the
n → ꢃ* and ꢃ → ꢃ* electron transitions.
80
423 nm
60
489 nm
40
20
0
400
450
500
550
Wavelength(nm)
Fig. 5. Solid-state fluorescence spectra of BOTN.

P. Zhao et al. / Spectrochimica Acta Part A 79 (2011) 219–225
225
3.6. Fluorescence spectra
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3-(1H-Benzo[d][1,2,3]triazol-1-yl)-1-oxo-1-m-tolylpropan-2-
yl-nicotinate (BOTN) has been synthesized by four-step reactions
and characterized by IR and UV–vis spectra. The crystal structure
determinations show that the compound crystallizes in mono-
clinic, space group P2(1)/c. B3LYP/6-311G** method can simulate
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Acknowledgements
This work was supported by Jiangsu Key Laboratory for Chem-
istry of Low-Dimensional Materials, PR China (JSKC10078) and
Huaian Science & Technology Bureau, Jiangsu Province, PR China
(HAG2010027).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.saa.2011.02.040.
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