Indian Journal of Chemistry

Vol. 52A, April 2013, pp. 480-485

DFT and TD-DFT studies on copper(II) complexes with tripodal tetramine ligands
Duran Karakaş* & Koray Sayin
Department of Chemistry, Faculty of Science, Cumhuriyet University, Sivas 58140, Turkey
Email: [email protected]
Received 6 December 2012; revised and accepted 18 March 2013

Copper(II) complexes, containing aliphatic tripodal tetramine ligand, [Cu(trpn)(NH3)]2+ (1), [Cu(tren)(NH3)]2+ (2),
[Cu(332)(NH3)]2+ (3) and [Cu(322)(NH3)]2+ (4) are optimized at B3LYP/ LANL2DZ and B3LYP/GEN levels of
theory in gas phase (where (trpn), (tren), (332) and (322) are N(CH2CH2CH2NH2)3, N(CH2CH2NH2)3,
N[(CH2CH2CH2NH2)2(CH2CH2NH2)] and N[(CH2CH2CH2NH2)(CH2CH2NH2)2], respectively). The optimization results
show that the copper(II) center is trigonal bipyramidal for the studied complexes. Charge distributions on the donor and
acceptor atoms are evaluated by natural population analysis. The charge distribution indicates that the ligands transfer their
negative charges to copper(II) ions during formation of the complexes. Electronic excitation energies of copper(II)
complexes are calculated with time dependent density functional theory in gas phase. It is found that the most intense bands
at electronic spectra of complexes stem from dxz, dyz→dz2 or dx2-y2, dxy→dz2 transitions.

Keywords: Theoretical chemistry, Density functional calculations, Time dependent density functional calculations,
Tripodal tetramine ligands, Copper

Iron, zinc and copper ions are the most common reported that copper complexes with TT ligand might
transition metal ions in biological systems1, 2. Copper lead to very reactive tetrahedral Cu(I) complexes
has a significant role in biological systems as an which react rapidly with dioxygen. Copper complexes
essential trace metal or a constituent of complexes. with TT ligand (Fig. 1) have been used to model the
The role of copper in biological systems is well active site in copper proteins containing dicopper
reported3-5 and the involvement of copper has been center such as hemocyanin25. Although the action of
described from medical, chemical6 and biochemical copper in biological systems has been intensively
perspective7, focusing on the molecular physiology of investigated, the clinical picture of copper complexes
copper transport8. A number of binary copper(II) is not always so straightforward, and less is known
chelate complexes with Schiff base ligand exhibit about the role of copper complexes in medicine.
biological activities such as anticancer9-12, Compared with the copper complexes containing
antibacterial , anti inflammatory12, chemical
13-20
Schiff base ligands, less is known about the
nucleases14,15 and apoptosis inducer21,22. coordination chemistry of copper complexes with TT
Copper complexes with tripodal tetramine ligand ligand. The purpose of the present study is to
(TT) have been synthesized by Duggan et al.23 and investigate the coordination chemistry of copper
Andreas et al.24 The structures of complexes have complexes with the TT ligands (Fig. 1) by using
been determined by X-ray difraction methods and are density functional theory (DFT), and, time dependent
reported to have trigonal bipyramidal geometry. It is density functional theory (TD-DFT) calculations.

Fig. 1 – Schematic structures of copper(II) complexes.

Molecular geometries for copper(II) complexes with TT As can be seen from Table 1, acceptable results
ligand have been investigated by using B3LYP method were obtained by DFT/B3LYP method with
with LANL2DZ and GEN basis sets. NPA atomic LANL2DZ and GEN basis sets for complexes (1) and
charge distributions on complexes and on donor atoms (2). Calculated values of bond angles obtained
of ligands are calculated at the B3LYP/LANL2DZ level. by using B3LYP/LANL2DZ level are more
Electronic excitation energies for mentioned complexes appropriate than the B3LYP/GEN level. Therefore,
have been obtained by using TD-DFT/B3LYP method DFT/B3LYP/LANL2DZ level was preferred to
with LANL2DZ basis set in gas phase. B3LYP/GEN level for determining the molecular
structure. The largest differences of bond angles were
Methodology taken into account for determining agreement
The input files of the copper(II) complexes were between experimental and theoretical structures. The
prepared with GaussView 5.0.826. All calculations largest difference between experimental and
were made using Gaussian 09 rev. A.0227 by the theoretical values (i.e., 9.5°) is observed for the
DFT/B3LYP method. LANL2DZ and 6-31G(d,p) are N3-Cu-N4 bond angle. Molecular geometries can be
the standard basis sets. 6-31G(d,p) is a popular predicted by calculating τ values from Eq. (1)33,
polarized basis set which adds p functions to
β−α
hydrogen atoms in addition to the d functions on τ= …(1)
heavy atoms, while LANL2DZ is a basis set for post- 60
third-row atoms. This basis set uses effective core
potentials in calculations. In this study, we used a
standard basis set and a mix basis set. In the first step,
the geometries were fully optimized at the
B3LYP/LANL2DZ level for all atoms in the gas
phase28-30. In the second step, the geometries were
fully optimized at the B3LYP/GEN level by using
6-31G(d,p) basis set for H, C, N atoms and
LANL2DZ basis set for Cu atom in the gas phase31.
GEN is a keyword which combines 6-31G(d,p) and
LANL2DZ standard basis sets. The analyses of
vibrational frequencies indicated that optimized Fig. 2 – The optimized structures of (a) complex (1) and
(b) complex (2). [Hydrogen atoms are omited for clarity].
structures of complexes were at stationary points
corresponding to local minima without imaginary Table 1  Selected bond lengths (Å) and angles (deg.) for
frequencies. There are different methods for complexes (1) and (2)
determining the charge distributions of atoms in Complex (1) Complex (2)
compounds, one of which is natural population LANL2DZ GEN Expt. LANL2DZ GEN Expt.
analysis (NPA). The NPA were made at the Bond lengths (Å)
B3LYP/LANL2DZ level. The electronic spectrum Cu-N1 2.127 2.139 2.060 2.090 2.105 2.041
was predicted by calculating the excitation energies Cu-N2 2.179 2.189 2.074 2.168 2.153 2.082
between the states. Electronic spectrum calculations Cu-N3 2.183 2.191 2.117 2.168 2.150 2.082
of the complexes were made by using time dependent Cu-N4 2.185 2.189 2.108 2.169 2.151 2.082
Cu-N5 2.142 2.153 2.066 2.081 2.046 2.023
density function theory (TD-DFT)/B3LYP method
with LANL2DZ basis set in gas phase32. Bond angles (deg.)
N1-Cu-N2 91.7 91.2 90.7 84.6 83.7 84.9
Results and Discussion N1-Cu-N3 91.6 91.2 92.7 84.6 83.8 84.9
N1-Cu-N4 91.7 91.2 90.1 84.6 83.8 84.9
Geometry optimization N1-Cu-N5 179.9 179.9 176.6 180.0 179.9 -
Copper(II) complexes were optimized at N2-Cu-N3 120.1 119.6 122.2 119.1 118.6 119.2
B3LYP/LANL2DZ and B3LYP/GEN levels in gas N2-Cu-N4 120.3 119.9 127.9 119.1 118.7 119.2
N2-Cu-N5 88.3 88.8 87.2 95.4 96.3 95.1
phase. Figure 2 shows the optimized molecular N3-Cu-N4 119.3 120.3 109.8 119.1 119.2 119.2
structures and atomic numbering scheme for N3-Cu-N5 88.4 88.9 90.6 95.4 96.1 95.1
complexes (1) and (2). Some structural parameters of N4-Cu-N5 88.3 88.7 89.2 95.4 96.2 95.1
these complexes are listed in Table 1. Experimental values taken from Refs 23 and 24.
482 INDIAN J CHEM, SEC A, APRIL 2013

where α and β are the equatorial and axial bond theoretical bond angles is for the N3-Cu-N4 bond
angles, respectively shown in Fig. 1. If the molecular angle (3.8°). For complex (4), the biggest difference
geometry is trigonal bipyramidal, τ must be 1. If the between experimental and theoretical values is for the
geometry is square pyramidal, τ must be 0. If τ is N2-Cu-N3 bond angle (6.1°). For complex (3),
between 0 and 0.5 the molecular geometry is distorted α (N2-Cu-N3) is equal to 106.7° and β (N1-Cu-N5) is
square pyramidal, while τ between 0.5 and 1 indicates equal to 170.9°. From these bond angles, τ value was
that the molecular geometry is distorted trigonal calculated as 1.07. For complex (4), α (N2-Cu-N3) is
bipyramidal. For complex (1), α (N2-Cu-N3) is equal equal to 107.8° and β (N1-Cu-N5) is equal to 174.1°
to 120.1 and β (N1-Cu-N5) is equal to 179.9. From and τ value is calculated as 1.10. For complex (3) and
these bond angles, τ value was calculated to be 0.996. (4), the values of τ is equal to ~1.0, indicating that the
For complex (2), α (N2-Cu-N3) is 119.1 and copper(II) center is trigonal bipyramidal geometry for
β (N1-Cu-N5) is 180.0, giving the τ value as 1.01. For complexes (3) and (4).
complex (1) and (2), the values of τ is equal to about 1. There is no equality in equatorial bond distances
These results show that the copper(II) center is and axial bond distances due to asymmetric ligands in
trigonal bypiramidal geometry. complexes (3) and (4). The calculated Cu-N distances
The two Cu-N bond lengths, (Cu-N1 and Cu-N5), are longer than experimental values. For all copper
are shorter than the three Cu-N bond lengths in complexes, the central nitrogen atom of the tetramine
trigonal bipyramidal complexes. The shorter Cu-N
bonds are present in the axial position and the longer
Cu-N bonds in the equatorial position. This is
contrary to Bent's rule34. However, the axial and
equatorial bond lengths are interesting in trigonal
bipyramidal complexes. In the most of the trigonal
bipyramidal complexes, the equatorial bonds are
longer than axial linkages35, which can be explained
by hybridization. While trigonal bipyramidal
complexes have dsp3 hybrid orbitals, trigonal
bipyramidal compounds of main elements have sp3d Fig. 3 – The optimized structures of (a) complex (3) and
hybrids. The dsp3 hybrid orbitals occur from (n-1) d, (b) complex (4). [Hydrogen atoms of ligands are omited for clarity].
ns and np orbitals whereas the sp3d hybrid orbitals Table 2  Selected bond lengths (Å) and angles (deg.) for
comprise ns, np and nd orbitals. Since (n-1) d orbitals complexes (3) and (4)
in trigonal bipyramidal complexes are closer to the Complex (3) Complex (4)
nucleus than the nd orbitals, the axial bond distances LANL2DZ GEN Expt. LANL2DZ GEN Expt.
are shorter than the equatorial bonds. Although the
Bond lengths (Å)
calculated bond distances for complexes (1) and (2)
are longer than the experimental values, the calculated Cu-N1 2.107 2.138 2.078 2.108 2.125 2.064
Cu-N2 2.114 2.116 2.045 2.142 2.145 2.069
results are acceptable, since the differences between Cu-N3 2.246 2.230 2.191 2.226 2.185 2.153
theoretical and experimental values of bond lengths Cu-N4 2.139 2.127 2.047 2.141 2.129 2.037
are generally less than 0.1 Å. Cu-N5 2.133 2.090 2.022 2.110 2.071 1.993
Figure 3 shows the optimized molecular structure Bond angles (deg.)
of complexes (3) and (4) with atomic numbering N1-Cu-N2 91.1 92.9 90.5 95.3 96.0 92.8
scheme. The selected optimized geometric parameters N1-Cu-N3 95.2 94.4 93.1 84.1 83.3 83.9
N1-Cu-N4 84.8 83.9 84.6 84.9 84.3 84.7
of the complexes are listed in Table 2. N1-Cu-N5 170.9 172.2 171.4 174.1 173.3 175.3
As can be seen from Table 2, the N2-Cu-N3 106.7 108.8 108.0 107.8 111.3 101.7
B3LYP/LANL2DZ level is more appropriate to N2-Cu-N4 148.1 143.7 150.5 134.7 128.3 140.4
N2-Cu-N5 90.0 90.1 89.9 90.6 90.6 91.5
calculate bond angles and bond distances than the N3-Cu-N4 105.1 107.6 101.3 117.3 120.0 117.2
B3LYP/GEN. Therefore, B3LYP/LANL2DZ level N3-Cu-N5 93.1 91.4 95.0 93.7 93.0 97.3
was preferred to B3LYP/GEN level. For complex (3), N4-Cu-N5 89.4 89.4 90.9 91.2 92.8 90.7
the largest difference between experimental and Experimental values taken from Ref. 24.
 KARAKAŞ & SAYIN: DFT/TD-DFT STUDIES ON Cu(II) COMPLEXES WITH TT LIGANDS 483

Table 3  NPA atomic charge disributions for complexes and Table 4  Electronic excitation energies (nm) and the oscillator
donor atoms of free ligands
coefficient of the most intense bands

Complex (1) Complex (2) Complex (3) Complex (4) Complexes Excitation energy Oscillator strength
Atoms Comp. Lig. Comp. Lig. Comp. Lig. Comp. Lig. (nm)
Cu +0.950 - +0.914 - +0.940 - +0.926 -
N1 –0.554 –0.587 –0.554 –0.579 –0.560 –0.591 –0.556 –0.594 [Cu(trpn)(NH3)]2+ (1) 355.2 0.1223
N2 –0.938 –0.949 –0.935 –0.974 –0.922 –0.931 –0.932 –0.931 [Cu(tren)(NH3)]2+ (2) 338.3 0.0984
N3 –0.938 –0.949 –0.935 –0.974 –0.949 –0.951 –0.943 –0.930 [Cu(332)(NH3)]2+ (3) 340.4 0.0902
N4 –0.938 –0.949 –0.935 –0.973 –0.922 –0.949 –0.931 –0.952 [Cu(322)(NH3)]2+ (4) 341.8 0.1043
N5 –1.108 –1.168 –1.102 –1.168 –1.108 –1.168 –1.104 –1.168

ligands and ammonia nitrogen atom were located on Table 5  The contributions of 3d-atomic orbitals to
the axial position and the other nitrogen atoms were 63-67β molecular orbitals
located on equatorial position. If there is an 63β 64β 65β 66β 67β
agreement between theoretical and experimental dz2 0.28620 0.30410 0.58304 –0.08915 –0.39592
bond lengths and angles, it indicates that other dx2-y2 0.16988 0.17102 0.32814 –0.05659 0.69650
properties of mentioned complexes can be explained dxy 0.30111 0.64965 –0.41080 0.22647 –0.00098
theoretically. The results show that there is a good dxz 0.65430 –0.29982 –0.22007 –0.40820 –0.00805
agreement between theoretical and experimental dyz 0.34303 –0.33688 0.11016 0.66903 0.00136
structures. Therefore, the atomic charge and
Electronic excitation energies and the absorption
electronic spectrum calculations can be made
coefficient of the most intense bands are given in
theoretically.
Table 4.
Atomic charge analysis
The α and β frontier orbitals containing unpaired
electrons are present in the complexes. Frontier
Atomic charge distributions on donor-acceptor
orbitals of studied complexes are found to be similar.
atoms of the studied complexes and donor atoms of
HOMO-1, HOMO, LUMO and LUMO+1 orbital
free ligands were calculated at B3LYP/LANL2DZ
surfaces and energies for complex (1) are given in
level of theory. Charge distributions between donor
Fig. 4.
atoms of ligands and acceptor atoms of complexes
were evaluated by natural population analysis (NPA) A band with large oscilator coefficient for complex
in gas phase. The charge distribution results are listed (1) appears at 355.2 nm. This band comprises the
in Table 3. 63β→67β (0.15692) and 64β→67β (0.98053)
Comparing the atomic charges in Table 3, it can be electronic transitions (coefficients of the wave
seen that the electron density of the donor atoms in function for each transition are given in parentheses).
the complexes decreased as compared to that in the The 67β orbital is LUMO, whereas 63β and 64β
free ligand, while the electron density of copper(II) orbitals are HOMO-3 and HOMO-2, respectively.
cation increased. For instance, before complexation, The contributions of 3d-atomic orbitals to 63-67β
the charge on copper is +2, while the charge of the molecular orbitals are given in Table 5.
copper in complexes (1) is +0.950. This indicates that As can be seen from Table 5, the highest
ligands transfer their negative charges to copper(II) contribution to the 67β orbital is from the dx2-y2 and
ions during formation of the complexes. In addition, dz2 orbitals of copper(II) ions, while that to the 63β
the electron density of copper increases in the order: molecular orbital is from the dxz, dyz and to 64β
(2) > (4) > (3) > (1). This result shows that the tren orbital it is from dxy, dyz orbitals. According to
ligand has better donor atoms than the other ligands Krishnamurthy and Schaap36, energy ranking of
and the increase in number of carbon atoms between d-orbitals at trigonal bipyramidal geometry are
the nitrogen atoms in the ligand chain decreases dxz = dyz<dxy = dx2-y2 < dz2. In the present case, the
transfer of charge.
band at 355.2 nm can be said to occur due to the dxz,
Electronic spectra dyz→dz2 or dx2-y2 and dxy→dz2 transitions. This
Electronic excitation energies of the studied prediction is consistent with prediction in the
complexes were calculated by using TD-DFT/B3LYP literature37. A similar prediction can be made for
method with LANL2DZ basis set in gas phase. other studied complexes.
484 INDIAN J CHEM, SEC A, APRIL 2013

Fig. 4 – HOMO-1, HOMO, LUMO and LUMO+1 orbital surfaces and energies for complex (1).

Conclusions Acknowledgement
Ab inito calculations were performed on the copper We thank the Scientific Research Projects
complexes by DFT/B3LYP method with LANL2DZ of Cumhuriyet University, Sivas, Turkey
basis set. Bond lengths and angles were calculated (Project No. F-308) for financial support.
and are in a good agreement with the experimental
results. Electronic structures of the complexes were References
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