Accepted Manuscript

The role of metals and dithiolate ligands on structural, electronic

and optical properties of [M(bipyridine)(dithiolate)] complexes: A
theoretical study

Sepideh Samiee, Samira Taghvaiean

PII: S1386-1425(18)30201-4
DOI: doi:10.1016/j.saa.2018.03.010
Reference: SAA 15882
Spectrochimica Acta Part A: Molecular and Biomolecular
To appear in:
Spectroscopy
Received date: 29 November 2017
Revised date: 7 February 2018
Accepted
4 March 2018
date:

Please cite this article as: Sepideh Samiee, Samira Taghvaiean , The role of metals
and dithiolate ligands on structural, electronic and optical properties of
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 ACCEPTED MANUSCRIPT

The role of metals and dithiolate ligands on

structural, electronic and optical properties

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of [M(bipyridine)(dithiolate)] complexes; A

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theoretical study

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Sepideh Samiee*, Samira Taghvaiean

Department of Chemistry, Faculty of Science, Shahid Chamran University of Ahvaz, Ahvaz, Iran
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*Corresponding author. Tel: +986133331042; Fax: +986133337009; E-mail address:

s.samiee@scu.ac.ir and samiee.sepideh@gmail.com

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Abstract

A series of [M(diimine)(dithiolate)] complexes of general formula [M(bpy)(dithiolate)] {bpy =

2,2´-bipyridine;dithiolate = 1,2-benzenedithiolate (bdt2-), 3,4-toluenedithiolate (tdt2-) and 4-

cyanobenzene-1,2-dithiolate (cbdt2-); M = Ni(II), Pd(II) and Pt(II)} have been studied by density

functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations.

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The geometries, stabilities, electronic structures, optical absorption spectra in different phases as

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well as thermodynamic parameters are explored. The changes of metal ion center and dithiolate

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ligands on some molecular properties are also discussed. These calculated results are in good

agreement with the experimental data. The bonding analyses show that the M–S bond is covalent

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so that always polarized towards sulfur atom, whereas the M–N bond exhibits a considerable
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amount of electrostatic interaction. Detailed NBO analysis indicates that these complexes can be

easily oxidized than reduced, and acts as the reducing agent. The HOMO-LUMO energy gaps of
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all complexes under study are founded about 2 eV and the strong absorption from 400 to 700 nm
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which match with the solar spectra very well. Besides, the simulated absorption spectra are in

accordance with the trends of energy gaps. Comparison of the absorption spectra in
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dichloromethane solution with those in gas phase show that the solvatochromic effect. The order
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of magnitude for light harvesting efficiencies (LHE) of all complexes is Pt > Pd > Ni and cbdt2- >

bdt2-> tdt2-. Our results confirm the effect and role of metals and dithiolate ligands on enhancing
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the optical properties of these complexes. Thus, the result of this work can serve as a rational

tool for the design and synthesis of diimine-dithiolate complexes and broadens the scope for

further investigations into potential dyes for use in the field of dye-sensitized solar cells (DSSC).

Keywords: DFT, Diimine-dithiolate complex, Charge transfer, Absorption spectra

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1. Introduction

Research on metal dithiolenes has remained continuously active since its inception in the

early 1960s by Schrauzer [1]. The intense interest in dithiolene complexes is the result of both

their intrinsic interest and their potential applications as non-linear optics [2–5], superconductor

[6–9], Q-switch laser dyes [10–12], light energy conversion materials [13–17], pesticides

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[18,19], and can be potentially used as biocatalysts [20,21]. This wide range of applications

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derives from unusual magnetic properties and the unique electronic structures [22–27], and also

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their reversible redox behavior [28,29].

Over the past thirteen years, a great deal of interest has been observed in the

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photophysical properties of the M(diimine)(dithiolate) complexes of group VIII metals. The
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reason for such interest is the observation that these compounds photoluminesce, not only in

glassy media at low-temperature, but also in fluid solution at room temperature [30]. These
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compounds represent unique properties such as solvatochromism, solution luminescence, large

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long-lived excited state oxidation potentials and large molecular hyperolarizabilities [31–35],

which might be utilized in applications as dyes for solar cells [36–37] and for the sensitization of
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the excited states of oxygen [38], cation sensors [39], non-linear optical (NLO) materials [40]
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and molecular photochemical devices (MPD). The specific structure is explained by the

existence of two different unsaturated chelating ligands in the same molecule. The first one, a
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dithiolate ligand, is a good π*-donor, while the second, a diimine, is a good π*-acceptor, so one

of which is more easily reduced (dithiolate) and the other more easily oxidized (diimine) [41].

Note that the precise details of the photophysical properties can be fine tuned by peripheral

modification of the dithiolate ligand [42]. In general, the hetero aromatic ligands each have low-

energy π*orbitals that are involved in charge-transfer (CT) excited states of their corresponding

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complexes. For most latter complexes, the intense solvatochromic band in the low energy region

of their electronic spectra is considered to involve the highest occupied molecular orbital

(HOMO), which is a mixture of metal and dithiolate orbital character, and the lowest unoccupied

molecular orbital (LUMO), which is a π* orbital of the diimine and has been termed a “mixed-

metal/ligand-to-ligand charge transfer” )MMLL´CT or MLCT/LLCT( as recently has

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abbreviated [43–44]. These complexes generally absorb light in the visible and ultraviolet

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regions.

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Density Functional Theory (DFT) has been proven to be extremely useful to obtain

almost accurate molecular orbital energies and other properties of transition metals complexes

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[45] especially if there is a comparison among the calculated properties of the compounds of the
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same class and the existed experimental ones [46,47]. On the other hand, it seems that the

knowledge of the nature of the frontier orbital as well as the nature of the energy transitions
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would be unambiguously a helpful tool in synthesis or design of functional molecules and for a
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mechanistic analysis of their photochemistry and electrochemistry. Moreover, the structural

factors influence the excited-state properties of these entitled complexes. Due to, we are
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interested a series of diimine-dithiolate complexes of the type [M(diimine)(dithiolato)] (diimine

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= 2,2´-bipyridine (bpy); dithiolate = 1,2-benzenedithiolate (bdt2-), 3,4-toluenedithiolate (tdt2-) or

4-cyanobenzene-1,2-dithiolate (cbdt2-); M = Ni(II), Pd(II) or Pt(II)) have been investigated with

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Density Functional Theory (DFT) and time-dependent density functional theory (TDDFT)

method. The goals of our present work are (i) to compare the structures and stability of

[M(bpy)(dithiolato)] complexes, iii) to derive general trends to understand the influence of

different dithiolate ligands and metal atoms on molecular properties (iii) to compare absorption

spectra in gas and solution phase on the basis of the optimized complexes.

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2. Computational details

All the calculations in this study were performed with Gaussian 09 package [48]. The

molecular models in the present work are shown in Scheme 1. The geometry of the entitled

diimine-dithiolat complexes were fully optimized at the DFT [49] level of theory by using the

three-parameter hybrid functional B3LYP [50,51]. The standard 6-31G (d) polarized double- ζ

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basis set is for H, C, N, O and S atoms (all light atoms) [52], and taking into account the

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relativistic effect, the effective core potential (ECP) double- ζ (DZ) basis set of LanL2DZ is for

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Ni, Pd and Pt atoms [53]. The B3LYP/6-31G(d) conjugated with LanL2DZ is generally used for

diimine-dithiolate complexes [41]. To check the consistency of our calculation, the results were

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compared with available experimental data. The results show that the deviation value of key
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bond length parameters is in very good agreement to X-ray data [54-56].

Scheme 1.here
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Binding energies (BE) were calculated with respect to the sum of the electronic energies
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of structures according to the following definition as Eq. (1):

Ebind = Ecomplex – E(bpy) – E[dithiolate]2- – EM2+ (1)

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where Ecomplex is the energy of complex [M(bpy)(dithiolato)], E(bpy)is the energy of free
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bipyridine ligand, E[dithiolate]2- is the energy of free dithiolate ligand (bdt2-,tdt2- or cbdt2-) and EM2+

is the divalent metal ions (Ni, Pd or Pt).

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In continues, the natural bond orbital (NBO) analyses [57] and frequencies calculations were

performed on all the studied using the B3LYP functional with the above-mentioned basis set.

The effective valence denotes the actual charge of an atom in a molecule and here is defined as

the natural charge obtained from NBO analysis. Accordingly, the effective valence (q) of atom A

can be calculated by the Eq. (2):

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q = ∑𝑖 𝑞𝑖 (2)

where the natural population (qi) of the natural atomic orbital (øi) on atom A is the diagonal

density matrix element in the natural atomic orbital basis [58].

The Wiberg bond index (WBI) closely relates to the bond character, that is, larger WBI

means stronger covalent character. The WBI value arises from the manipulation of the density

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matrix in the orthogonal natural atomic orbital basis derived through the natural population

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analysis. The WBI expresses the sum of squares of density matrix elements (pjk) and equals two

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times the charge density in the atomic orbital (pjj) minus the square of the charge density, and so

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is mathematically defined as Eq. (3):

WBI   p2jk  2p jj  p2jj (3)

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k
The HOMO–LUMO gap is an important parameter to characterize the electronic structure of

molecules. It is well known that the energy gap retains close connection to some molecular
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properties. Herein, we consider the energy gap since it is known to be the index of both kinetic
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stability (reactivity) and electrical conductivity [59]. Finally, on the basis of the optimized
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ground state structures, absorption spectrum in gas phase and dichloromethane solutions were

carried out by using TDDFT at the same level of theory associated with the polarized continuum
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model (PCM). Also, we have calculated the light harvesting efficiency (LHE) of all complexes

using the formula [60]:

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LHE = 1 – 10-f (4)

where f is the oscillator strength of the designed complexes. According to Eq. (4), the bigger f is,

the higher LHE will be.

3. Results and discussion

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3.1. Molecular structure

The optimized geometries of all the [M(bpy)(dithiolate)] complexes under study are

shown in Fig. 1. All of the calculated structures have C2v (substituted bdt2-) and Cs symmetry

(substituted tdt2- and cbdt2-) and are energetic minima, that is, they have no imaginary vibrational

frequency. The important optimized geometrical parameters of the studied complexes are listed

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in Table 1. Theses calculated parameters are also very close to experimental values found by X-

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ray diffraction [54-57] and collected in Table 1S. Based on these facts the overall agreement

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between theory and experiment is judged as satisfactory.

Fig. 1 here

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Table 1.here
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As can be seen in Fig 1., for all nine optimized complexes, the metal atom is coordinated

by two N atoms of the bipyridine ligand and two S atoms of the dithiolate ligand forming a
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slightly distorted square planar geometry with the two five membered rings (MS2C2 and MN2C2)
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lying on the same plane. From Table 1, comparing different metal complexes, the average M–S

and M–N bond lengths in Ni(II) complexes are shorter than that for Pd(II) and Pt(II) complexes
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(Pd ≈ Pt > Ni), in keeping with the similar bonding radii of the second- and third-row transition
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metals [61]. These imply that the interactions between Ni and coordinated atom are stronger than

those of series Pd(II) and Pt(II) complexes. Note that the average M–N bond length is shorter
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than the M–S and the bond angle N–M–N is smaller than S–M–S. This trend is presented atomic

radius effect on the structural parameters. As expected, we do not observe any significant

difference between the geometrical parameters for the complexes with various dithiolate

substituent. For example, the calculated distances and angles in [Ni(bpy)(bdt)] complex are

essentially equal to those for [Ni(bpy)(tdt)] and [Ni(bpy)(cbdt)]) complexes (see Table 1).

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Inspecting the data in Table 1, we observed that the average calculated values of C–S and

C–C bond lengths in the dithiolene moieties were 1.767 Å and 1.405 Å, respectively. These

values are considerably shorter and longer than for both C–S and C–C olefin bond lengths, which

can be explained by the various oxidation state of a dithiolene ligand in the entitled complexes. It

is worth mentioned that bidentate dithiolate ligands are known potentially to be redox active non-

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innocent ligands, meaning that they can represent a variety of redox states and that frequently

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show interesting optical properties [62,63]. In addition, one can easily conclude that the M–N

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bond lengths are longer than those observed in bis-diimine compounds, while the M–S distances

have been contracted, as compared to those of the related bis-dithiolenes [64]; which nicely

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reflects the a direct consequence of significant trans-influence. In Table 1, it is clear that the two
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of C–S bond lengths are slightly different due to present of substitution group in dithiolate ligand

whiles the two of C–N bond lengths are equal.

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3.2. Electronic structure

The next step is the study of the electronic structure of the complex. To investigate the
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analysis of the bonding situation in the diimine-dithiolate complexes, NBO calculation were
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performed using the B3LYP/6-31G(d) (LanL2DZ basis set on metal atom) method. The results

are given in Tables 2.

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Table 2.here

First, the calculated NBO charge distribution indicates that the metal atoms always carry

a positive charge, while the nitrogen and sulfur atoms carry a negative charge. Also, nitrogen is

significant more negative charged than sulfur. On the other side, all atomic charge values of

metal atoms are less than the expected oxidation number of +2. Therefore, there is a decrease in

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the charge distribution on the metal and dithiolat ligand reflecting charge transfer from the

dithiolate to the metal and bipyridine ligand. Comparing computed complexes with different ion

metals show that the positive charge on the metal atoms decrease in the order Ni > Pd > Pt,

which is consistent with increase the electronegativities of these metals. This latter value for

complexes with different dithiolate also decreases in the order cbdt2- > bdt2- ≈ tdt2-, which show

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the influence of different groups (CN- or Me) on phenyl ring in dithiolate ligands. Thus, the

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[Ni(bpy)(cbdt)] complexes have the largest positive charge on metal other than studied

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complexes.

Second, as can be seen in Table 3, the WBI values of M–S and M–N are only slightly rise

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as Pt > Ni > Pd, and the other WBI are essentially the same. Thus, the covalent character of the
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metal-ligand for platinum(II) in complexes is stronger than Ni(II) and Pd(II) complexes. This is

in accord with the above conclusion deduced from the charge distribution. Along the same line,
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for all investigated complexes, the WBI value of the M–S bond (≈0.8) is larger than the M–N
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bond (0.4), so the M–S bond has a stronger covalent character than the M–N bond.

Third, to quantify intuitive concept such as the electronic and hybridization effects, which
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can be associated with the bonding orbital interactions, a definitive picture of the M–S and M–N
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bonding is obtained through a NBO analysis of the delocalized Kohn-Sham orbital. In entitled

complexes, the occupations of M–S bonding orbital fall in the range of 1.88–1.93, and are also
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polarized towards the two sulfur atoms of dithiolate ligands. This value decrease in the following

sequence: Pt > Ni > Pd. This is in agreement with the above results of Wiberg bond values. It

should be note that no metal-ligand bonding orbitals are observed for two M–N bonds due to the

interaction between the metal atom and bipyridin ligand is an electrostatic interaction. Besides,

NBO analyses show that the M–S covalent bonds result from valence bonding electron density

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overlap between the sp0.5d hybridized valence orbitals of the metal atom and the sp6 hybridized

sulfur atoms. The hybridization of the M–S bond at the sulfur atoms has p character of almost

85% of the total AO contribution. The hybridization of this bond at the metal atom has d

character of about 50% and p character of about 15% of the total AO contribution. As expected,

on going from Ni to Pt the % contribution of d character in M–S bonds increases. Meantime,

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there is no a common trend or an effect influence for various dithiolate ligands in all complexes.

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In continuous, the NBO electronic populations of all complexes under study are collected

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in Table 3. Based on our knowledge, the formal electron configurations of Ni, Pd and Pt atoms

are 3d84s2, 4d85s2 and 5d86s2, respectively. As shown in this table, compared with these formal

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electron configurations, the all of the np and (n – 1)d populations increase while ns populations
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decrease. As a consequence, the population excess over the formal configuration mainly arises

from strong donations from lone-pair electrons on coordinated sulfur atoms as well as σc-s and σc-
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c orbitals of the dithiolate ligands, also consistent with the observed above result of charge
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distribution on the metal atoms.

Table 3.here
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The molecular orbital (MO) diagrams are depicted in Fig. 2. Typical three-dimensional
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pictures of the HOMO and LUMO for all complexes are illustrated in Fig. 1S. The graphical

representations of frontier orbital indicate that the contribution of the metal is increased in both
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HOMO and LUMO for Pt compared to Ni and Pd complexes. This trend is attributed to the

better metal–ligand overlap induced by the 5d-orbitals of Pt compared to 4d- of Pd and 3d-

orbitals of Ni. Our DFT calculation conclude that the HOMO is localized largely of sulfur 3pz

orbitals that form antibonding interactions with metal dxz orbitals and carbon 2pz orbitals on the

chelating ring. The high contribution of 3pz on the HOMO orbitalis probably the reason that

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these complexes are easily oxidized to give sulfinated and sulfonated derivatives as has been

reported before [65,66]. On the other hand, LUMO is exclusively located on diimine whereas a

limited contribution of metal and dithiolate ligand still exists. More precisely, apart from the

interactions between carbon atoms of the carbohydrated core, anti bonding interactions of the 2pz

nitrogen orbitals with the dxz metal orbital are also present. The aforementioned pattern,

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consistent with π*-back-bonding theory, indicates that electron back-donation to bpy is reduced

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by the presence of dithiolate as compared with other diimine complexes [67]. Not that the band

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gap is an important measure of stability [68,69] which influences the light absorption ability of a

molecule and discussed in following.

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Fig. 2 here
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As shown in Fig 2., the band gap of the complexes was found to be 1.76–2.09 eV. Note

that the calculated frontier orbital energies and band gap energies are given in Table 2S. These
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values has the order Pd > Pt > Ni for varying metal ions and cbdt2- > bdt2- > tdt2- for varying
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dithiolate ligands. As is well known, the smaller energy gap corresponds to the higher reactivity.

Thus, a comparison between the gap energy of all complexes suggested that tdt2- can consider as
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the most reactive dithiolate ligand and nickel can consider as the most reactive metal atom. A
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closer inspection of Table 2S revealed that the addition of the cyanide group to the structure of

complexes has increased about 0.2 eV in the calculated band energy gap. This result is in
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agreement with–CN group is a good π*-accepting group as compared to –H and/or –Me group.

Also, the influence of a -CN substituent can be defined by the low lying orbital (LUMO+4) of

[M(bpy)(cbdt)] complexes. It is interesting to note that the HOMO -1 to HOMO energy gap is

about 0.13 eV, which is larger than the energy gap between LUMO to LUMO + 1 ( ≈0.5 eV) as

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seen in Table 5. Indeed, the nine studied complexes will be easier to be oxidized than reduced,

and acts as the reducting agent.

Although energy gaps are important indices when estimating the optoelectronic

properties, UV–Vis absorption spectra are more reliable and direct data to evaluate how these

sensitizers will perform in the solar cells. Thus, we have simulated the UV–Vis absorption of the

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all studied complexes and the spectra with corresponding transition assignments are discussed

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especially in next section.

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3.3. Absorption spectroscopy

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TD-DFT calculations are performed for heteroleptic biypridine-dithiolate complexes
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studied here in gas phase and dichloromethane solution. The effect of the solvent was simulated

by the polarize continuum model (PCM) included in the Gaussian 03 program. The calculated
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absorptions associated with the excitation energies and oscillator strengths as well as the
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assignments of all complexes are summarized in Table 4-6 (for dichloromethane phase) and in

Table 3S-5S (for gas phase). The absorption spectra in two studied phase are plotted in Fig.3.
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The obtained results seem to nicely agree with the corresponding experimental data [58,70].
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Table 4-6.here

Fig. 3.here
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In comparison, the calculated absorptions of all complexes in the gas phase and

dichloromethane solution show that the lowest energy absorption have a comparatively strong

solvatochromic effect and made blue shift while the other absorptions show little. Taking

[Ni(bpy)(bdt)] as an example, the absorptions at 802 nm, 546 nm and 385 nm in gas phase

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correspond to the absorptions at 557 nm, 416 nm and 326 nm in the dichloromethane solution,

respectively (see Fig 3,a).

From Table 6-8 induced that the charge-transfer bond of complexes stretches from 400 to

600 mainly corresponded to the transition of the HOMO to LUMO or mixed HOMO-1 to

LUMO. This CT can be assigned to occur from a HOMO consisting of a mixture of M(d) and

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dithiolate(p) orbital character to a low-energy π* orbital LUMO located on the bpy [70], and

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which are therefore mixed metal–ligand to ligand charge transfer (MMLL´CT) transitions

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analogous to the one observed to all [M(diimine)(dithiolate)] complexes. The absorption in the

visible region with the highest oscillator strength of the electromagnetic spectrum is well within

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the acceptable range required for a DSSC sensitizer as reported previously [71-74]. Also, an
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intense band in the UV regions at approximately 300 nm can be assigned to the intraligand

transition of the bpy ligand (π→π*) [75]. Therefore, the dual-band characteristic makes the
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absorption broad, which is beneficial for light-harvesting if the absorption spectrum covers
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visible region.

A comparison between the role of various metals and dithiolate ligands on absorption
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bands are presented in Fig. 4. The calculated absorption bands of Pt complexes have longer
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wavelengths than those of Ni, and Pd complexes. On the other hand, the higher oscillator

strengths are observed for the Pt complexes comparing with the Pd and Ni ones, in accordance
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with the molar extinction coefficient [76,77]. This observation strongly supports metal orbital

involvement in the charge-transfer to diimine excited state since it could indicate the higher

participation of the metal to charge transfer procedure due to the greater metal d-orbital content.

Along the same lines, the sequences of the calculated absorptions of complexes with various

dithiolate are found as tdt2- > bdt2-> cbdt2-. Thus, attaching the strong electron-donor group on

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the phenyl positions will induce the red shift of the absorption spectra which means the energy

decrease needed for the optical transition. As a result, the changing of dithiolate ligand has more

effect on the transition energy and the changing of metal ions enhances more the oscillator

strength.

Fig. 4.here

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Besides the absorption, according to Eq. (4), the corresponding light harvesting

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efficiencies (LHE) of these complexes were also estimated (see Table 9), which are closest to

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their magnitude of the oscillator strength f. The trend of increasing LHE is found to be: Pt > Pd >

Ni; cbdt2- > bdt2- ≈ tdt2-. Thus, the [Pt(bpy)(cbdt)] complex have the higher absorption efficiency

between other complexes.

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3.4. Thermodynamic parameters
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In the final section, to understand and compare the thermodynamic stability of the studied
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complexes, the binding energy (ΔEbind), Gibbs free energy changes (ΔG°), enthalpy changes

(ΔH°), and entropy changes (ΔS°) of the process were calculated at 1 atmosphere and 298K (see
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Table 7).
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Table 7.here

The results in Table 7 indicate that all of the binding energies are negative, and it seems
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that the nine studied complexes are thermodynamically stable. The calculated parameters show

that these complexes can be readily synthesized at room temperature which is in excellent

consistency with the synthesis report by Cocker et al. [58]. From Table 7, the relative stability of

all complexes is as Pt > Pd > Ni and tdt2- > bdt2-> cbdt2- for the different metal ions and dithiolate

groups, respectively. One can conclude that the complexes are thermodynamically the most

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stable one compared to the other complexes at room temperature and 1 atm. Although the

binding energies always are negative because of the more stability of the diimine-dithiolate

complexes compared to their isolated ligands, but it cannot give information about the absolute

stability. Thus, it is essential to calculate the other thermodynamic parameters such as the

standard Gibbs free energy (ΔG°), enthalpy of formation (ΔH°) and entropy change (ΔS°).Table

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6 reveals that the ΔG° values of all complexes are negative, which imply that its formation may

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be thermodynamically spontaneous process.

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4. Conclusions

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In this contribution, we report a DFT/TDDFT study on a series of M(diimine)(dithiolate)
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complexes of Group VIII metals. These molecules are important in their relevance to the area of

solar cell dyes and also more generally for their optical and electronic functionality. The bond
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lengths performed at B3LYP/6-31G* (LanL2DZ basis set on metal) level, reproduced X-ray
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structures of all members of the series within the deviation less than 0.1 Ǻ, and the deviation

between the calculated and experimental bond angles for S–M–S and N–M–N are only about 2°.
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The M–S bond lengths in the series of metal dithiolenes increase on passing from Ni to Pt. The
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bonding analysis of the title compounds show that the M–S bonds are more covalent than M–C

bond, and are always polarized towards sulfur. Any electron occupancies do not found for M–N
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bonds complexes. Thereby, there are no metal–ligand bonding orbitals and the electrostatic

interaction indicates the corresponding metal–ligand interaction. The calculated frontier orbital

energies show that the band gap energies of the complexes were found to be 1.76–2.09 eV.

Further, we have systematically investigated the UV–Vis absorption spectra and electronic

transition characters of selected diimine-dithiolate complexes and reported their spectral

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properties for DSSC applications. From our results, we found that the Pt complexes can increase

the molar extinction coefficients as well as red-shift the overall spectra. Also, the substitution of

dithiolate ligands enhance the overall absorption spectrum can be red shifted significantly. The

appearance of the absorption band at both UV and visible to near-IR region with high molar

extinction coefficients including significant intraligand transition and mixed metal–ligand to

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ligand charge transfer is suitable for efficient sensitizer. Thermodynamic analysis indicates that

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the formations of these complexes are exothermic; moreover, the Ni complexes are easier to

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decompose than Pd and Pt complexes. In this regard, the sequence of binding strengths are Pt >

Pd > Ni and tdt2-> bdt2-> cbdt2-, thus the complex [Pt(bpy)(tdt)] is most stable. Briefly, we

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investigated some metal diimine-dithiolate complexes which have suitable optoelectronic
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properties and we believe that these molecules can be used as an efficient sensitizes in the DSSC

applications.
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Acknowledgements

Support of this work by Shahid Chamran University of Ahvaz, Iran (Grant No. 1395) is
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gratefully acknowledged. We are grateful to Dr. Z. B. Mahdavifar for valuable assistance and
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many good suggestions.

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Scheme 1. Schematic view of the investigated diimine-dithiolate complexes hererin.

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[Ni(bpy)(bdt)] [Pd(bpy)(bdt)] [Pt(bpy)(bdt)]

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[Pt(bpy)(tdt)]
[Ni(bpy)(tdt)] [Pd(bpy)(tdt)]
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[Ni(bpy)(cbbdt)] [Pd(bpy)(cbbdt)] [Pt(bpy)(cbbdt)]

Fig. 1. Optimized geometry structures of all complexes under study at B3LYP/6-31G* (LanL2DZ basis set on metal) method.

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Fig. 2. Energy diagram and graphical representation of frontier orbitals for nine studied systems.

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Fig. 3. Calculated absorption spectra of a) [M(bpy)(bdt)] b ) [M(bpy)(tdt)]c) [M(bpy)(cbdt)]complexes in gas phase (red) and in
dichloromethane solution (blue).

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a) Role of the metal ions b) Role of the dithiolate ligands

[M(bpy)(bdt)] [Ni(bpy)(dithiolate)]

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[M(bpy)(tdt)] [Pd(bpy)(dithiolate)]

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[M(bpy)(cbdt)] [Pt(bpy)(dithiolate)]
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Fig. 4. The role of changing of the a) metal ions and b) dithiolate ligands in simulated absorption spectra for[M(bpy)(dithiolate)]
complexes in dichloromethane, calculated by the TD-B3LYP with PCM calculation.

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Table 1. Selected optimized geometrical parameters for the [M(bpy)(dithiolate)] complexes; bond lengths are in(Å) and angles are in
degrees (°).
M Ni Pd Pt
dithiolate bdt tdt cbdt bdt tdt cbdt bdt tdt cbdt
Bond length
M–N 1.978 1.978 1.979 2.132 2.133 2.131 2.091 2.091 2.092
M–Sa 2.192 2.192 2.193 2.300 2.298 2.300 2.312 2.312 2.314
C(1)–S 1.767 1.767 1.759 1.775 1.775 1.767 1.772 1.772 1.764
C(2)–S 1.768 1.767 1.765 1.776 1.775 1.773 1.772 1.772 1.770
C=N 1.359 1.359 1.358 1.358 1.358 1.358 1.364 1.364 1.363
C=Cdithiol 1.404 1.403 1.407 1.403 1.403 1.406 1.404 1.404 1.407
C=Cbpy 1.403 1.478 1.404 1.469 1.478 1.467 1.420 1.420 1.402

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Bond angle

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N–M–N 82.31 82.37 82.37 77.67 77.64 77.78 78.21 78.21 78.25
S–M–S 89.84 89.82 89.83 87.98 87.96 87.97 88.16 88.14 88.18
S–M–Nb 176.26 176.27 176.35 174.85 174.83 175.01 175.04 175.03 175.12

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S–M–Nb 176.20 176.27 176.18 174.83 174.83 174.79 174.99 175.03 174.95
N–M–Sc 93.89 93.90 93.81 97.16 97.19 97.00 96.78 96.82 96.69
N–M–Sc 93.94 93.90 93.97 97.17 97.19 97.22 96.83 96.82 96.86
a
The average value of both distances. b trans and ccispositions, respectively.

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Table 2. Wiberg bond indices and results of the NBO analysis of the [M(bpy)(dithiolate)] complexes.
M Ni Pd Pt
dithiolate bdt tdt cbdt bdt tdt cbdt bdt tdt cbdt
NBO charges
M 0.168 0.168 0.178 0.119 0.120 0.129 0.102 0.102 0.109
N -0.435 -0.435 -0.435 -0.432 -0.432 -0.432 -0.430 -0.430 -0.428
S -0.051 -0.052 -0.043 -0.022 -0.024 -0.012 -0.005 -0.006 -0.002

Wiberg bond
M–N 0.378 0.378 0.377 0.343 0.343 0.343 0.449 0.450 0.447
M–Sa 0.876 0.876 0.867 0.818 0.817 0.810 0.878 0.877 0.870
C=Cdithiol 1.323 1.314 1.312 1.329 1.320 1.316 1.325 1.317 1.313

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C=Cbpy 1.314 1.323 1.312 1.320 1.329 1.316 1.317 1.325 1.313
C=N 1.290 1.291 1.293 1.296 1.295 1.298 1.263 1.263 1.267

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C–S 1.090 1.089 1.099 1.086 1.085 1.095 1.090 1.088 1.098

M–S σ bond

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occupancy 1.924 1.924 1.924 1.889 1.889 1.890 1.938 1.939 1.939
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%a 29.97 29.98 29.77 33.15 33.15 32.94 34.98 34.98 34.66
%s 34.84 34.86 34.67 36.65 36.65 36.44 38.11 38.11 38.02
%p 17.32 17.29 17.45 13.99 13.99 14.16 12.24 12.23 12.38

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%d 47.84 47.85 47.88 49.36 49.36 49.41 49.66 49.66 49.60
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%a 70.03 70.02 70.23 66.85 66.85 67.06 65.02 65.02 65.34
%s 13.77 13.76 13.85 11.94 11.91 12.00 16.19 16.18 16.32
%p 86.13 86.14 86.05 87.89 87.92 87.83 83.60 83.60 83.46
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Table 3. NBO electronic populations of all studied complexes.

Natural electron config. Natural atomic orbital occupancies
(n–1)dxy (n–1)dxz (n–1)dyz (n–1)d𝑥 2 − 𝑦 2 (n–1)d𝑧 2
[Ni(bpy)(bdt)] 4s0.38 3d8.91 4p0.53 1.05323 1.93119 1.97901 1.98329 1.96006
[Pd(bpy)(bdt)] 5s0.39 4d9.05 5p0.43 1.22309 1.92956 1.97701 1.97335 1.95008
[Pt(bpy)(bdt)] 6s0.58 5d8.84 6p0.46 1.15044 1.86641 1.95835 1.95844 1.90772
[Ni(bpy)(tdt)] 4s0.38 3d8.91 4p0.53 1.06872 1.93105 1.97892 1.96775 1.96004
[Pd(bpy)(tdt)] 5s0.39 4d9.05 5p0.43 1.23367 1.92920 1.97686 1.96260 1.95003
[Pt(bpy)(tdt)] 6s0.58 5d8.84 6p0.46 1.16252 1.86616 1.95802 1.94637 1.90767
[Ni(bpy)(cbdt)] 4s0.38 3d8.91 4p0.52 1.08174 1.93806 1.97876 1.94706 1.96047
[Pd(bpy)(cbdt)] 5s0.39 4d9.05 5p0.42 1.24258 1.93587 1.97659 1.94698 1.95067
[Pt(bpy)(cbdt)] 6s0.58 5d8.84 6p0.46 1.17415 1.87517 1.95760 1.92916 1.90806

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Table 4. Calculated optical data and transition assignments for the [M(bpy)(bdt)] complexes by TDDFT calculation in
dichloromethane solution.
System λ (nm) ΔEb (eV) fc (a.u.) LHEd Compositione
[Ni(bpy)(bdt)] 575(557) a
2.22 0.1027 0.211 H → L (95%)
544 2.27 0.0008 H-1 → L (95%), H-2 → L+1 (2%)
434 2.85 0.0035 H-10 → L+1 (63%), H-7 → L+1 (27%), H-
15 → L+1 (7%)
416 2.97 0.0008 H-2 → L (94%), H-1 → L+2 (2%)
407 3.041 0.0012 H-1 → L (98%)

[Pd(bpy)(bdt)] 558(510)a 2.21 0.1385 0.273 H → L (99%)

556 2.22 0.0018 H-1 → L (99%)

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411 3.01 0.0056 H → L+1 (95%)
399 3.10 0.0001 H-1 → L+3 (96%), H-3 → L+3 (3%)

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397 3.11 0.0031 H-1 → L+3 (94%), H → L+2 (5%)

[Pt(bpy)(bdt)] 589)598) a 2.10 0.0037 H-1 → L (98%)

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564 2.19 0.1822 0.342 H → L (98%)
419 2.96 0.0148 H → L+1 (96%), H-1 → L+2 (3%)
412 3.01 0.007 H-1 → L+1 (93%), H→ L+2 (5%)
387 3.27 0.0237 H → L+2 (92%), H-5 → L (2%), H-1 →
L+1 (4%)

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Experimental value in parentheses comes from Ref. [54]. bVertical transition energy. cOscillator strength. dlight harvesting
efficiency. eCompositions of electronic transitions are expressed in terms of contributing excitations between ground-state
Kohn-Sham molecular orbitals.
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Table 5. Calculated optical data and transition assignments for the [M(bpy)(tdt)] complexes by TDDFT calculation in
dichloromethane solution.
System λ (nm) ΔEa (eV) fb (a.u.) LHEc Compositiond
[Ni(bpy)(tdt)] 575 2.15 0.0878 0.183 H → L (98%)
551 2.24 0.0182 H-1 → L (95%), H-2 → L+1 (3%)
434 2.85 0.0035 H-10 → L+1 (61%), H-7 → L+1 (27%), H-
14 → L+1 (8%)
417 2.96 0.0008 H-2 → L (84%), H-9 → L+1 (2%), H-4 →
L+1 (7%)
416 2.97 0.0012 H → L+2 (98%)

H → L (90%), H-1 → L (9%)

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[Pd(bpy)(tdt)] 578 2.14 0.0905 0.188
560 2.21 0.0538 H-1 → L (89%), H → L (9%)
H → L+1 (97%)

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420 2.95 0.0054
402 3.08 0.0033 H-1 → L+1 (92%), H → L+2 (4%)
401 3.30 0.0128 H → L+2 (92%), H-1 → L+1 (4%)

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[Pt(bpy)(tdt)] 601 2.06 0.0167 H-1 → L (52%), H → L (47%)
572 2.16 0.1745 0.331 H-1 → L (47%), H → L (52%)
426 2.90 0.0137 H → L+1 (95%), H → L+2 (2%)
415 2.98 0.0084 H-1 → L+1 (93%), H-1 → L+2 (3%), H →
L+2 (2%)

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384 3.22 0.0302 H → L+2 (87%), H-5 → L (2%), H-1 →
L+1 (3%), H-1 → L+2 (6%)
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Vertical transition energy. bOscillator strength. clight harvesting efficiency. dCompositions of electronic transitions are
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Table 6. Calculated optical data and transition assignments for the [M(bpy)(cbdt)] complexes by TDDFT calculation in
dichloromethane solution.
System λ (nm) ΔEa (eV) fb (a.u.) LHEc Compositiond
[Ni(bpy)(cbdt)] 659 1.88 0.0001 H-3 → L+1 (22%), H-1 → L+1 (59%), H-12
→ L+1 (2%), H-8 → L+1 (7%)
510 2.42 0.1064 0.217 H → L (98%)
493 2.51 0.0082 H-1 → L (96%)
434 2.85 0.0032 H-10 → L+1 (62%), H-7 → L+1 (28%), H-
16 → L+1 (2%), H-15 → L+1 (2%)
404 3.07 0.0009 H-2 → L (97%)

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[Pd(bpy)(cbdt)] 517 2.39 0.1328 0.263 H → L (95%), H-1 → L (4%)
504 2.45 0.0222 H-1 → L (95%), H → L (4%)
H → L+3 (97%)

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401 3.08 0.0057
385 3.21 0.007 H→ L+3 (98%)
384 3.22 0.0001 H-1 → L+3 (96%), H-4 → L+3 (2%)

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[Pt(bpy)(cbdt)] 543 2.27 0.0121 H-1 → L (78%), H → L (21%)
527 2.35 0.1948 0.361 H-1 → L (21%), H → L (78%)
396 3.12 0.0181 H → L+1 (96%), H-1 → L+2 (2%)
386 3.20 0.007 H-1 → L+1 (93%), H → L+2 (5%)

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Vertical transition energy. bOscillator strength. clight harvesting efficiency. dCompositions of electronic transitions are
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Table 7. Thermodynamic parameters for all studied complexes [M(bpy)(dithiolate)].

M Ni Pd Pt
dithiolate bdt tdt cbdt bdt tdt cbdt bdt tdt cbdt
ΔEbind -828.30 -834.57 -803.20 -834.57 -840.85 -803.20 -859.67 -865.95 -834.57
ΔH° -814.99 -813.42 -787.79 -824.43 -822.85 -797.07 -854.29 -852.74 -826.66
ΔG° -792.50 -791.04 -765.53 -801.75 -800.20 -774.51 -830.71 -829.17 -803.17
ΔS° -0.075 -0.075 -0.074 -0.076 -0.076 -0.075 -0.079 -0.079 -0.078
ΔEbind(eV) is the binding energy of the process; ΔH° (Kcal/mol) is the enthalpy change of the process; ΔG° (Kcal/mol) is the Gibbs free
energy change of the process; ΔS = (ΔH-ΔG)/T (cal/mol.K) is the entropy change of the process.

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Graphical abstract-Pictogram

The role of metals and dithiolate ligands on structural, electronic and optical
properties of [M(bipyridine)(dithiolate)] complexes; A theoretical study

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Sepideh Samiee*, Samira Taghvaiean

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Department of Chemistry, Faculty of Science, Shahid Chamran University of Ahvaz, Ahvaz, Iran

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To what extent can we impact the

properties of diamine-dithiolate
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complexes by changing metal atoms

and dithiolate ligands?
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e
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H-1 → L

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Highlights
The role of metals and dithiolate ligands on structural, electronic and optical
properties of [M(bipyridine)(dithiolate)] complexes; A theoretical study

SepidehSamiee*, SamiraTaghvaiean
Department of Chemistry, Faculty of Science, ShahidChamranUniversity of Ahvaz, Ahvaz, Iran

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A series of nine [M(bpy)(dithiolate)]complexes of group VIII metals were studied by DFT

method.

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The electronic structures of all complexes are explored by TDDFT method and NBO
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analysis.
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Calculations confirm the role of the metal atom and substitution of dithiolate moiety on

the electronic properties.

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 The light harvesting efficiencies (LHE) were examined.

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 The thermochemical properties indicate the synthesis of all studied complexes is feasible

at room temperature.

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