Chinese Journal of Chemical Engineering 28 (2020) 532–540

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Chinese Journal of Chemical Engineering

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Article

A DFT and TD-DFT study on electronic structures and UV-spectra

properties of octaethyl-porphyrin with different central metals
(Ni, V, Cu, Co)
Xiaoqin Wang 1, Shiyi Li 2, Liang Zhao 2,⁎, Chunming Xu 2, Jinsen Gao 2
1
College of Science, China University of Petroleum (Beijing), Beijing 102249, China
2
State Key Laboratory of Heavy Oil Processing, China University of Petroleum (Beijing), Beijing 102249, China

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

Article history: In this work, the octaethyl-porphyrins with different central metals (M-OEP, M = Ni, VO, Cu, Co) were used to
Received 26 December 2018 investigate the ground-state molecular structure, electron distribution and UV-spectra properties on molecular
Received in revised form 3 July 2019 level by density functional theory (DFT). The results showed that the calculation structure parameters of
Accepted 15 July 2019
metalloporphyrins agreed well with the experimental value. According to the Natural Bond Orbital (NBO) anal-
Available online 24 July 2019
ysis, the charge distribution of different metalloporphyrins was found that the charge values of the central metal
Keywords:
M decreased with the order of VO b Ni b Co b Cu, while the bonding strength between M and the coordinating
Metallic impurity atom N was VO N Ni N Co N Cu. At the same time, the frontier molecular orbital calculations showed that the
Metalloporphyrin SOMO energy of VO (OEP) molecules in the open-shell system was higher than that of Co (OEP) and Cu (OEP),
Asphaltenes which means that its UV absorption characteristic peak would be red-shifted. In addition, the IEFPCM model of
Quantum chemistry Time-dependent Density functional theory (TD-DFT) was further utilized to simulate the four substance in tolu-
UV–vis spectrum ene solution: Co (OEP), Ni (OEP), Cu (OEP) and VO (OEP), and the Soret band peaks were calculated respectively
as: 382 nm, 383 nm, 391 nm and 401 nm. Furthermore, the quantitative simulation analysis of metalloporphyrins
was combined with experimental data. It could be found that the location rules of the four kinds of
metalloporphyrins calculated absorption characteristic peaks were consistent with the experimental ones, and
the relative errors of each peak were within 3%. These methods used above provide a theoretical path for analyz-
ing and identifying unknown porphyrin compounds in petroleum.
© 2019 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All rights
reserved.

1. Introduction porphyrin is complex and diverse, and limited by the level of analytical
instruments. At present, the complete understanding of the structure of
Porphyrin is a kind of macromolecular heterocyclic compound petroleum porphyrin has not yet been formed.
formed by the interconnection of the Cα atoms of four pyrrole subunits Metalloporphyrins in petroleum are mainly identified and recog-
with a methine bridge (_CH\\). When porphyrin is coordinated with a nized by some techniques such as chromatography, spectroscopy and
metal ion in the center, it is called metalloporphyrin. Metalloporphyrin mass spectrometry [9,10]. UV–visible absorption spectroscopy is the
compounds widely exist in nature, and almost all metal elements can be earliest and most common quantitative analysis method. For example,
coordinated with a porphyrin macrocycle. Metalloporphyrin has the special macrocyclic π-bond conjugated structure of
attracted intensive attention due to their unique π-conjugated system metalloporphyrins can obtain a unique Soret absorption peak by ultra-
[1–3]. At the same time, some metalloporphyrins have also been violet spectrum detection. This absorption peak is usually used for
found in petroleum, especially in heavy oils, which are mainly vana- quantitative calculation [1,11]. However, the analysis of
dium or nickel porphyrin compounds as an important form of metal metalloporphyrin by ultraviolet spectroscopy is often restricted by
in petroleum [4–6]. It has been suggested that porphyrin has a close re- some following factors. Firstly, the quality of metalloporphyrin can be
lationship with the organic origin of petroleum [7,8]. Therefore, study- enriched when the experiment is very limited, which causes inaccuracy
ing the structure of porphyrin has an important significance for in UV spectral analysis. Some researchers extracted metalloporphyrins
exploring the theory of petroleum origin. However, the structure of with different solvents, and found that they all had a low extraction
rate. It was difficult to obtain a sufficient amount of extract for qualita-
⁎ Corresponding author at: State Key Laboratory of Heavy Oil Processing, China
tive analysis [12]. Secondly, most metal porphyrins are difficult to be
University of Petroleum, 18 Fuxue Road, Beijing, China, 102249. enriched and separated, and various metal porphyrins are mixed with
E-mail address: [email protected] (L. Zhao). each other, which makes structural identification difficult [13]. Thirdly,

https://doi.org/10.1016/j.cjche.2019.07.008
1004-9541/© 2019 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All rights reserved.
 X. Wang et al. / Chinese Journal of Chemical Engineering 28 (2020) 532–540 533

the influence of other substances is also one of the factors affecting spec- functional, basis sets, and solvent effect. For metalloporphyrins, the
tral analysis. For example, Baker [14,15] found that the visible absorp- structures were often optimized by Becke's 3 parameter hybrid func-
tion peaks of ETIO, DPEP and Rhodo had different characteristics, and tional using the Lee–Yang–Parr correlation functional (B3LYP) [31,32].
Ramachandran [16] believed that the characteristic spectral features of By analyzing the transition metal such as V, Ni, Co and Cu, LANL2DZ
the vanadyl species closely resemble those of pure vanadyl porphyrins. basis set was selected as the appropriate basis set for optimization cal-
Therefore, it is necessary to establish a method for identifying culation, and 6-31 ++G (d, p) basis set was adopted by non-metal
metalloporphyrin molecules based on the corresponding laws of metal atoms. The calculated result has been proved to exhibit good matching
porphyrin structure and ultraviolet spectrum by developing theoretical with the experimental data for these model compounds [33].
methods. This has important effects and significance for the analysis of A natural bond orbital (NBO) [34] analysis was performed for each
ultraviolet spectroscopy, identification of porphyrin structure, and pre- complex to understand the electronic distribution, molecular orbital
diction of the characteristics of porphyrin mixture before the experi- and some other intramolecular interactions. The absorption spectra
ment. This work is the part of the preliminary theoretical study that within the visible region were calculated by using time-dependent den-
laid the method. sity functional theory (TD-DFT). The solvent effect simulation was
Density functional theory (DFT) is one of the most common methods achieved by using IEF-PCM model [35,36], and the electron transition
to study the molecular configuration of metalloporphyrin, and it has be- information and excitation energy could be obtained to compare with
come the preferred method for calculating a variety of molecular prop- the experimental UV spectrum. All the computations in this study
erties and been successfully applied to understand the electronic were carried out by the Gaussian 09 program package.
structure of molecular systems [17–19]. Compared with some calcula-
tion methods based on wave function theory, DFT has some characteris- 3. Results and Discussion
tics like more simple, convenient and accurate, which can accurately
describe the molecular structure and spectral characteristics. Barbee 3.1. Ground-state geometric configuration
et al. [17] employed the DFT method to reveal the effects of substituent
group on electronic structure and geometric configurations. These stud- The octaethyl-porphyrin has a special entirely symmetrical struc-
ies set the bench mark to consider the possible existing forms of ture, and the main body structure is porphin. The calculated model
metalloporphyrins. Biktagirov group [18] explained the electron- and key atoms are marked as shown in Fig. 1. In this paper, the series
nuclear double resonance features of crude oil by density functional the- of metal porphyrins were optimized by DFT method to obtain the low-
ory calculations and it could be attributed to some known vanadium- est energy configurations. The optimized results and molecular confor-
based porphyrin structural forms. However, the different metals in por- mations were shown in Fig. 2. According to the optimized structure, the
phyrins and their intramolecular effects on the macrocyclic conjugated porphyrin structures of Ni, Co and Cu have the symmetry of planarity
π-system are still unclear, as well as the law between the molecular and D4h, while the structure of the porphyrin central cavity with vana-
structure of porphyrins and the changes in the ultraviolet spectrum. dium oxide has C4v symmetry.
Therefore, this paper aims to grasp the relationship between the central The calculated molecular model parameters were compared with
metal and the physicochemical properties of porphyrins from the mo- the experimental data of the X-ray diffraction crystal structure [25,28,
lecular level of the porphyrin spatial geometry, electronic arrangement 33]. The results are shown in Table 1. It could be found that, although
and molecular orbital properties, and expects to predict and guide ex- the calculated key parameters were well-matched, subtle difference
perimental research. still existed in the geometric structures of the metalloporphyrin with
As we all know, different metal octaethyl-porphyrins and their crys- different central metals, and the calculated bond lengths were slightly
tal molecular structures have been widely studied [20–23]. Since the longer than the experimental values. However, the error value was
1970s, various kinds of parameters have been obtained, such as bond less than 0.01 nm, and the bond angle errors were no more than 1°.
length, bond angle and dihedral angle, by X-ray crystal diffraction ex- Above all, the calculated results were greatly close to the experimental
periment. Meyer [24] and his coworkers first got the crystal structure values, and the calculated bond length between the different central
data of Ni (OEP), where after, Molinaro [25] studied crystal and molec- metal and ligand N was followed by: V\\N N Cu\\N N Co\\N N Ni\\N,
ular structure of VO (OEP), Robert Scheidt [26,27] successively mea-
sured crystal and molecular structure data of Co (OEP) and Cu (OEP)
and then a series of metalloporphyrins were compared [28]. In the
1990s, a variety of structures in the solution and their properties have
been further evaluated [29,30]. Recently, the four kinds of typical
metalloporphyrins (Ni-OEP, VO-OEP, Cu-OEP and Co-OEP) were se-
lected to recognize their intramolecular effects. The interaction of struc-
ture and visible absorption spectra of the four kinds of complexes has
been analyzed by time-dependent DFT (TD-DFT) in combination with
the conductor-like polarizable continuum model (CPCM). In order to
verify the accuracy of the calculation, the optimized structure parame-
ters were compared with X-ray crystal diffraction data. For
metalloporphyrins, the electronic structure is crucial for properties, be-
cause metalloporphyrin has the potential to provide good electron
donor and the oxidation potential. In this paper, the aim of this work
is to study the core metal electrons effect to the ligand electronic distri-
bution, which changes the energy level of the frontier molecular or-
bitals. Some other intramolecular interaction forces and bonding
relationships could be calculated by the DFT structure optimization.

2. Calculation Methods

Accurate geometry structure and spectroscopic description of the

calculation result depended on many factors strongly such as density Fig. 1. Molecular structure of octaethyl-porphyrin. (Central metal M_Ni, Co, Cu and V_O).
534 X. Wang et al. / Chinese Journal of Chemical Engineering 28 (2020) 532–540

Fig. 2. Optimized structures of octaethyl-porphyrins at B3LYP/LANL2DZ level of calculation in a front and side view: (a) Co(OEP), (b) Cu(OEP), (c) Ni(OEP), (d) V(OEP).

which was also consistent with the experimental data of X-ray crystal macrocyclic frame were listed in Table 2, which included: porphyrin
diffraction. This regularity indicated that the central metal had some in- ring nitrogen atoms N, and pyrrole ring atom Cα and Cβ, and the Cm of
fluence on the geometric structure of metalloporphyrin. In other words, binding pyrrole rings and center metal M (That was, each atomic posi-
the difference in electronic distribution might change the property of tion was shown in Fig. 1.). Meanwhile, besides the four kinds of typical
bonds. As the result, the length of C\\C covalent bonds on porphyrin metalloporphyrins, the unstable magnesium porphyrin that was previ-
rings was almost between single-bond and double-bond, which was ously investigated [37] was chosen for comparison to prove the essen-
caused by the conjugation of big π bond of porphyrin. Therefore, the tial influence of central metal on electronic distribution and stability of
C\\C covalent bonds not only had single-bond properties, but also had porphyrin structures.
the properties of double-bond. However, the C\\C covalent bonds on From Table 2, the results showed that the charge distribution on the
different sites of the porphyrin rings were slightly different. Therefore, porphyrin macrocyclic performed nonuniform, the Cα atoms connected
it could be speculated that the imparity was mainly due to the molecu- to the N and the Cm atoms which binded pyrrole rings presented higher
lar geometric configurations, and central metal d orbital electron distri- charge value than the Cβ atom. It means that the porphyrin conjugated π
bution as well as the interaction with porphyrin ligands changes. It bond produced electron delocalization effect. Furthermore, the charge
could be further discussed by using the natural bonding orbital (NBO) distribution deviations of different metalloporphyrins were mainly con-
analysis method to study the difference of electronic structure and centrated on the center metal M and the N atoms in porphyrin ring. The
bonding patterns of these molecules. charge values of the atoms indicated the imparity of their reactivity, and
the charge values of the central metal M existed in the following order:
3.2. Electronic structure and molecular orbital VO b Ni b Co b Cu b Mg. On the other hand, ligand N atoms bear charge
values that were contrary order to the central metal: Mg N Cu N Co N Ni
NBO method is often used to analyze the electron distribution of mo- N VO. The regularity reflected the stability of molecular structure, which
lecular structure, bonding type, bond order, hybrid orbital, charge trans- means that the lower the central metal charge value was, the more sta-
fer and so on. Due to the delocalized π bond system in ble the structure was. Above all, the analysis showed that the type of
metalloporphyrin, the electron distribution has critical impact on its central metal had important influence on the stability of molecular
properties, and NBO analysis can provide enough information about structure, intramolecular interaction and electronic distribution. The
the interaction among the atoms in molecular. most direct manifestation performed at the sequence of chemical
bonds, which could also be analyzed by the NBO method.
3.2.1. NBO method computes charge and electron density distribution Molecular surface electrostatic potential distribution was often used
The model structures of optimized porphyrin were analyzed by NBO as an effective tool to analyze the active site, surface charge distribution,
method to investigate the charge distribution of different part in molecular interaction and molecular initial recognition. The molecular
metalloporphyrins. The charges of key position atoms in the porphyrin electrostatic potential distribution of the metalloporphyrins with differ-
ent centers was shown in Fig. 3. Different colors in each molecule repre-
sented different electrostatic potentials. The red area indicated that the
Table 1
electrostatic potential around the atom was negative, and the positively
Parameter comparison of calculated and experimentally determined structures of the four
metalloporphyrins charged particles, which were closed to this area, would have a strong

Parameter Ni(OEP) VO(OEP) Co(OEP) Cu(OEP)

Table 2
DFT X-ray DFT X-ray DFT X-ray DFT X-ray
Calculated NBO charges of different metal octaethyl-pophyrins
Bond length/nm
M–N 0.1985 0.1929 0.2083 0.2099 0.1999 0.1971 0.2031 0.1998 NBO Charges
N–Cα 0.1390 0.1387 0.1389 0.1380 0.1390 0.1370 0.1386 0.1382 Atom Ni(OEP) VO(OEP)① Co(OEP) Cu(OEP) Mg(OEP)
Cα–Cβ 0.1455 0.1449 0.1455 0.1447 0.1455 0.1442 0.1458 0.1450
Cβ–Cβ 0.1374 0.1362 0.1378 0.1359 0.1375 0.1361 0.1377 0.1347 M 0.699 0.802 0.785 0.964 1.441
Cα–Cm 0.1381 0.1373 0.1389 0.1388 0.1384 0.1375 0.1389 0.1370 N4 −0.504 −0.494 −0.515 −0.568 −0.664
N11 −0.504 −0.494 −0.545 −0.568 −0.664
Angles/(°) N17 −0.505 −0.494 −0.515 −0.567 −0.664
N–Cα–Cm 125.1 124.0 125.0 124.3 125.1 124.8 125.1 124.2 N23 −0.505 −0.493 −0.545 −0.568 −0.664
N–Cα–Cβ 110.9 110.6 110.2 110.0 110.7 111.4 110.0 110.2 O – −0.342 – –
Cα–Cm–Cα 124.6 124.1 126.1 127.4 125.2 124.9 126.2 127.1 Cα 0.175 0.187 0.177 0.175 0.170
Cα–N–Cα 105.0 105.1 106.1 106.0 105.3 104.6 106.4 105.5 Cβ −0.038 −0.033 −0.037 −0.039 −0.042
Cβ–Cα–Cm 123.9 125.0 124.8 125.6 124.3 123.8 125.0 125.7 Cm −0.245 −0.239 −0.245 −0.245 −0.249
Cα–Cβ–Cβ 106.6 106.8 106.8 107.0 106.7 106.3 106.8 107.1 ①
The central metal of vanadium porphyrin exists in the form of vanadyl.
 X. Wang et al. / Chinese Journal of Chemical Engineering 28 (2020) 532–540 535

Fig. 3. Electrostatic potential distributions of different metalloporphyrins.

interaction, or even bonded. Correspondingly, the blue part showed that energy value E(2) was the second-order stabilization perturbation en-
the electrostatic potential around the atom was positive, and the nega- ergy. The greater the value, the stronger the electron delocalization
tively charged particles were easy to approach and combined with it. As was, and the stronger the interaction between atoms, which contrib-
shown in Fig. 3, the vanadium oxygen root of the vanadium porphyrin uted to the stability of the molecular system. Reed [40] defined this in-
had a strong electronegativity, indicating that it might interact with teraction as electron transfer interaction model (donor–acceptor model
other positively charged particles. This could make a preliminary judg- or charge transfer model). The NBO [34] analysis provided information
ment that in the asphalt and colloid, vanadium oxide porphyrin was about the Lewis and the non-Lewis (Rydberg) structure. It
likely to produce a strong association with other molecules. This pro- corresponded to the hypothetical structure of Lewis. Therefore, the elec-
vided a strong theoretical support for the prediction of non-porphyrin trons were classified as bonding electrons (BD) (electron pairs centered
structures. on two atoms), lone pairs (LP) (electron pairs centered on one atom)
and core pairs (CR) (electron pairs centered on the core of one atom),
3.2.2. Calculation and analysis of the Wiberg bond order and RY was referred as the Rydberg orbit that was beyond of the valence
In quantum chemistry, bond order [38] was the physical quantity, shell. For analyzing the interaction between central metal and ligand,
which was widely used to describe the bond strength level between ad- the electron delocalization was estimated by the second- order pertur-
jacent atoms, and Wiberg bond order was a good parameter corre- bation theory (Table 4) from the energy E(2) associated with the
sponding to chemical bonds and present bond character. In the donor-acceptor interaction between two NBOs.
metalloporphyrin structures, the bonding of metal ions and porphyrin It could be seen from the result that the charge transfer of ligand to
ligand present variability with high reactivity, Oertling [39] and this metal had some difference with different central metal. Although the
group compared the structure properties of octaethylporphyrin with function of NBOs mainly presented as the LP N atoms of ligand to LP
the mentioned bond character. Table 3 showed the calculated bond metal atom transfer, the delocalization degree was certain imparity. It
order index, the Ni (OEP) had a bond order of 2.1954, which was simi- means that some important interactions really occurred between cen-
larly equaled to double bond property in experimental recognition. tral metal and ligand. In the planar porphyrin configurations of Ni
And Mg (OEP) had the weakest bond strength of 1.0277, which means (OEP), Co (OEP) and Cu (OEP), the second-order stable perturbation en-
it had weaker stability than others. That was, the metal magnesium ergy order acted as: Ni N Co N Cu, which was consistent with the bond
was easy to remove from the molecule in the nature. In conclusion, length of optimized geometry structure. As shown in Table 1, metal Ni
the bond order offered the information of strength between metal and and ligand had stronger electron delocalization effect, and it had the
ligand as follow: VO N Ni N Co N Cu N Mg. The result also reflected the sta- shortest bond length: 0.1985 nm. The Co\\N and Cu\\N bond length
bility of the molecular structures, and matched with the result which were 0.1999 nm and 0.2031 nm, respectively. The configuration of VO
was analyzed by NBO method. The intramolecular interaction between (OEP) ligand field acted as the central pyramidal tip, in addition to the
ligands and metal ions could also be estimated by the perturbation transfer of ligand N atoms to LP metal, there was also the LP metal elec-
energy. trons feedback to ligand RY orbital, and the feedback effects contributed
to the stability of molecular structure. As a result, the bond order analy-
3.2.3. Second-order perturbation theory sis revealed that VO (OEP) had better stability.
According to perturbation theory, the orbital overlap of bond and
antibond (empty) orbitals could reduce system energy. The reducing
3.2.4. Frontier molecular orbital
Table 3 In molecular orbital theory, the frontier molecular orbitals can pro-
Wiberg bond order index(WBI) between central metal and ligand N vide an explanation for a chemical reaction, which is the determining
Wiberg bond order index (WBI)
factor of the reaction system [41]. The frontier molecular orbital energy
level distribution is closely related to the redox reaction and character-
Central metal Totals by M-N4 M-N11 M-N17 M-N23 Sum of
istic absorption spectra, which directly reflects the reaction characteris-
(M) atom M-N
tics of the system. Therefore, it was essential to discuss the frontier
Ni 2.1954 0.4831 0.4832 0.4837 0.4835 1.9335
molecular orbitals of these different metalloporphyrins for finding
V① 4.6971 0.5457 0.5446 0.5454 0.5454 2.1811
O① 2.4986 their characteristics. Ghosh [42] and his group studied the interactions
Co 2.1018 0.4676 0.4661 0.4672 0.466 1.8669 between metal d orbit and ligand orbitals. However, the influence of
Cu 1.4884 0.3315 0.3317 0.3312 0.3317 1.3261 the frontier molecular orbital distribution on the characteristic absorp-
Mg 1.0277 0.2322 0.2323 0.2320 0.2323 0.9288 tion spectrum needed to be further improved. Then, the frontier molec-
①
The central metal of vanadium porphyrin exists in the form of vanadyl. ular orbitals of the optimized porphyrin configurations were studied in
536 X. Wang et al. / Chinese Journal of Chemical Engineering 28 (2020) 532–540

Table 4
Second-order perturbation energy E(2) (donor to acceptor) (kcal·mol−1) calculated at the B3LYP/6-31++G (d,p) level calculation for the donor to acceptor interactions with higher
energy

VO(OEP) Ni(OEP) Co(OEP) Cu(OEP)

Donor Acceptor E(2) Donor Acceptor E(2) Donor Acceptor E(2) Donor Acceptor E(2)
①
LP (1) N4 LP (2) V 29.33 LP (1) N4 LP (5)Ni 35.8 LP (1) N4 LP (5)Co 17.62 LP (1) N4 LP (6)Cu 21.09
LP (1) N4 LP①(3) V 19.30 LP (1) N4 LP①(6)Ni 45.7 LP (1) N4 LP①(6)Co 23.32 LP (1) N4 LP①(7)Cu 21.09
LP (1) N4 LP①(5) V 13.91 LP (1) N4 LP①(8)Ni 25.75 LP (1) N4 LP①(8)Co 14.57 LP (1) N11 LP①(6)Cu 21.13
LP (1) N11 LP (2) V 29.23 LP (1) N11 LP (5)Ni 35.82 LP (1) N11 LP (5)Co 20.07 LP (1) N11 LP①(8)Cu 15.44
LP (1) N11 LP①(3) V 19.21 LP (1) N11 LP①(6)Ni 45.74 LP (1) N11 LP①(6)Co 23.49 LP (1) N17 LP①(6)Cu 21.07
LP (1) N11 LP①(6) V 14.03 LP (1) N11 LP①(7)Ni 25.80 LP (1) N11 LP①(7)Co 14.59 LP (1) N17 LP①(7)Cu 15.44
LP (1) N17 LP (2) V 29.22 LP (1) N17 LP (5)Ni 35.95 LP (1) N17 LP (5)Co 17.60 LP (1) N23 LP①(6)Cu 21.13
LP (1) N17 LP①(3) V 19.24 LP (1) N17 LP①(6)Ni 45.81 LP (1) N17 LP①(6)Co 23.31 LP (1) N23 LP①(8)Cu 15.44
LP (1) N17 LP①(5) V 13.66 LP (1) N17 LP①(8)Ni 25.8 LP (1) N17 LP①(8)Co 14.57
LP (1) N23 LP (2) V 29.33 LP (1) N23 LP (5)Ni 35.84 LP (1) N23 LP (5)Co 20.06
LP (1) N23 LP①(3) V 19.20 LP (1) N23 LP①(6)Ni 45.75 LP (1) N23 LP①(6)Co 23.49
LP (1) N23 LP①(6) V 13.48 LP (1) N23 LP①(7)Ni 25.78 LP (1) N23 LP①(7)Co 14.59
LP①(3) V RY①(2) N4 26.91
LP①(3) V RY①(3) N4 11.74
LP①(3) V RY①(2) N11 26.59
LP①(3) V RY①(3) N11 14.00
LP①(3) V RY①(2) N17① 26.83
LP①(3) V RY①(3) N17 12.19
LP①(3) V RY①(2) N23 26.79
LP①(3) V RY①(3) N23 12.68
①
The subscripts 4, 11, 17, and 23 present the nitrogen number on ligand pyrrole ring.

this paper. Fig. 4 had shown Kohn–Sham frontier orbital diagram, and with porphyrin ligand molecular orbital symmetry. According to the
the energy level distribution diagram were shown in Fig. 5. molecule orbit theory, metalloporphyrin not only formed σ bond be-
Four orbital model theory [43] considers that, the character peaks of tween the ligand and the central metal, but also existed π bond between
porphyrin derive from the degree of degeneracy of the highest occupied the metal d electron and the ligand lone pair electrons. As for open shell
molecular orbital (HOMO) and HOMO-1 associating with orbital energy system, VO (OEP) SOMO present as dxy orbital with characteristic of an-
level transition to the lowest unoccupied molecular orbital (LUMO) and tibonding orbital and have little impact to energy level of ligand orbital.
LUMO+1. As shown in Fig. 4, the HOMO and HOMO-1 of Ni (OEP) had On the other hand, only one electron of VO porphyrin occupied on dxy
the similar orbital properties compared with the single occupied molec- orbital, its dπ orbital would not interact with porphyrin ligand molecular
ular orbital (SOMO) SOMO-1 and SOMO-2 of the other three orbitals. Conversely, the dπ orbitals of Co (OEP), Cu (OEP) and Ni (OEP)
metalloporphyrins, which were mainly composed of the degenerate Pz were occupied four electrons, and which could form feedback π bond
orbit of C and N atoms on the porphyrin ring, and belonged to the big with porphyrin ring. As a consequence, Co (OEP) and Cu (OEP) SOMO
π orbital of porphyrin rings. The LUMO and LUMO+1 of Ni (OEP) also would be slightly lower than VO (OEP) molecule SOMO, and the
had similar π orbitals compared with the LUMO and LUMO + 1 of LUMO and LUMO + 1 energies of VO (OEP) would stay at a lower
other three metalloporphyrins. However, the atomic orbitals of the level. In other words, the feedback π bond would arise the transition en-
LUMO and LUMO+1 of the Ni (OEP) were different from those of the ergy from ground state to excited state. According to the formula: λ =
other three metalloporphyrins, which could be caused by the difference hc/ΔE(ΔE is the energy difference between two transition orbits; h is
of the electron delocalization due to the interaction between porphyrin the Plunk constant; c is the velocity of light), the ultraviolet characteris-
ring ligands and central metals. Combining the frontier orbital shape tic absorption peaks of VO (OEP) would appear in a relatively long
(Fig. 4) with molecular orbital energy level diagram (Fig. 5), the impar- wavelength or absorption peaks would occur redshift. The speculation
ity of SOMO energies was caused by the differences of d orbit electron would be verified in Section 3.3 through the analysis of ultraviolet
distribution. As a consequence, this could explain the root cause of the spectrum.
similarity and dissimilarity of ultraviolet absorption band that belonged
to different metalloporphyrins, which was indeed found in the simu- 3.3. Excited state and UV absorption spectra properties
lated UV spectra, as detailed below.
The electroneutral Ni (OEP) molecule has an even number of elec- The wavelength distribution of ultraviolet absorption spectrum is
trons, and the ground state is singlet state with closed shell system. determined by the energy difference between the transition energy
On the other hand, the electroneutral VO (OEP), Co (OEP) and Cu levels, which reflects the distribution of energy levels within the mole-
(OEP) molecules have an odd number of electrons, and they are open cule, and is an important basis for the qualitative analysis. According to
shell system. Their ground states are doublet state, and they all have Gouterman's four orbital theory model, the ultraviolet absorption spec-
the single occupied molecular orbital (SOMO). However, the SOMO tra characteristic peaks of metalloporphyrin compounds belong to π →
was turned out to be significantly different, and it was the result of π* transitions on porphyrin macrocyclic ring. The electronic absorption
the metal d orbital energy level splitting which was affected by ligand spectra of metalloporphyrin will be affected by central metal ions and
field and the occupied electronic numbers of metal d orbitals. According the around substituents. Different structure types of porphyrin com-
to the ligand field theory [44,45], the 5 items of d orbitals split into four plexes present definitely different ultraviolet absorption spectrum
groups in the D4h field, energy level from high to low respectively are: with characteristic peaks. Chin-Kuen Tai [46] and his group studied
dx2-y2, dxy, dz2, dxz and dyz，in C4v field, energy level form high to the zinc porphyrin and the influence of side chains and substitute
low are: dx2-y2, dz2, dxy, dxzd and yz. As could be seen from the VO groups. As a result, they found some groups caused ultraviolet spectrum
(OEP) molecular diagram of Fig. 4, the SOMO was mainly made up of redshift and broaden peaks. Stoyanov [18,47] researched porphyrin
dxy orbital of V atom. However, Co (OEP) molecular SOMO was mainly axial coordination heteroatomic group influence on absorption spec-
formed of dz2 orbital of Co atom, and Cu (OEP) molecular SOMO was trum, and found that the axial ligand made molecular response intensity
mainly made up of dx2-y2 orbital of Cu atom, and both of them matched reduced, and the location of the characteristic peak shifted.
 X. Wang et al. / Chinese Journal of Chemical Engineering 28 (2020) 532–540 537

+1 +1 +1 +1

Fig. 4. Frontier orbitals of four kinds of metal octaethyl-porphyrins.

To explore the root cause of the different band position in the spec-
trum, TD-DFT method combining with IEFPCM under 6-31 ++G (d,
p) and LANL2DZ basis set was quite appropriate for simulation and
had been successfully applied [48,49]. The absorption spectra of four
kinds of metalloporphyrins in toluene solvent were simulated, and the
absorption peaks of four kinds of metalloporphyrins in toluene solvent
were analyzed by ultraviolet spectrophotometer. The calculation and
experimental results were summarized in Fig. 6.
It could be found from Fig. 6 that the quantum chemistry calculation
method could efficiently simulate the characteristic absorption band of
ultraviolet absorption spectra. Due to the calculation model in a
completely ideal state, the result of characteristic peaks had a little dif-
ference. However, it can be found that the location rules of the four
kinds of metalloporphyrins calculated absorption characteristic peaks
were consistent with the experimental ones, and the Soret band peaks
were calculated respectively: Co (OEP): 382 nm b Ni (OEP): 383 nm
b Cu (OEP): 391 nm b VO (OEP): 401 nm, as shown in Table 5. The rel-
ative errors of each peak and the experimental data were within 3%, in-
dicating that the calculated results could match the experimental
Fig. 5. Orbital energies of the frontier orbitals. results very well. Moreover, the TD-DFT method could obtain the
538 X. Wang et al. / Chinese Journal of Chemical Engineering 28 (2020) 532–540

Fig. 6. Comparison of simulated electronic absorption spectra of four metal octaethyl-porphyrins and experimental result of UV spectra.

molecular orbital, energy and vibration intensity of each absorption transition between two of the highest occupied molecular orbitals
peak. The characteristic peak electron transitions and the molecular or- HOMO (SOMO) and HOMO-1 (SOMO-1), and two of the lowest unoccu-
bitals showed a great deal of information for the molecular properties. pied degenerate molecular orbital LUMO and LUMO-1. The transition
The results could not only reproduce the experimental spectra, but energy of Soret band absorption characteristic peaks was at about 3.1
also analyze the attribution problem of the electron transition of absorp- to 3.2 eV, Q band absorption characteristic peak transition energies
tion characteristic peaks in detail, and the specific results were summa- were at around 2.3 eV to 2.4 eV, which was mainly caused by different
rized in Table 6. molecular orbital energy levels. In addition, in the relatively high con-
As can be seen from the results of Table 6, in order to clarify the elec- centration metalloporphyrin samples, the experimental ultraviolet ab-
tronic transition of different central metal porphyrin derivatives, the sorption spectrum could be found that some transition response with
calculated spectra of these compounds were analyzed in detail of band low-rise strength appeared in the 300–360 nm band of the spectrum.
wavelength, oscillator strength and MO configurations. Basically, the The calculation analysis which showed that these transitions were
four kinds of metalloporphyrin Soret band and Q band had the same SOMO-4 (HOMO-4), SOMO-5 and SOMO-6 (HOMO-6) to the lowest un-
types of transition, which also conformed to the Gouterman's Four Or- occupied orbital, these transitions also belonged to π → π* transitions on
bital Theory. The characteristic peaks were derived from the electron the porphyrin rings with electrons in different atoms. Thus, from the
perspective of the calculated ultraviolet spectrum, the electronic transi-
Table 5 tion of porphyrins had such common characters: the characteristic ab-
Comparison of simulated characteristic peak and experimental data of four metal sorption bands mainly occurred on π electron conjugated system of
octaethyl-porphyrins UV spectra the porphyrin macrocycle; In addition to the characteristic absorption
Molecular Absorption peak λcal./nm λexp./nm Relative error bands, some low intensity absorption peaks could clearly be seen in ex-
periment by increasing the concentration of porphyrin samples, and
Ni(OEP) Soret 383 393 2.5%
Q 513 518 1.0%
this could be verified by simulation; The difference was that the electron
552 configuration of the center metal or substituents on macrocyclic ring
VO(OEP) Soret 401 407 1.5% would induce the electron delocalization, and it would make the posi-
Q 534 534 0 tion and intensity of ultraviolet characteristic peak difference.
571
As a result, the location and intensity of the ultraviolet peaks would
Co(OEP) Soret 382 394 3.0%
Q 513 518 1.0% shift with the structure and central metal changes. These thought-
552 provoking findings induced the conjecture that many undiscovered
Cu(OEP) Soret 391 400 2.3% conceivable porphyrin derivative might also exist in nature, the reasons
Q 521 526 1.0% for the structures could not be detected might be that: firstly, the inter-
562
actions between metalloporphyrin and some asphaltene in heavy oil led
 X. Wang et al. / Chinese Journal of Chemical Engineering 28 (2020) 532–540 539

Table 6
Calculated wavelengths (nm), oscillator strengths (f), and composition in terms of molecular orbital excitations for the most relevant transitions of octaethyl-porphyrins

Compound Absorption wavelengths/nm f ΔE/eV MO/character

Ni(OEP) 513.34 0.0449 2.4153 H-1 → L(8.7%),H-1 → L + 1(25.4%),H → L(47.7%),H → L + 1(16.3%)

383.17 1.1412 3.2357 H-1 → L(33.1%),H-1 → L + 1(27.4%),H → L(15.4%),H → L + 1(18.6%)
348.84 0.041 3.5542 H-4 → L(72.7%),H-4 → L + 1(20.7%)
316.54 0.1533 3.9169 H-6 → L(85.4%),H-6 → L + 1(10.7%)
VO(OEP) 533.77 0.0315 2.3228 S-1 → L + 1(18.1%),S → L(31.5%),S-2 → L(β)(18.8%),S-1 → S(β)(30.4%)
533.64 0.0312 2.3234 S-1 → L(18.1%),S → L + 1(31.3%),S-2 → S(β) (18.7%),S-1 → L(β)(30.3%)
401.37 0.9243 3.089 S-1 → L + 1(21.4%),S → L(13.3%),S-2 → L(β) (21.9%),S-1 → S(β)(13.2%)
401.16 0.9262 3.0906 S-1 → L(21.4%),S → L + 1(13.3%),S-2 → S(β) (21.9%),S-1 → L(β)(13.2%)
356.52 0.0445 3.4776 SOMO→LUMO+2(87.8%)
355.93 0.0414 3.4833 SOMO→LUMO+3(84.9%)
344.14 0.1825 3.6027 SOMO-1 → LUMO+2(83.1%)
343.61 0.1786 3.6083 SOMO-1 → LUMO+3(83.9%)
329.03 0.1777 3.7682 SOMO-6 → LUMO(45.7%),SOMO-6 → SOMO(β)(47.3%)
328.96 0.1807 3.7689 SOMO-6 → LUMO+1(46.2%),SOMO-6 → LUMO(β)(47.8%)
Co(OEP) 513.58 0.0506 2.4141 S-1 → L + 1(17.2%),S → L(31.9%),S-2 → L(β)(17.3%),S-1 → S(β)(33.2%)
511.71 0.035 2.4229 S-1 → L(18.7%),S → L + 1(30.4%),S-2 → S(β) (18.8%),S-1 → L(β)(30.9%)
382.13 1.1801 3.2446 S-1 → L(28.1%),S → L + 1(17.9%),S-2 → S(β)(28%),S-1 → L(β)(18.2%)
380.95 1.12004 3.2546 S-1 → L + 1(30.1%)S → L(16.7%),S-2 → L(β)(30.0%),S-1 → S(β)(17.0%)
351.78 0.1195 3.5245 SOMO-4 → LUMO(43.5%),SOMO-5 → SOMO(β)(46.9%)
347.47 0.0774 3.5682 SOMO-4 → LUMO+1(44.9%),SOMO-5 → LUMO(β)(47.3%)
318.90 0.1279 3.8878 SOMO-5 → LUMO(48.2%),SOMO-6 → SOMO(β)(48.5%)
316.86 0.1462 3.9129 SOMO-5 → LUMO+1(48%),SOMO-6 → LUMO(β)(48.1%)
Cu(OEP) 521.49 0.0346 2.3775 S-1 → L + 1(20.1%),S → L(28.2%),S-2 → L + 1(β)(17.5%),S-1 → L(β)(33.0%)
521.32 0.0338 2.3783 S-1 → L(20.2%),S → L + 1(28.1%),S-2 → L(β)(17.6%),S-1 → L + 1(β)(32.9%)
390.78 1.0427 3.1727 S-1 → L(27.1%),S → L + 1(16.7%),S-2 → L(β) (26.4%),S-1 → L + 1(β) (17.6%)
390.72 1.0608 3.1732 S-1 → L + 1(30.1%),S → L(16.7%),S-2 → L + 1(β)(30.0%),S-1 → L(β) (17.0%)
387.19 0.013 3.2021 SOMO-6 → SOMO(β)(93.2%)
386.87 0.0185 3.2048 SOMO-5 → LUMO(88.1%)
357.57 0.0211 3.4674 S-4 → L(11.0%),S-3 → L(15.9%),S-2 → L(22.9%),S-5 → L(β)(41.0%)
357.10 0.0195 3.472 S-4 → L + 1(14.0%),S-3 → L + 1(14.5%),S-2 → L + 1(20.6%),S-5 → L(β)(42.7%)
323.84 0.2178 3.8286 SOMO-6 → LUMO(48.1%),SOMO-6 → LUMO(β)(47.4%)
323.73 0.2191 3.8298 SOMO-6 → LUMO+1(48.0%),SOMO-6 → LUMO+1(β)(47.3%)

to the change of the porphyrin ring structure, which changed the elec- the same rule for electronic transition. In addition, the simulation re-
tron transition rule in the porphyrin ring and caused the undetectable search on absorption peak further found that in the experiment, some
spectra [42]; Secondly, outer substituent group changed the electron low-rise absorption ultraviolet peaks between 300 and 360 nm bands
delocalization circumstance of porphyrin macrocycle, so that it could were verified by increasing the concentration of the samples. It indi-
not be detected by ultraviolet spectra; Thirdly, some similar molecules cated that the absorption peak electronic transitions and their attribu-
with different constituent atoms existed in porphyrin derivatives, tion research deserve further excavation, which would help to find
which interfered with identification. The above studies provide theoret- more porphyrin structures and new series of spectra laws.
ical basis and data support for discovering more metalloporphyrins and
proposing a new method to identify porphyrin structures.
Acknowledgements
4. Conclusions
The authors acknowledge the supports from the National Natural
Science Foundation of China (21822810, 21476260, and 21838011),
Using DFT method of quantum chemistry, the optimized structures,
and are grateful to Quan Shi professor in the State Key Laboratory of
electronic properties and some other bond rules for four different cen-
Heavy Oil Processing, China University of Petroleum (Beijing).
tral metal octaethyl porphyrins were obtained. The internal interaction
between central metal and ligand was evaluated by NBO method. Tak-
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