Distinctive features of the structure of hemihexaphyrazine complexes with Y, La, and Lu according to quantum chemical data

Accepted Manuscript Distinctive features of the structure of hemihexaphyrazine complexes with Y, La, and Lu according to quantum chemical data Yuriy A. Zhabanov, Nina I. Giricheva, Alexander V. Zakharov, Mikhail K. Islyaikin PII:

S0022-2860(16)30704-9

DOI:

10.1016/j.molstruc.2016.07.033

Reference:

MOLSTR 22736

To appear in:

Journal of Molecular Structure

Received Date: 14 May 2016 Revised Date:

5 July 2016

Accepted Date: 9 July 2016

Please cite this article as: Y.A. Zhabanov, N.I. Giricheva, A.V. Zakharov, M.K. Islyaikin, Distinctive features of the structure of hemihexaphyrazine complexes with Y, La, and Lu according to quantum chemical data, Journal of Molecular Structure (2016), doi: 10.1016/j.molstruc.2016.07.033. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT Distinctive features of the structure of hemihexaphyrazine complexes with Y, La, and Lu according to quantum chemical data Yuriy A. Zhabanova, Nina I. Girichevab, Alexander V. Zakharova, Mikhail K. Islyaikina. a

Ivanovo State University of Chemistry and Technology, Research Institute of Chemistry

of Macroheterocyclic Compounds, Sheremetev av. 7, 153000 Ivanovo, Russian Federation. Fax: b

RI PT

+7 (4932) 417995; Tel: +7 (4932)359874; E-mail: [email protected] Ivanovo State University, Ermak st. 39, 153025 Ivanovo, Russian Federation.

Dedicated to Prof. Georgiy V. Girichev on the Occasion of his 70th birthday. Abstract

SC

The molecular structure of Y, La, and Lu complexes with hemihexaphyrazine (Нр), a sixlink heteroazaporphyrinoid of АВАВАВ type, has been studied by DFT. It has been found that

M AN U

these MHp (M = Y, La, Lu) complexes have a non-planar structure of Cs symmetry with the metal atom dislocated from the center of the cavity to one of the thiadiazole rings. The average lengths of coordination bonds formed by the metal atom with six nitrogen atoms of the thiadiazole moieties are 2.389, 2.566, and 2.358 Å in YHp, LaHp, and LuHp, respectively. Different degrees of deviation from planar structure have been determined in La complex and Y and Lu complexes, characterized by the values of the N-N...N-N torsion angle between

TE D

nonequivalent N-N bonds in two thiadiazole rings (38.2, 56.0, and 58.6 degrees, respectively). At the same time the internal circumferences of the macrocycle are the same in all three complexes. It has been shown that the planar structures of the complexes of the D3h symmetry

EP

are saddle points on the PES. The transition barriers between the structures of Cs and D3h symmetries have been computed (40.5, 4.6, and 52.4 kJ/mol for YHp, LaHp, and LuHp, respectively).

AC C

An NBO analysis of the electron density distribution in MHp complexes has been carried

out and the nature of coordination bonds in the complexes has been examined. We suppose the coordination bonds in the complexes as three-center ones involving atom M and two nitrogen atoms of Nt-Nt bond in the thiadiazole moieties , and the Hp ligand as a quasi tridentate one, despite the fact that the metal atom is bonded to six nitrogen atoms of the ligand. The value of the lanthanide contraction ∆rLn (0.208 Å) in the examined LnHp complexes with one ligand has been determined, which turned out to be close to ∆rLn values in the series of lanthanide halogenides with three monovalent ligands and in the series of lanthanide compounds with three bidentate ligands.

ACCEPTED MANUSCRIPT

Keywords: macroheterocycle, hemihexaphyrazine, yttrium, lanthanum and lutetium complexes, molecular structure, nature of coordination bonds, transition barriers, lanthanide contraction. Introduction Among the huge diversity of macroheterocyclic compounds (Mc) a special attention can be

RI PT

drawn on six-link heteroazaporphyrinoids of АВАВАВ type whose macroheterocyclic backbone is formed by alternating thiadiazole (А) and pyrrole/isoindole (В) cycles linked together by azabridges [1-3].

Since the unsubstituted Мс turned out to be extremely difficult to solve in organic solvents

SC

[4], the synthesis was mostly directed to obtaining АВАВАВ type heteroazaporphyrinoids with bulky substituents [5-9], allowing to perform their chromatographic purification. The obtained Мс were characterized by mass spectrometry, IR and NMR spectroscopy, elemental analysis,

M AN U

and quantum chemical calculations carried out at the semiempirical level [10]. The structure of the АВАВАВ type Мс was determined for the first time for the tri(tert-butyl)substituted compound [11, 12], followed by the unsubstituted one [13], with the application of a joint method combining gas-phase electron diffraction with mass spectrometric monitoring of the gas phase

composition

and

density

functional

theory

calculations.

The

structure

of

TE D

hexa(pentoxy)substituted Мс in the solid state was investigated by X-ray analysis [14]. On the ground of these studies it has been determined that the structure of the АВАВАВ type Мс is based on the six-link macrocycle having a planar structure, whose internal conjugation system is a [30]heteroannulene. Thiadiazole moieties are oriented in such a way that

EP

their nitrogen atoms form stable intramolecular hydrogen bonds with hydrogen atoms of cyclic imino groups, substantially stabilizing the molecule.

AC C

Such structure suggests the development of extraordinary coordination properties (compared

to porphyrins and phthalocyanines): the enlarged coordination cavity is able to accommodate up to three atoms of transition metals [1, 2, 7, 15]. The structure of the complexes is validated by the data of mass spectrometry, IR and NMR spectroscopy, and elemental analysis. The ability of the АВАВАВ type Мс to coordinate metals with large covalent radii, for example, lanthanides, is especially interesting. There is a description in the literature [16] of an attempt to obtain complexes of tert-butyl-substituted АВАВАВ type Мс with lanthanum, lutetium and thulium. On the basis of mass spectrometry data the authors concluded that, considering their large covalent radii, these metals are able to form complexes of 1:1 composition.

ACCEPTED MANUSCRIPT

In the present study the prediction of the molecular structure of hemihexaphyrazine complexes with Y(III), La(III), and Lu(III) has been made, their electronic characteristics have been computed, and the nature of the coordination bond has been described based on the analysis of the electron density distribution. The La atom has one of the largest covalent radii among trivalent atoms. Consideration and comparison of properties of the La and Lu complexes is important for determining the value of lanthanide contraction, which may differ significantly

RI PT

from the lanthanide contraction in series of other lanthanide compounds, such as Ln(thd)3 [1719] (where thd is a bidentate ligand, O2C11H19) or LnHal3 [20-24] (Hal = F, Cl, Br, I), containing three ligands in contrast to hemihexaphyrazine complexes. The Y atom (a d-block element) has been chosen for comparison with the Lu atom of their ability to form complexes. These atoms

SC

and their triple-charged ions have similar sizes, significantly smaller than the atom and ion of lanthanum. Therefore, the study is focused on the direction and the value of hemihexaphyrazine

Computational details

M AN U

ligand deformation depending on the size and nature of the central atom.

The study of the molecular structure of МC30N15H12S3 (М = Y, La, Lu) has been carried out by the density functional theory method (DFT, B3LYP functional) with the use of DZV [25] and cc-pVTZ [26, 27] basis sets for describing the electron shells of C, N, S, and H atoms. For describing the core electron shells of the yttrium atom three different pseudopotentials combined

TE D

with corresponding basis sets were used. In all three cases (RSC 1997 [28], cc-pVTZ-PP [29], and def2-TZVPP [30]) 28 core electron shells were described by pseudopotentials and 11 valence electrons were described by basis sets. In case of the lanthanum atom 46 core electron

EP

shells were described by pseudopotentials and 11 valence electrons were described by LANL2DZ [31] and Def2-TZVPP [30] basis sets, correspondingly. For the description of 11 valence electrons of the Lu atom a double-ζ valence [32] and triple-ζ valence [32, 33] basis sets

AC C

were used and 60 core shells were described by an effective core pseudopotential [34] developed by the Stuttgart group. All calculations were carried out using the Firefly QC package [35], which is partially based on the GAMESS (US) [36] source code. Results and discussion

Molecular structure of the complexes. Since the metal-free hemihexaphyrazine (H3Hp) has a planar structure whose internal conjugation system is a [30]heteroannulene [13], a structure with the metal atom in the center of the planar Hp ligand has been chosen as a starting point. Irrespective of the basis sets used in the geometry optimization, a structure of Cs symmetry (Fig. 1), in which the ligand has a non-planar structure and the metal atom is dislocated from the center of the cavity to one of the thiadiazole rings, has been obtained for all three complexes. Major geometrical parameters of the Сs

ACCEPTED MANUSCRIPT

symmetry equilibrium geometry of the complexes are given in Table 1. The magnitude of dislocation of the metal atom from the ligand center is reflected by the difference of three M-Nt values (Table 2), which amounts to 0.04 Å in YHp complex, 0.06 Å in LuHp, and a lower value of 0.016 Å in LaHp. At the same time the three isoindole cycles are located at almost the same distances from the central atom (Table 1, М...N distance between the metal atom and the nitrogen atoms in the isoindole moieties).

RI PT

Fig. 1 shows the optimized structures of three MHp complexes. Different degrees of the deviation from planarity in La complex and Y and Lu complexes are clearly visible. It may be characterized by the value of Nt-Nt...Nt-Nt torsion angle between nonequivalent Nt-Nt bonds of two thiadiazole rings, which is significantly lower in LaHp complex (Table 1). It is interesting

SC

to note that the central metal atom and the nitrogen atoms of the isoindole moieties are located almost in the same plane (Table 1, N...N...N...M torsion angle is close to zero) in all three

AC C

EP

TE D

M AN U

complexes of the Сs symmetry.

ACCEPTED MANUSCRIPT

b

AC C

EP

TE D

M AN U

SC

RI PT

a

c

Fig. 1. Optimized structures of LaHp (top, a), LuHp (center, b) and YHp (bottom, c) complexes. The view of YHp demonstrates non-planar deformation of the complex.

ACCEPTED MANUSCRIPT

In molecules of metallocomplexes of porphyrins, porphyrazines and phthalocyanines, depending on the size of the central atom, ligand conformations of dome, twisting, saddle, ruffling [37-47], etc. types may appear, but in all these cases all the four coordination bonds are of the same length. Since the ligand in the complexes under consideration is a cyclic trimer (АВ)3 and not a non-equality of coordination bonds appears.

RI PT

tetramer, its deformation may be conditionally referred as a saddle-type deformation, in which a

Structural nonrigidity of YHp, LaHp, and LuHp complexes and deformation directions of the ligand in the complexes.

Structural nonrigidity of the considered complexes may be due to the transition between

SC

the saddle and planar configurations. In order to estimate the barrier of such transition, geometry optimization and vibrational frequency calculations within the limits of D3h symmetry of the

EP

TE D

M AN U

complexes have been carried out (Fig. 2).

AC C

Fig. 2. Molecular structure of the complexes of D3h symmetry, which is a saddle point, (left)

and geometrical structure of the triple-charged Нр3- ligand (right).

It has turned out that the structures of D3h symmetry are second-order saddle points. The

modes of vibration of the doubly degenerate imaginary frequencies correspond to non-planar deformation of the macrocycle. The energy differences between planar and saddle-type structures of metallocomplexes are shown in Table 1. It appears that Y and Lu complexes may be considered rigid, while a low barrier of transition between the structures of Cs and D3h symmetries in the lanthanum complex shows its structural nonrigidity. Since complex compounds are usually represented as consisting of a positively charged central ion and a negatively charged ligand, in order to compare geometrical and electronic

ACCEPTED MANUSCRIPT

characteristics of the complexes and to find the causes of stability of Cs structures we have determined the equilibrium structure of the ligand ion (having 3- charge), which has been found to have D3h symmetry. We should note the following interesting fact: the internal macrocycle circumference remains constant, equal to 36.10(5) Å, irrespective of the nature of the metal and the macrocycle symmetry (Cs and D3h), same as in Нр3- ligand ion and in H3Hp metal-free compound [13].

RI PT

In all planar structures of the considered metallocomplexes and the Hp3- ion (D3h symmetry) the isoindole moieties are at the same distance from each other (re(N…N) is equal to 6.701, 6.695, and 6.702 Å for Y, La, and Lu complexes, respectively). The thiadiazole moieties are shifted to the direction of the central atom in the complexes, which causes an elongation of Nt-Nt

SC

and Ct -Nt bonds and an insignificant shortening of other bonds in the internal macrocycle, compared to ones in Hp3- (Table 1). The largest changes are in the values of C-Nm-Ct, Nm-Ct-Nt,

M AN U

and Nm-C-N valence angles.

By comparing the structures of Сs and D3h symmetries it may be shown (Table 1) that the molecular structure of the studied metallocomplexes of Cs symmetry may be explained by the adjustment of the ligand cavity to the size of the central ion in a way that produces shortening and strengthening of the coordination bonds without changing the internal macrocycle

AC C

EP

TE D

circumference.

ACCEPTED MANUSCRIPT Table 1: Some geometrical parameters (Å, degrees) of the Hp3- ligand ion, the averaged parameters of MHp metallocomplexes of Cs symmetry and the parameters of planar D3h structures. The relative energies ∆E (kJ/mol) of the complexes of planar and non-planar structures. YHp

Nt -Nt

1.331

M...N

Cs

D3h

Cs

2.389

2.478

2.566

1.375

1.387

1.373

3.615

3.869

3.761 1.328

1.315

1.331

1.342

Ct-Nm

1.357

1.347

1.345

C-Nm

1.321

1.315

1.307

C-N

1.350

1.344

∠(C-Nm-Ct)

121.9

117.8

∠(Nm-Ct-Nt)

129.0

131.5

∠(Nm-C-N)

129.7

124.6

∠(Nt-Nt...Nt-Nt)

0

56.0

∆E, DZV ∆E, cc-pVTZ

Cs

D3h

2.598

2.358

2.459

1.378

1.378

1.390

3.865

3.588

3.869

1.333

1.331

1.343

1.343

1.342

1.347

1.346

1.314

1.311

1.316

1.307

1.337

1.349

1.346

1.343

1.336

119.1

119.6

120.2

117.4

118.9

134.8

131.2

132.4

131.5

135.2

123.6

125.9

125.5

124.4

123.3

0

38.2

0

58.6

0

-3.3

0

-1.0

0

-4.3

0

0

52.7

0

6.0

0

67.5

0

40.5

0

4.6

0

52.4

TE D

∠(N...N...N...M)

D3h

M AN U

Ct -Nt

LuHp

SC

M-Nt *

LaHp

RI PT

Hp3-

EP

* Signification on atoms is shown in figure 1. The nature of coordination bond in the studied complexes

AC C

Usually donors of lone electron pairs in macroheterocyclic compounds are nitrogen atoms found in pyrrole or isoindole moieties. However, in case of the complexes considered in the present study the M...N internuclear distances between the central atom and the nitrogen atoms in the isoindole moieties are large (Table 1) and, consequently, these atoms are not within the coordination sphere of the central atom. Among ligand atoms the closest to the central atom are the nitrogen atoms of the thiadiazole moieties. In works [48-51] structures of complexes where each pyrazole moiety forms coordination bonds with two adjacent copper atoms, and each copper atom – with two pyrazole moieties (Fig. 3) were studied. The considered complexes have a fundamentally different nature of coordination bonds when compared to both porphyrins, porphyrazies, and phthalocyanines and to complexes similar to those studied in works [48-51].

RI PT

ACCEPTED MANUSCRIPT

SC

Fig. 3. Structural formula of Cu3(µ 3-O)(µ-pz)3Cl31- complex studied in work [48].

M AN U

NBO analysis of electron density distribution currently is a demonstrative method of describing the nature of bonds in molecules of different classes [52]. We performed such analysis for all studied complexes of Y, La, and Lu (at DFT/B3LYP/cc-pVTZ level). Electronic configurations of atoms in molecule, energies of donor-acceptor interactions (E(2)) between lone pairs of Nt atoms and unoccupied orbitals of central atoms, computed by second-order perturbation theory, and NPA atom charges (Tables 2 and 3) have been examined.

TE D

The mentioned characteristics allow to describe the nature of coordination bonds in these complexes.

Table 2. Internuclear distances (R, Å), bond orders (B) estimated using Wiberg scheme, sums of energies ΣE(2) (kcal/mol) of donor-acceptor interaction between lone pairs of Nt nitrogen

EP

atoms and the nd and (n+1)s orbitals of the central atom. YHp

LuHp

B

ΣE(2) a

R

B

ΣE(2)

R

B

ΣE(2)

AC C

R

LaHp

M-Ntb

2.409

0.182

37.8

2.578

0.181

42.3

2.380

0.183

42.8

M-Ntb

2.370

0.198

38.0

2.562

0.189

42.0

2.334

0.200

43.3

M-Ntb

2.388

0.198

35.3

2.559

0.191

43.9

2.361

0.199

35.8

M-Ntc

2.478

0.179

30.5

2.597

0.182

35.5

2.459

0.173

31.2

a

The interactions between lone pairs of nitrogen atoms and dxy and dx222-y222 atomic orbitals of

the metal make the main contribution (Fig. 4). b

Complexes of Cs symmetry have three pairs of non-equivalent nitrogen atoms and three

different bond distances M-Nt. c

Characteristics of the coordination bond in the complexes of planar D3h structure;

ACCEPTED MANUSCRIPT

Bond orders of M-Nt bonds (Table 2) allow to argue that this bond, along with an ionic component (Table 3), has a covalent component. Moreover, the M-Nt bond order В in the complexes under consideration is close to M-O bond orders in such coordination compounds as B(thd)3, Al(thd)3, Ga(thd)3, In(thd)3, Tl(thd)3 [54] and is higher than these ones in the series of Ln(thd)3 [19], except for Lu(thd)3. It may be seen from the data presented in Tables 2 and 3 that the highest energy of the donor-acceptor interaction for M-Nt bonds is in the La complex. The

RI PT

strongest interaction appears between lone pairs of nitrogen atoms and dxy and dx222-y222 atomic orbitals of the atom of metal (Fig. 4). Unlike the Cu3(µ 3-O)(µ-pz)3Cl31- [49] complex (Fig. 3), where a lone pair of one of the nitrogen atoms of Nt-Nt bond interacts with a d-shell orbital of one copper atom and a lone pair of the other nitrogen atom of Nt-Nt bond interacts with a d-shell

SC

orbital of another copper atom, in the complexes considered in this study both lone pairs of the two nitrogen atoms of Nt-Nt bond interact with a d-shell orbital of the central atom (see Fig. 4).

M AN U

Therefore, two nitrogen atoms of Nt-Nt bond in the studied MHp complexes can be considered as a single donor unit, and the Hp ligand as a quasi tridentate, despite the fact that the atom of

EP

TE D

metal is bonded to six nitrogen atoms of the ligand.

b

c

b

c

AC C

a

a

ACCEPTED MANUSCRIPT

Fig. 4. Lone pairs of the nitrogen atoms of the Nt-Nt bond (a), dxy atomic orbital and dx2-y2 atomic orbital of the central atom (b), and the result of their donor-acceptor interaction (c).

Table 3. NPA atom charges (Q) and electronic configurations of atoms in HpH3 ligand, its ion Hp3- and complexes of Cs symmetry.

-

-

2.243

2.264

2.250

-

-

[core]5s0.114d0.63

[core]6s0.074f0.125d0.54

[core]6s0.135d0.60

-0.302

-0.236

-0.458 -0.474

-0.454 -0.458

-0.457 -0.477

[core]2s1.382p4.04

[core]2s1.392p4.06

-0.536 -0.540

-0.534 -0.544

[core]2s1.362p4.15

[core]2s1.352p4.16

[core]2s1.362p4.15

-0.578 -0.596

-0.578 -0.589

-0.579 -0.599

[core]2s1.412p4.15

[core]2s1.422p4.14

[core]2s1.412p4.16

[core]2s1.402p3.87 [core]2s1.392p3.81 -0.504

-0.571

-0.534 -0.543

[core]2s1.342p4.14 [core]2s1.352p4.19 Q

-0.580

-0.497

SC

Q

[core]2s1.392p4.06

RI PT

LuHp

M AN U

N

LaHp

[core]2s1.282p4.29 [core]2s1.422p4.05

Electronic configurations of the central atoms in the complexes show that the concept of complexes as systems consisting of M3+ metal ions and Hp3- ligands is in need of refinement. The total occupancy of the valence orbitals of the central atom is about 0.7. Moreover, d-shell orbital is the most occupied, and in case of La atom the occupancy of 4f shell atomic orbitals is

TE D

Nm

Q

YHp

noticeable, which is due to their high energy (close to the energy of 5d shell orbitals) and to their larger size, compared to similar 4f shell orbitals of lutetium atom that may be considered core orbitals, [53]. NPA charges on the central atoms (Table 3) as well as their electronic

EP

Nt

Q

Hp3-

configurations, gave evidence of the migration of electron density from the ligand ion, 3-, to the metal ion, 3+.

In this case, the electron density of the ligands in complexes redistributed, so as to provide

AC C

M

HpH3

the formation of strong coordination bonds. Thus, the donor nitrogen atoms Nt have 2s1.371.39

2p4.04-4.06 electronic configuration,

ascertaining the presence of a negative charge on these

atoms, which is noticeably larger in these complexes than in HpH3 and its Hp3- ion. Lanthanide contraction The value of lanthanide contraction ∆rLn, which may be estimated as a difference between r(La-Nt) и r(Lu-Nt) distance values, is equal to 0.208 Å for the complexes of Сs symmetry. The averaged values of r(Ln-Nt), presented in Table 1, were used in the calculation. It should be noted that the obtained value of ∆rLn is close to similar experimental values in the series of LnL3 with monovalent ligands, such as the series of trichlorides (0.186(8) Å), tribromides (0.185(8)

ACCEPTED MANUSCRIPT

Å), and triiodides (0.193(8) Å) [20-24, 53], as well as in the series of compounds with bidentate ligands, for example, in the series of tris-dipivaloylmethanates (0.186(6)Å)

[17-18]. The

closeness of ∆rLn in lanthanide compounds with three ligands and in LnHp complexes with one ligand considered in the present study indicates that, irrespective of the size of the central atom in the lanthanide series, hemihexaphyrazine is sufficiently flexible as a ligand to form robust coordination bonds with the central atom. However, if the rigidity of the ligand is increased by

RI PT

restricting its ability of non-planar deformation (retaining D3h symmetry), the value of lanthanide contraction (Table 1) becomes only 0.139 Å. At the same time r(La-Nt) is elongated only by 0.032 Å from the optimal value in the complex of Cs symmetry, and r(Lu-Nt) is elongated by 0.101 Å. Hence, the size of the lanthanum atom is just right while the lutetium atom is too small

SC

for the planar ligand.

Since the existence of LaHp and LuHp complexes is validated by mass-spectrometric

M AN U

data [16], the analysis of computation results allows to conclude that the considered complexes have a non-planar structure, and the coordination cavity of the ligand is able to deform for creating the strongest possible coordination bonds. Conclusion

It has been found that, unlike the metal-free hemihexaphyrazine, which has a planar structure, its complexes with Y, La, and Lu have non-planar macrocycle structure of Cs

TE D

symmetry, where LaHp complex has the lowest distortion of the macrocycle from planarity, since the size of the central atom corresponds best of all to the size of the coordination cavity of the ligand.

It has been shown that the ligand cavity can adjust itself to the size of the central atom in

EP

a way that result in contraction and strengthening of the coordination bonds without changing the circumference of the internal macrocycle.

AC C

It has been found that the LaHp complex possesses a structural nonrigidity agreeing with a low barrier of transition between the structures of Cs and D3h symmetries. The nature of coordination bonds in MHp complexes has been examined. It has been

shown that two nitrogen atoms of the Nt-Nt bonds in thiadiazole moieties of the ligand can be considered as a single donor unit, and the Hp ligand as a quasi tridentate one, despite the fact that the metal atom is bonded to six nitrogen atoms of the ligand. The value of the lanthanide contraction ∆rLn in the studied LnHp complexes with one ligand has been determined, which turned out to be close to ∆rLn in the series of lanthanide halogenides with three monovalent ligands and in the series of lanthanide compounds with three bidentate ligands. Acknowledgment: this work was supported by grant of the President of the Russian Federation (project MK-6073.2016.3).

ACCEPTED MANUSCRIPT

AC C

EP

TE D

M AN U

SC

RI PT

[1] M.K. Islyaikin, E.A. Danilova, L.D. Yagodarova, M.S. Rodríguez-Morgade, T. Torres, Org. Lett. 3(14) (2001) 2153–2156. [2] N. Kobayashi, S. Inagaki, V.N. Nemykin, T. Nonomura, Angew. Chem., Int. Ed. 40(14) (2001) 2710–2712. [3] J.L. Sessler, D. Seidel, Angew. Chem. Int. Ed. 42(42) (2003) 5134–5175. [4] O.N. Trukhina, Yu.A. Zhabanov, A.V. Krasnov, E.A. Danilova, M.K. Islyaikin, Journal of Porphyrins and Phthalocyanines 15(11-12) (2011) 1287-1291. [5] E.A. Danilova, T.V. Melenchuk, O.N. Trukhina, A.V. Zakharov, M.K. Islyaikin, Macroheterocycles 2(5) (2010) 33-37. [6] N.V. Bumbina, E.A. Danilova, V.S. Sharunov, S.I. Filimonov, I.G. Abramov, M.K. Islyaikin, Mendeleev Commun 18(5) (2008) 289-290. [7] M.S. Filatov, O.N. Trukhina, M.K. Islyaikin, Macroheterocycles 7(3) (2014) 281-286. [8] E.A. Danilova, N.V. Bumbina, M.K. Islyaikin, Macroheterocycles 4(1) (2011) 47-49. [9] E.A. Danilova, M.K. Islyaikin, S.Yu. Shtrygol, Izvestiya Akademii nauk. Seriya Khimicheskaya 7 (2015) 1610-1615. [10] M.K. Islyaikin, E.A. Danilova, L.D. Yagodarova, Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol., 46(2) (2003) 3-7. [11] A.V. Zakharov, S.A. Shlykov, N.V. Bumbina, E.A. Danilova, A.V. Krasnov, M.K. Islyaikin, G.V. Girichev, Chem. Commun. (2008) 3573–3575. [12] A.V. Zakharov, S.A. Shlykov, E.A. Danilova, A.V. Krasnov, M.K. Islyaikin, G.V. Girichev, Phys. Chem. Chem. Phys. 11 (2009) 8570–8579. [13] Yu.A. Zhabanov, A.V. Zakharov, S.A. Shlykov, O.N. Trukhina, E.A. Danilova, O.I. Koifman, M.K. Islyaikin, Journal of Porphyrins and Phthalocyanines 17(03) (2013) 220-228. [14] O.N. Trukhina, M.S. Rodríguez-Morgade, S. Wolfrum, E. Caballero, N. Snejko, E.A. Danilova, E. Gutiérrez-Puebla, M.K. Islyaikin, D.M. Guldi, T. Torres, J. Am. Chem. Soc. 132(37) (2010) 12991–12999. [15] E.A. Danilova, M.K. Islyaikin, Macroheterocycles 5(2) (2012) 157-161. [16] N.V. Bumbina, E.A. Danilova, M.K. Islyaikin, Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol. 51(6) (2008) 15-17. [17] N.I. Giricheva, N.V. Belova, S.A. Shlykov, G.V. Girichev, N. Vogt, N.V. Tverdova, J. Vogt, Journal of Molecular Structure 605(2–3) (2002) 171-176. [18] N.V. Belova, G.V. Girichev, S.L. Hinchley, N.P. Kuzmina, D.W.H. Rankin, I.G. Zaitzeva, Dalton Transactions (11) (2004) 1715-1718. [19] V.V. Sliznev, N.V. Belova, G.V. Girichev, Computational and Theoretical Chemistry 1055 (2015) 78-87. [20] N.I. Giricheva, A.V. Zakharov, S.A. Shlykov, G.V. Girichev, Journal of the Chemical Society, Dalton Transactions (19) (2000) 3401-3403. [21] A.V. Zakharov, N. Vogt, S.A. Shlykov, N.I. Giricheva, J. Vogt, G.V. Girichev, Structural Chemistry 14(2) (2003) 193-197. [22] A.V. Zakharov, N. Vogt, S.A. Shlykov, N.I. Giricheva, I.E. Galanin, G.V. Girichev, J. Vogt, Journal of Molecular Structure 707(1–3) (2004) 147-152.

AC C

EP

TE D

M AN U

SC

RI PT

ACCEPTED MANUSCRIPT [23] S.A. Shlykov, N.I. Giricheva, E.A. Lapykina, G.V. Girichev, H. Oberhammer, Journal of Molecular Structure 978(1–3) (2010) 170-177. [24] N.I. Giricheva, S.A. Shlykov, E.A. Lapykina, H. Oberhammer, G.V. Girichev, Structural Chemistry 22(2) (2011) 385-392. [25] T.H. Dunning, The Journal of Chemical Physics 53(7) (1970) 2823-2833. [26] J. Dunning, J. Chem. Phys. 90(2) (1989) 1007-1024. [27] D.E. Woon, T.H.J. Dunning, J. Chem. Phys. 98(2) (1993) 1358-1372. [28] M. Dolg, H. Stoll, H. Preuss, R.M. Pitzer, J. Phys. Chem. 97(22) (1993) 5852–5859. [29] K.A. Peterson, D. Figgen, M. Dolg, H. Stoll, Journal of Chemical Physics 126(12) (2007) 124101-124113. [30] F. Weigend, R. Ahlrichs, Phys. Chem. Chem. Phys. Design and assessment of accuracy 7(18) (2005) 3297-3305. [31] P.J. Hay, W.R. Wadt, J. Chem. Phys. 82(1) (1985) 270-284. [32] J. Yang, M. Dolg, Theor. Chem. Acc. 113(4) (2005) 212-224. [33] A. Weigand, X. Cao, J. Yang, M. Dolg, Theoretical Chemistry Accounts 126(3) (2009) 117-127. [34] M. Dolg, H. Stoll, A. Savin, H. Preuss, Theoretica chimica acta 75(3) (1989) 173-194. [35] A.A. Granovsky, Firefly version 8, www http://classic.chem.msu.su/gran/firefly/index.html. [36] M.W. Schmidt, K.K. Baldridge, J.A. Boatz, S.T. Elbert, M.S. Gordon, J.H. Jensen, S. Koseki, N. Matsunaga, K.A. Nguyen, S. Su, T.L. Windus, M. Dupuis, J.A. Montgomery, J. Comput. Chem. 14(11) (1993) 1347-1363. [37] V. V. Sliznev, A. E. Pogonin, A. A. Ischenko, G. V. Girichev, Macroheterocycles 7(1) (2014) 60-72. [38] T. Vangberg, A. Ghosh, Journal of the American Chemical Society 121(51) (1999) 12154-12160. [39] P.M. Kozlowski, J.R. Bingham, A.A. Jarzecki, The Journal of Physical Chemistry A 112(50) (2008) 12781-12788. [40] E. Meyer, Jnr, Acta Crystallographica Section B 28(7) (1972) 2162-2167. [41] P.M. Kozlowski, T.S. Rush, A.A. Jarzecki, M.Z. Zgierski, B. Chase, C. Piffat, B.-H. Ye, X.-Y. Li, P. Pulay, T.G. Spiro, The Journal of Physical Chemistry A 103(10) (1999) 1357-1366. [42] K.K. Anderson, J.D. Hobbs, L. Luo, K.D. Stanley, J.M.E. Quirke, J.A. Shelnutt, Journal of the American Chemical Society 115(26) (1993) 12346-12352. [43] N. Kobayashi, R. Kondo, S. Nakajima, T. Osa, Journal of the American Chemical Society 112(26) (1990) 9640-9641. [44] A.F. Cozzolino, Q. Yang, I. Vargas-Baca, Crystal Growth & Design 10(11) (2010) 4959-4964. [45] Y. Zorlu, U. Kumru, U. Isci, B. Divrik, E. Jeanneau, F. Albrieux, Y. Dede, V. Ahsen, F. Dumoulin, Chemical Communications 51(30) (2015) 6580-6583. [46] S.O. Sanusi, E. Antunes, T. Nyokong, Journal of Porphyrins and Phthalocyanines 17(10) (2013) 920-927. [47] T. Kojima, T. Nakanishi, T. Honda, S. Fukuzumi, Journal of Porphyrins and Phthalocyanines 13(01) (2009) 14-21.

AC C

EP

TE D

M AN U

SC

RI PT

ACCEPTED MANUSCRIPT [48] P.A. Angaridis, P. Baran, R. Boča, F. Cervantes-Lee, W. Haase, G. Mezei, R.G. Raptis, R. Werner, Inorganic Chemistry 41(8) (2002) 2219-2228. [49] G. Mezei, J.E. McGrady, R.G. Raptis, Inorganic Chemistry 44(21) (2005) 7271-7273. [50] L.-L. Wang, Y.-M. Sun, Z.-Y. Yu, Z.-N. Qi, C.-B. Liu, The Journal of Physical Chemistry A 113(39) (2009) 10534-10539. [51] Y. Sanakis, M. Pissas, J. Krzystek, J. Telser, R.G. Raptis, Chemical Physics Letters 493(1–3) (2010) 185-190. [52] E.D. Glendening, J.K. Badenhoop, A.E. Reed, J.E. Carpenter, J.A. Bohmann, C.M. Morales, F. Weinhold, http://www.chem.wisc.edu/~nbo5 (2004). [53] A.A. Ischenko, G.V. Girichev, Yu.I. Tarasov, Difraktciya elektronov: struktura i dinamika svobodnykh molekul i kondensirovannogo sostoyaniya veshestva, Fizmatlit (2012). [54] N.V. Belova, V.V. Sliznev, T.A. Zhukova, G.V. Girichev, Computational and Theoretical Chemistry 967(1) (2011) 199-205.

ACCEPTED MANUSCRIPT

AC C

EP

TE D

M AN U

SC

RI PT

It has been found that, complexes with Y, La, and Lu have non-planar macrocycle structure of Cs symmetry. It has been shown that the ligand cavity can adjust itself to the size of the central atom in a way that result in contraction and strengthening of the coordination bonds without changing the circumference of the internal macrocycle. It has been found that the LaHp complex possesses a structural nonrigidity agreeing with a low barrier of transition between the structures of Cs and D3h symmetries. It has been shown that two nitrogen atoms of the Nt-Nt bonds in thiadiazole moieties of the ligand can be considered as a single donor unit, and the Hp ligand as a quasi tridentate one, despite the fact that the metal atom is bonded to six nitrogen atoms of the ligand. The value of the lanthanide contraction ∆rLn in the studied LnHp complexes with one ligand has been determined, which turned out to be close to ∆rLn in the series of lanthanide halogenides with three monovalent ligands and in the series of lanthanide compounds with three bidentate ligands.