Introductory Chapter: Chirality from Molecular Electronic States

*Takashiro Akitsu*

## **1. Chiral assembly of proteins and metal complexes**

Needless to say, chirality is an important concept along the fields of biology, chemistry, and physics. Not only steric fitness (stereochemical aspects) but also electronic properties (or electronic states as origin) may be important in such cases, which is a motivation to emphasis the concept of this book.



#### **Table 1.**

*GOLD scores of docking copper(II) complexes into lysozyme. Detailed study of the best four complexes will be reported elsewhere.*

In recent years, in order to prepare "artificial metalloproteins" composed of natural proteins (typically egg white lysozyme) including synthesized metal complexes (salen-type Cu(II) complexes), we searched and investigated candidate metal complexes using crystal structure databases (CSD [1–24] and PDB). In this context, we used a GOLD program to search well docking features between proteins and ligand of small molecules structurally and obtained docking scores (**Table 1**). As for molecular structures, DFT calculations from a Gaussian 09 program may be useful to obtain not only optimized structures but also detailed electronic states of metal complexes in principle.

At least proteins must be a hard target to discuss. Once I asked to my collaborator of computational chemical physics, "I will ask you DFT calculations of

**3**

**Figure 1.**

*Simulated UV-vis and CD spectra for La(III)-Cu(II) complex [27].*

*Introductory Chapter: Chirality from Molecular Electronic States*

molecules, I can simulate it and improve the assignments."

simulated IR spectra of them. Moreover, I also want to know simulated IR spectra of amide I, II, and some other bands for typical proteins such as lysozyme." Then he replied, "When you'll send me the data, I'll continue with the assignment. I don't know how long do you like the discussion of the vibrational bands, and what are the most interested bands for you. Additionally, strong bands corresponding to intermolecular H-bands appear in the exp. spectrum. If you have the X-ray data of these

Even employing achiral metal complexes, such hybrid assembly must be a chiral

In the case of chiral salen-type metal complexes, it is not easy to investigate their electronic properties using both experimental and theoretical methods. Previously, we have systematically studied on preparations, crystal structures, and electronic states for mononuclear (3d) [25–27] and binuclear (3d-4f) [28–32] complexes. Besides X-ray crystallography and IR spectra, CD and UV-vis spectra, XAS spectra, fluorescence spectra, and magnetic measurements were used. However, not all

material, which can be experimentally elucidated by means of chiroptical spectroscopy (CD or VCD) [25] as well as quenching of fluorescence intensity (obeying Stern-Volmer plot) [26]. However, calculations of electronic state for such hybrid assembly must be difficult only by means of these conventional or commercially available programs at present [27]. In this way, supramolecular chirality may be one

**2. Chiral metal complexes by spectroscopy, magnetism, and** 

*DOI: http://dx.doi.org/10.5772/intechopen.83835*

of the challenging targets in near future.

**computational interpretation**

#### *Introductory Chapter: Chirality from Molecular Electronic States DOI: http://dx.doi.org/10.5772/intechopen.83835*

*Chirality from Molecular Electronic States*

**2**

**Table 1.**

*reported elsewhere.*

metal complexes in principle.

In recent years, in order to prepare "artificial metalloproteins" composed of natural proteins (typically egg white lysozyme) including synthesized metal complexes (salen-type Cu(II) complexes), we searched and investigated candidate metal complexes using crystal structure databases (CSD [1–24] and PDB). In this context, we used a GOLD program to search well docking features between proteins and ligand of small molecules structurally and obtained docking scores (**Table 1**). As for molecular structures, DFT calculations from a Gaussian 09 program may be useful to obtain not only optimized structures but also detailed electronic states of

*GOLD scores of docking copper(II) complexes into lysozyme. Detailed study of the best four complexes will be* 

At least proteins must be a hard target to discuss. Once I asked to my collaborator of computational chemical physics, "I will ask you DFT calculations of simulated IR spectra of them. Moreover, I also want to know simulated IR spectra of amide I, II, and some other bands for typical proteins such as lysozyme." Then he replied, "When you'll send me the data, I'll continue with the assignment. I don't know how long do you like the discussion of the vibrational bands, and what are the most interested bands for you. Additionally, strong bands corresponding to intermolecular H-bands appear in the exp. spectrum. If you have the X-ray data of these molecules, I can simulate it and improve the assignments."

Even employing achiral metal complexes, such hybrid assembly must be a chiral material, which can be experimentally elucidated by means of chiroptical spectroscopy (CD or VCD) [25] as well as quenching of fluorescence intensity (obeying Stern-Volmer plot) [26]. However, calculations of electronic state for such hybrid assembly must be difficult only by means of these conventional or commercially available programs at present [27]. In this way, supramolecular chirality may be one of the challenging targets in near future.

## **2. Chiral metal complexes by spectroscopy, magnetism, and computational interpretation**

In the case of chiral salen-type metal complexes, it is not easy to investigate their electronic properties using both experimental and theoretical methods. Previously, we have systematically studied on preparations, crystal structures, and electronic states for mononuclear (3d) [25–27] and binuclear (3d-4f) [28–32] complexes. Besides X-ray crystallography and IR spectra, CD and UV-vis spectra, XAS spectra, fluorescence spectra, and magnetic measurements were used. However, not all

**Figure 1.** *Simulated UV-vis and CD spectra for La(III)-Cu(II) complex [27].*

methods are valid at the same time for one complex of a certain combination of 3d and 4f metal ions, for example, some complexes were diamagnetic, and some complexes did not exhibit emission. Hence, we also carried out DFT or semiempirical molecular orbital calculations as well as these experiments. However, 4f metal ions having many electrons usually took a long time to calculate with DFT accurately and the results often deviated from the corresponding experimental data largely (for example, simulated CD spectrum shown in **Figure 1**).

In conclusion, beyond stereochemical aspects, chirality may be important, though there are limited methods to elucidate their electronic states in particular theoretically such as chiroptical spectra and expanding supramolecular functions at present.

## **Author details**

Takashiro Akitsu Department of Chemistry, Faculty of Science, Tokyo University of Science, Tokyo, Japan

\*Address all correspondence to: akitsu2@rs.tus.ac.jp

© 2019 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

**5**

*Introductory Chapter: Chirality from Molecular Electronic States*

[7] Freiburg C, Reichert W, Melchers M, Engelen B. N,N'-Ethylenbis(1 iminomethyl-2-naphtholato)kupfer(II) und N,N'-Ethylenbis(1-iminomethyl-2-naphtholato)nickel(II) Acta

Crystallographica B. 1980;**36**:1209-1211. DOI: 10.1107/S056774088000564X

[8] Karakas A, Elmali A, Unver H, Kara H, Yahsi Y. Synthesis, Structure, Spectroscopic Studies and ab-initio Calculations on First Hyperpolarizabilities of N,N'-Bis(2-hydroxy-1-

naphthylmethylidene)-1-methyl-1,2 diaminoethane-N,N',O,O'-copper(II). Zeitschrift für Naturforschung B.

[9] Li F, Mei C, Tao R. Henan Daxue Xuebao. Ziran Kexueban. 2006;**36**:32

Debnath M, Jana AD, Ali M. Copper(II) induced oxidative modification and complexation of a schiff base ligand: synthesis, crystal structure, catalytic oxidation of aromatic hydrocarbons and DFT calculation. RSC Advances. 2014;**4**:34248-34256. DOI: 10.1039/

[11] Xie QF, Chen YM, Huang ML. {4, 4′-Dibromo-2, 2′-[ethane-1, 2-diylbis (nitrilomethylidyne)] diphenolato} copper (II). Acta Crystallographica E. 2009;**65**:m903-m903. https://doi. org/10.1107/S1600536809024015

[12] Clegg W, Harrington RW. CCDC ANEMAJ (Private Communication)

[13] Rigamonti L, Demartin F, Forni A, Righetto S, Pasini A. Copper(II) complexes of salen analogues with two differently substituted (push-pull) salicylaldehyde moieties. A study on the modulation of electronic asymmetry and nonlinear optical properties. Inorganic Chemistry. 2006;**45**:10976- 10989. DOI: 10.1021/ic0613513

[10] Biswas S, Dutta A, Dolai M,

2006;**61**:968-974

C4RA06078D

*DOI: http://dx.doi.org/10.5772/intechopen.83835*

[1] Bhadbhade MM, Srinivas D. Effects on molecular association, chelate conformation, and reactivity toward substitution in copper Cu(5-X-salen) complexes, salen2- = N,N'-ethyleneb is(salicylidenaminato), X = H, CH3O, and Cl: Synthesis, X-ray structures, and EPR investigations. Inorganic Chemistry. 1993;**32**:6122-6130. DOI:

10.1021/ic00078a037

**References**

10.1039/B406009A

1997;**34**:355-366

1998;**17**:4179-4187

2010.533762

[2] Thomas F, Jarjayes O, Duboc C, Philouze C, Saint-Aman E, Pierre JL. Intramolecularly hydrogen-bonded versus copper(II) coordinated monoand bis-phenoxyl radicals. Dalton Transactions. 2004:2662-2669. DOI:

[3] Yao HH, Huang WT, Lo JM, Liao FL, Wang SL. European. Journal of Solid State Inorganic Chemistry.

[4] Bunce S, Cross RJ, Farrugia LJ, Kunchandy, S, Meason LL, Muir KW, Odonnell M, Peacock RD, Stirling D, Teat SJ. Chiral Schiff base complexes of copper (II), vanadium (IV) and nickel (II) as oxidation catalysts. X-ray crystal structures of [Cu (R-salpn) (OH2)] and [Cu (±-busalcx)]. Polyhendron.

[5] Raisanen MT, Kinga M, Nieger M, Repo T, Structural and spectroscopic characterization of Cu(salen) complexes bearing long alkoxy chains. Journal of Coordination Chemistry. 2010;**63**:4280- 4289. https://doi.org/10.1080/00958972.

[6] Paschke R, Balkow D, Sinn E. Lowering Melting Points in Asymmetrically Substituted Salen-Copper(II) Complexes Exhibiting Mesomorphic Behavior. Structure of the Mesogen Cu(5-hexyloxySalen). Inorganic Chemistry. 2002;**41**:1949- 1953. DOI: 10.1021/ic010875u

*Introductory Chapter: Chirality from Molecular Electronic States DOI: http://dx.doi.org/10.5772/intechopen.83835*

## **References**

*Chirality from Molecular Electronic States*

**4**

**Author details**

Takashiro Akitsu

Japan

provided the original work is properly cited.

\*Address all correspondence to: akitsu2@rs.tus.ac.jp

© 2019 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium,

Department of Chemistry, Faculty of Science, Tokyo University of Science, Tokyo,

methods are valid at the same time for one complex of a certain combination of 3d and 4f metal ions, for example, some complexes were diamagnetic, and some complexes did not exhibit emission. Hence, we also carried out DFT or semiempirical molecular orbital calculations as well as these experiments. However, 4f metal ions having many electrons usually took a long time to calculate with DFT accurately and the results often deviated from the corresponding experimental data largely

In conclusion, beyond stereochemical aspects, chirality may be important, though there are limited methods to elucidate their electronic states in particular theoretically such as chiroptical spectra and expanding supramolecular functions at present.

(for example, simulated CD spectrum shown in **Figure 1**).

[1] Bhadbhade MM, Srinivas D. Effects on molecular association, chelate conformation, and reactivity toward substitution in copper Cu(5-X-salen) complexes, salen2- = N,N'-ethyleneb is(salicylidenaminato), X = H, CH3O, and Cl: Synthesis, X-ray structures, and EPR investigations. Inorganic Chemistry. 1993;**32**:6122-6130. DOI: 10.1021/ic00078a037

[2] Thomas F, Jarjayes O, Duboc C, Philouze C, Saint-Aman E, Pierre JL. Intramolecularly hydrogen-bonded versus copper(II) coordinated monoand bis-phenoxyl radicals. Dalton Transactions. 2004:2662-2669. DOI: 10.1039/B406009A

[3] Yao HH, Huang WT, Lo JM, Liao FL, Wang SL. European. Journal of Solid State Inorganic Chemistry. 1997;**34**:355-366

[4] Bunce S, Cross RJ, Farrugia LJ, Kunchandy, S, Meason LL, Muir KW, Odonnell M, Peacock RD, Stirling D, Teat SJ. Chiral Schiff base complexes of copper (II), vanadium (IV) and nickel (II) as oxidation catalysts. X-ray crystal structures of [Cu (R-salpn) (OH2)] and [Cu (±-busalcx)]. Polyhendron. 1998;**17**:4179-4187

[5] Raisanen MT, Kinga M, Nieger M, Repo T, Structural and spectroscopic characterization of Cu(salen) complexes bearing long alkoxy chains. Journal of Coordination Chemistry. 2010;**63**:4280- 4289. https://doi.org/10.1080/00958972. 2010.533762

[6] Paschke R, Balkow D, Sinn E. Lowering Melting Points in Asymmetrically Substituted Salen-Copper(II) Complexes Exhibiting Mesomorphic Behavior. Structure of the Mesogen Cu(5-hexyloxySalen). Inorganic Chemistry. 2002;**41**:1949- 1953. DOI: 10.1021/ic010875u

[7] Freiburg C, Reichert W, Melchers M, Engelen B. N,N'-Ethylenbis(1 iminomethyl-2-naphtholato)kupfer(II) und N,N'-Ethylenbis(1-iminomethyl-2-naphtholato)nickel(II) Acta Crystallographica B. 1980;**36**:1209-1211. DOI: 10.1107/S056774088000564X

[8] Karakas A, Elmali A, Unver H, Kara H, Yahsi Y. Synthesis, Structure, Spectroscopic Studies and ab-initio Calculations on First Hyperpolarizabilities of N,N'-Bis(2-hydroxy-1 naphthylmethylidene)-1-methyl-1,2 diaminoethane-N,N',O,O'-copper(II). Zeitschrift für Naturforschung B. 2006;**61**:968-974

[9] Li F, Mei C, Tao R. Henan Daxue Xuebao. Ziran Kexueban. 2006;**36**:32

[10] Biswas S, Dutta A, Dolai M, Debnath M, Jana AD, Ali M. Copper(II) induced oxidative modification and complexation of a schiff base ligand: synthesis, crystal structure, catalytic oxidation of aromatic hydrocarbons and DFT calculation. RSC Advances. 2014;**4**:34248-34256. DOI: 10.1039/ C4RA06078D

[11] Xie QF, Chen YM, Huang ML. {4, 4′-Dibromo-2, 2′-[ethane-1, 2-diylbis (nitrilomethylidyne)] diphenolato} copper (II). Acta Crystallographica E. 2009;**65**:m903-m903. https://doi. org/10.1107/S1600536809024015

[12] Clegg W, Harrington RW. CCDC ANEMAJ (Private Communication)

[13] Rigamonti L, Demartin F, Forni A, Righetto S, Pasini A. Copper(II) complexes of salen analogues with two differently substituted (push-pull) salicylaldehyde moieties. A study on the modulation of electronic asymmetry and nonlinear optical properties. Inorganic Chemistry. 2006;**45**:10976- 10989. DOI: 10.1021/ic0613513

[14] Assey G, Butcher RJ, Gultneh Y. Acta Crystallographica E. {3,3′,5,5′-Tetramethoxy-2,2′-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato}copper(II)2010;**66**:m653-m653. https://doi.org/10.1107/ S1600536810017137

[15] Arici C, Ercan F, Atakol O, Cakirer O. Aqua[N,N'-bis(salicylidene)-1,3 propanediaminato]copper(II)Acta Crystallographica C. 1999;**55**:1654-1655. DOI: 10.1107/S010827019900894X

[16] Akhtar F, Drew MGB. Structures of N,N'-propylenebis[(2-hydroxy-1 naphthyl)methaniminato]nickel(II) and N,N'-propylenebis[(2-hydroxy-1-naphthyl)methaniminato] copper(II)–0.5-dimethyl sulphoxide. Acta Crystallographica B. 1982;**38**:1149- 1154. https://doi.org/10.1107/ S0567740882005184

[17] Li XW, Xue LW, Zhang CX. Synthesis, X-Ray Structures, and Antimicrobial Activities of Nickel(II) and Copper(II) Complexes With Tetradentate Schiff Bases. Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry. 2015;**45**:512-515. https://doi.org/10.1080 /15533174.2013.841217

[18] Kitajima N, Whang K, Moro-oka K, Uchida A, Sasada Y. Oxidations of primary alcohols with a copper(II) complex as a possible galactose oxidase model. Journal of the Chemical Society, Chemical Communications. 1986: 1504-1505. DOI: 10.1039/C39860001504

[19] Chen BH, Yao HH, Huang WT, Chattopadhyay P, Lo JM, Lu TH. Syntheses and molecular structures of three Cu(II) complexes with tetradentate imine-phenols. Solid State Sciences. 1999;**1**:119-131. https://doi. org/10.1016/S1293-2558(00)80069-2

[20] Elmali A, Zeyrek CT, Elerman Y, Svoboda I. [N,N′-Bis(5-bromosalicylidene)-1,3-diaminopropane]nickel(II) and [N,N′-bis(5-chlorosalicylidene)- 1,3-diaminopropane]copper(II). Acta Crystallographica C. 2000;**56**:1302- 1304. https://doi.org/10.1107/ S0108270100010428

[21] Wang X. Aqua{6,6-dimethoxy-2,2′-[propane-1,3 diylbis(nitrilomethylidyne)] diphenolato-κ4O,N,N′,O′}copper(II) acetonitrile solvate. Acta Crystallographica E. 2009;**65**:m1658-m1658. DOI: 10.1107/ S1600536809049137

[22] Habibi MH, Mokhtari R, Harrington RW, Clegg W. [N,N′-Bis(6-methoxysalicylidene)-1,3-diaminopropane] copper(II). Acta Crystallographica E. 2007;**63**:m1998-m1998. https://doi. org/10.1107/S1600536807030723

[23] Habibi MH, Harrington RW. CCDC ANEMOX (Private Communication)

[24] Odabasoglu M, Arslan F, Olmez H, Buyukgungor O. Synthesis, crystal structures and spectral characterization of trans-bisaquabis(o-vanillinato) copper(II), cis-aquabis(o-vanillinato) copper(II) and aqua[bis(o-vanillinato)- 1,2-ethylenediimin]copper(II). Dyes and Pigments. 2007;**75**:507-515. https:// doi.org/10.1016/j.dyepig.2006.06.033

[25] Tsuda E, Mitsumoto Y, Takakura K, Sunaga N, Akitsu T, Konomi T, et al. Electrochemical tuning by polarized UV light induced molecular orientation of chiral salen-type Mn(II) and Co(II) complexes in an albumin matrix. Journal of Chemistry and Chemical Engineering. 2016;**2**:53-59. DOI: 10.17265/1934-7375/2016.02.001

[26] Hayashi T, Akitsu T. Fluorescence, UV-vis, and CD Spectroscopic Study on Docking of Chiral Salen-Type Zn(II) Complexes and Lysozyme and HSA Proteins. Threonine: Food Sources, Functions and Health Benefits. NY, USA: Nova Science Publishers Inc.; 2015. ISBN:978-1634825542

**7**

*Introductory Chapter: Chirality from Molecular Electronic States*

*DOI: http://dx.doi.org/10.5772/intechopen.83835*

[28] Akitsu T, Hiratsuka T, Shibata H. Chiroptical Properties of 3d-4f Chiral Schiff Base Magnetic Complexes. Magnets: Types, Uses and Safety. NY, USA: Nova Science Publishers, Inc.;

[29] Hiratsuka T, Shibata H, Akitsu T. Structures and Properties of 3d-4f and 3d Chiral Schiff base Complexes. Crystallography: Research, Technology and Applications. NY, USA: Nova Science Publishers, Inc.; 2012. ISBN:

[30] Shibata H, Hiratsuka T, Hayashi T, Akitsu T. Structures and Electronic Properties of Photophysical Chiral Schiff Base 3d-4f Binuclear Complexes. Integrating Approach to Photofunctional Hybrid Materials for Energy and the Environment. NY, USA: Nova Science Publishers, Inc.; 2013.

[27] Akitsu T, Yamazaki A. Semiempirical molecular orbital calculations for 3d-4f complexes towards artificial metalloproteins.

International Journal of Pharma Sciences and Scientific Research. 2017;**3**:53-54. DOI: 10.25141/2471-6782-2017-2.0049

2012. ISBN: 978-1614702511

978-1620815748

ISBN: 978-1624176388

ECB.2013.2.49

[31] Hayashi T, Shibata H, Orita S, Akitsu T. Variety of structures of binuclear chiral Schiff base Ce(III)/ Pr(III)/Lu(III)-Ni(II)/Cu(II)/Zn(II) complexes. European Chemical Bulletin. 2013;**2**:49-57. DOI: 10.17628/

[32] Orita S, Akitsu A. Variety of crystal structures of chiral Schiff base Lu(III)-Ni(II)/Cu(II)/Zn(II) and their related complexes. Open Chemistry Journal. 2014;**1**:1-14. DOI: 10.2174/1874842201401010001

*Introductory Chapter: Chirality from Molecular Electronic States DOI: http://dx.doi.org/10.5772/intechopen.83835*

[27] Akitsu T, Yamazaki A. Semiempirical molecular orbital calculations for 3d-4f complexes towards artificial metalloproteins. International Journal of Pharma Sciences and Scientific Research. 2017;**3**:53-54. DOI: 10.25141/2471-6782-2017-2.0049

*Chirality from Molecular Electronic States*

[14] Assey G, Butcher RJ, Gultneh Y. Acta Crystallographica E.

https://doi.org/10.1107/ S1600536810017137

{3,3′,5,5′-Tetramethoxy-2,2′-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato}copper(II)2010;**66**:m653-m653.

and [N,N′-bis(5-chlorosalicylidene)- 1,3-diaminopropane]copper(II). Acta Crystallographica C. 2000;**56**:1302- 1304. https://doi.org/10.1107/

[21] Wang X. Aqua{6,6-dimeth-

diphenolato-κ4O,N,N′,O′}copper(II) acetonitrile solvate. Acta Crystallographica E. 2009;**65**:m1658-m1658. DOI: 10.1107/

[22] Habibi MH, Mokhtari R, Harrington RW, Clegg W. [N,N′-Bis(6-methoxysalicylidene)-1,3-diaminopropane] copper(II). Acta Crystallographica E. 2007;**63**:m1998-m1998. https://doi. org/10.1107/S1600536807030723

[23] Habibi MH, Harrington RW. CCDC ANEMOX (Private Communication)

[24] Odabasoglu M, Arslan F, Olmez H, Buyukgungor O. Synthesis, crystal structures and spectral characterization of trans-bisaquabis(o-vanillinato) copper(II), cis-aquabis(o-vanillinato) copper(II) and aqua[bis(o-vanillinato)- 1,2-ethylenediimin]copper(II). Dyes and Pigments. 2007;**75**:507-515. https:// doi.org/10.1016/j.dyepig.2006.06.033

[25] Tsuda E, Mitsumoto Y, Takakura K, Sunaga N, Akitsu T, Konomi T, et al. Electrochemical tuning by polarized UV light induced molecular orientation of chiral salen-type Mn(II) and Co(II) complexes in an albumin matrix. Journal of Chemistry and Chemical Engineering. 2016;**2**:53-59. DOI: 10.17265/1934-7375/2016.02.001

[26] Hayashi T, Akitsu T. Fluorescence, UV-vis, and CD Spectroscopic Study on Docking of Chiral Salen-Type Zn(II) Complexes and Lysozyme and HSA Proteins. Threonine: Food Sources, Functions and Health Benefits. NY, USA: Nova Science Publishers Inc.; 2015.

ISBN:978-1634825542

S0108270100010428

oxy-2,2′-[propane-1,3 diylbis(nitrilomethylidyne)]

S1600536809049137

[15] Arici C, Ercan F, Atakol O, Cakirer O. Aqua[N,N'-bis(salicylidene)-1,3 propanediaminato]copper(II)Acta Crystallographica C. 1999;**55**:1654-1655. DOI: 10.1107/S010827019900894X

[16] Akhtar F, Drew MGB. Structures of N,N'-propylenebis[(2-hydroxy-1 naphthyl)methaniminato]nickel(II) and N,N'-propylenebis[(2-hydroxy-1-naphthyl)methaniminato] copper(II)–0.5-dimethyl sulphoxide. Acta Crystallographica B. 1982;**38**:1149-

1154. https://doi.org/10.1107/

[17] Li XW, Xue LW, Zhang CX. Synthesis, X-Ray Structures, and Antimicrobial Activities of Nickel(II) and Copper(II) Complexes With Tetradentate Schiff Bases. Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry. 2015;**45**:512-515. https://doi.org/10.1080

[18] Kitajima N, Whang K, Moro-oka K, Uchida A, Sasada Y. Oxidations of primary alcohols with a copper(II) complex as a possible galactose oxidase model. Journal of the Chemical Society, Chemical Communications. 1986: 1504-1505. DOI: 10.1039/C39860001504

[19] Chen BH, Yao HH, Huang WT, Chattopadhyay P, Lo JM, Lu TH. Syntheses and molecular structures of three Cu(II) complexes with

tetradentate imine-phenols. Solid State Sciences. 1999;**1**:119-131. https://doi. org/10.1016/S1293-2558(00)80069-2

[20] Elmali A, Zeyrek CT, Elerman Y, Svoboda I. [N,N′-Bis(5-bromosalicylidene)-1,3-diaminopropane]nickel(II)

S0567740882005184

/15533174.2013.841217

**6**

[28] Akitsu T, Hiratsuka T, Shibata H. Chiroptical Properties of 3d-4f Chiral Schiff Base Magnetic Complexes. Magnets: Types, Uses and Safety. NY, USA: Nova Science Publishers, Inc.; 2012. ISBN: 978-1614702511

[29] Hiratsuka T, Shibata H, Akitsu T. Structures and Properties of 3d-4f and 3d Chiral Schiff base Complexes. Crystallography: Research, Technology and Applications. NY, USA: Nova Science Publishers, Inc.; 2012. ISBN: 978-1620815748

[30] Shibata H, Hiratsuka T, Hayashi T, Akitsu T. Structures and Electronic Properties of Photophysical Chiral Schiff Base 3d-4f Binuclear Complexes. Integrating Approach to Photofunctional Hybrid Materials for Energy and the Environment. NY, USA: Nova Science Publishers, Inc.; 2013. ISBN: 978-1624176388

[31] Hayashi T, Shibata H, Orita S, Akitsu T. Variety of structures of binuclear chiral Schiff base Ce(III)/ Pr(III)/Lu(III)-Ni(II)/Cu(II)/Zn(II) complexes. European Chemical Bulletin. 2013;**2**:49-57. DOI: 10.17628/ ECB.2013.2.49

[32] Orita S, Akitsu A. Variety of crystal structures of chiral Schiff base Lu(III)-Ni(II)/Cu(II)/Zn(II) and their related complexes. Open Chemistry Journal. 2014;**1**:1-14. DOI: 10.2174/1874842201401010001

Chapter 2

Abstract

carried out.

1. Introduction

solution of glucose etc.

metamaterial is carried out.

9

Medium

Andrey Nikolaevich Volobuev

detailed method, solitary waves, standing waves

material equations selected according to a problem.

acteristics of metamaterials for example chiral parameter.

The Nonlinear Analysis of Chiral

The principle of calculation of a plate from a metamaterial with inductive type chiral inclusions is submitted. It is shown that distribution of an electromagnetic wave to such substance can be investigated with the help of introduction of a chiral parameter and on the basis of a detailed method of calculation. By comparison of two methods the dependence of chiral parameter from frequency of electromagnetic radiation falling on a plate is found. With the help of a detailed method the nonlinear equation for potential on the chiral plate is found. It is shown that this equation has solutions as solitary and standing waves but not running waves. The analysis of the received solutions of the nonlinear equation is

Keywords: metamaterial, chiral medium, chiral parameter, nonlinear equation,

Now the metamaterials (Greek "meta" outside), i.e. composite materials with the various inclusions allocated both chaotically, and periodically are widely applied in particular in a radio engineering, at designing space devices, in medicine, etc. [1–3]. Due to these inclusions the received materials have many useful physical, electric, optical and other properties which are not present at natural substances. Among metamaterials the substances with chiral properties [4] which capable to rotate a polarization plane of electromagnetic waves are distinguished. In optics as analogue of similar substances are optical active substances, for example, quartz, a

However the methods of metamaterials calculation are enough limited [5]. Basically all calculations are based on the decision of the Maxwell's equations and the

The existing method has restrictions since are usually used only averaged char-

In the present work attempt of more detailed approach to properties of the chiral inclusions into metamaterials is made also the analysis of these properties on interaction of chiral elements with the electromagnetic wave falling on a plate from a

Chapter 2
