Abstract
Phthalocyanine (Pc), a conventional dyestuff exhibiting vivid blue or green color, has been utilized as a functional molecule for application in a variety of fields due to its excellent optical and electrochemical properties. Creation of novel π-conjugated systems based on the structure of Pc with the aim of further developing unique properties has, therefore, been of a prime importance. Despite the over a hundred-year history of phthalocyanine chemistry, progress in this regard has been fairly limited mainly due to the problems inherent in the synthesis of Pc. The authors have pioneered this research area by focusing on the control of the optical properties in the visible and near-infrared regions by (1) creation of the novel π-conjugated systems and (2) introduction of perturbation that is as simple as possible to the electronic structures and have reported a variety of unprecedented Pc analogues. Considerable attention has also been focused on the structure-optical property relationships of these novel Pc compounds. This chapter summarizes the contribution of the authors to the recent advances in the chemistry of phthalocyanine as functional chromophore systems.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
(a) Kadish KM, Smith KM, Guilard R (eds) (2003) The porphyrin handbook, vol 15–20. Academic Press, San Diego; (b) Leznoff CC, Lever ABP (eds) (1989–1996) Phthalocyanines: properties and applications, vol 1–4. Wiley-VCH, New York; (c) McKeown NB (1998) In: Phthalocyanine materials: synthesis, structure and function. Cambridge University Press, Cambridge; (d) Kobayashi N, Fukuda T (2006) In: Kim S (ed) Functional dyes. Elsevier, Oxford
Braun A, Tcherniac J (1907) Über die Produkte der Einwirkung von Acetanhydrid auf Phthalamid. Ber Dtsch Chem Ges 40:2709–2714
(a) Linstead RP, Rydon HN (1934) Investigation of the olefinic acids. Part XV. The effect of peroxides on the orientation of the addition of hydrogen bromide to vinyl- and allyl-acefic acids. J Chem Soc 2001–2003; (b) Linstead RP (1934) Phthalocyanines. Part I. A new type of synthetic colouring matters. J Chem Soc 1016–1017; (c) Dent CE, Linstead RP, Lowe AR (1934) Phthalocyanines. Part VI. The structure of the phthalocyanines. J Chem Soc 1033–1039; (d) Dent CE, Linstead RP (1934) Phthalocyanines. Part IV. Copper phthalocyanines. J Chem Soc 1027–1031; (e) Byrne GT, Linstead RP, Lowe AR (1934) Phthalocyanines. Part II. The preparation of phthalocyanine and some metallic derivatives from o-cyanobenzamide and phthalimide. J Chem Soc 1017–1022
Robertson JM (1936) An X-ray study of the phthalocyanines. Part II. Quantitative structure determination of the metal-free compound. J Chem Soc 1195–1209
Kadish KM, Smith KM, Guilard R (eds) (2003) The porphyrin handbook, vol 1–10. Academic Press, San Diego
(a) Gouterman M (1959) Study of the effects of substitution on the absorption spectra of porphin. J Chem Phys 30:1139–1161; (b) Gouterman M (1961) Spectra of porphyrins. J Mol Spectrosc 6:138–163
Fukuda T, Kobayashi N (2010) In: Kadish KM, Smith KM, Guilard R (eds) Handbook of porphyrin science, vol 9. World Scientific, Singapore
Kadish KM, Smith KM, Guilard R (eds) (2003) The porphyrin handbook, vol 13. Academic Press, San Diego
(a) Sessler JL, Weghorn SJ (1997) Expanded, contracted & isomeric porphyrins. Pergamon, Oxford; (b) Sessler JL, Seidel D (2003) Synthetic expanded porphyrin chemistry. Angew Chem Int Ed 42:5134–5175
Sugita I, Shimizu S, Fukuda T, Kobayashi N (2013) Nickel and palladium complexes of seco-tribenzoporphyrazines derived from one-pot condensation of 1,3–diminoisoindoline. Tetrahedron Lett 54:1599–1601
Nemykin VN, Polshyna AE, Makarova EA, Kobayashi N, Lukyanets EA (2012) Unexpected formation of the nickel seco-tribenzoporphyrazine with a tribenzotetraazachlorin-type absorption spectrum. Chem Commun 48:3650–3652
Linstead RP, Whalley M (1952) Conjugated macrocycles. Part XXII. Tetrazaporphin and its metallic derivatives. J Chem Soc 4839–4846
Fukuda T, Kobayashi N (2008) Hydrogenated tetraazaporphyrins - old but new core-modified phthalocyanine analogues. Dalton Trans 4685–4704
(a) Mani NS, Beall LS, White AJP, Williams DJ, Barrett AGM, Hoffman BM (1994) Serendipitous desymmetrisation during porphyrazine synthesis - an X-ray crystallographic study of 2,3,7,8,12,13,17,18-octakis(Dimethylamino)-2-secoporphyrazine-2,3-dione. J Chem Soc Chem Commun 1943–1944; (b) Montalban AG, Lange SJ, Beall LS, Mani NS, Williams DJ, White AJP, Barrett AGM, Hoffman BM (1997) Seco-porphyrazines: synthetic, structural, and spectroscopic investigations. J Org Chem 62:9284–9289
MacCragh A, Koski WS (1965) The phthalocyanine of gold. J Am Chem Soc 87:2496–2497
Wong EWY, Miura A, Wright MD, He Q, Walsby CJ, Shimizu S, Kobayashi N, Leznoff DB (2012) Gold(II) phthalocyanine revisited: synthesis and spectroscopic properties of Gold(III) phthalocyanine and an unprecedented ring-contracted phthalocyanine analogue. Chem Eur J 18:12404–12410
Fernandez-Lazaro F, Torres T, Hauschel B, Hanack M (1998) Hemiporphyrazines as targets for the preparation of molecular materials: synthesis and physical properties. Chem Rev 98:563–575
Shimizu S, Zhu H, Kobayashi N (2010) Subazaphenalenephthalocyanine: a subphthalocyanine analogue bearing a six-membered ring unit. Chem Eur J 16:11151–11159
(a) Shimizu S, Zhu H, Kobayashi N (2011) Azepiphthalocyanine-an unprecedented large twist of a Π-conjugation system upon core-odification with a seven-membered ring unit. Chem Commun 47:3072–3074; (b) Shimizu S, Uemura K, Zhu H, Kobayashi N (2012) Core-modified phthalocyanine analogues with a seven-membered ring unit in place of a five-membered ring unit. Tetrahedron Lett 53:579–581
(a) Fukuda T, Makarova EA, Luk’yanets EA, Kobayashi N (2004) Synthesis and spectroscopic and electrochemical studies of novel benzo- or 2,3-Naphtho-fused tetraazachlorins, bacteriochlorins, and isobacteriochlorins. Chem Eur J 10:117–133; (b) Kobayashi N, Fukuda T (2002) Mono-aromatic ring-fused versus adjacently di-aromatic ring-fused tetraazaporphyrins: regioselective synthesis and their spectroscopic and electrochemical properties. J Am Chem Soc 124:8021–8034; (c) Kobayashi N, Miwa H, Nemykin VN (2002) Adjacent versus opposite type di-aromatic ring-fused phthalocyanine derivatives: synthesis, spectroscopy, electrochemistry, and molecular orbital calculations. J Am Chem Soc 124:8007–8020; (d) Kobayashi N, Mack J, Ishii K, Stillman MJ (2002) Electronic structure of reduced symmetry peripheral fused-ring-substituted phthalocyanines. Inorg Chem 41:5350–5363; (e) Miwa H, Ishii K, Kobayashi N (2004) Electronic structures of zinc and palladium tetraazaporphyrin derivatives controlled by fused benzo rings. Chem Eur J 10:4422–4435
(a) Shimizu S, Kobayashi N (2014) Structurally-modified subphthalocyanines: molecular design towards realization of expected properties from the electronic structure and structural features of subphthalocyanine. Chem Commun 50:6949–6966; (b) Zhu H, Shimizu S, Kobayashi N (2010) Subazaphenalenephthalocyanine: a subphthalocyanine analogue bearing a six-membered ring unit. Angew Chem Int Ed 49:8000–8003; (c) Shimizu S, Nakano S, Kojima A, Kobayashi N (2014) A core-expanded subphthalocyanine analogue with a significantly distorted conjugated surface and unprecedented properties. Angew Chem Int Ed 53:2408–2412
Saito S, Osuka A (2011) Expanded porphyrins: intriguing structures, electronic properties, and reactivities. Angew Chem Int Ed 50:4342–4373
Bloor JE, Schlabitz J, Walden CC, Demerdac A (1964) Organic complexes of uranium: Part I. The synthesis and spectrum of uranyl phthalocyanine. Can J Chem 42:2201–2208
(a) Marks TJ, Stojakovic DR (1975) Macrocycle contraction reactions of 5,35 : 14,19-Diimino-7,12 : 21,26 : 28,33-trinitrilopentabenzo [c,h,m,r,w][1,6,11,16,21]pentaazacyclopentacosinato-dioxouranium(VI). JCS Chem Commun 28–29; (b) Day VW, Marks TJ, Wachter WA (1975) Large metal ion-centered template reactions. Uranyl complex of cyclopentakis(2-iminoisoindoline). J Am Chem Soc 97:4519–4527; (c) Marks TJ, Stojakovic DR (1978) J Am Chem Soc 100:1695–1705; (d) Cuellar EA, Marks TJ (1981) Large metal ion-centered template reactions. Chemical and spectral studies of the “superphthalocyanine” dioxocyclopentakis(1-iminoisoindolinato)uranium(VI) and its derivatives. Inorg Chem 20:3766–3770
Furuyama T, Ogura Y, Yoza K, Kobayashi N (2012) Superazaporphyrins: meso-pentaazapentaphyrins and one of their low-symmetry derivatives. Angew Chem Int Ed 51:11110–11114
Matsushita O, Derkacheva VM, Muranaka A, Shimizu S, Uchiyama M, Luk’yanets EA, Kobayashi N (2012) Rectangular-shaped expanded phthalocyanines with two central metal atoms. J Am Chem Soc 134:3411–3418
Ficken GE, Linstead RP, Stephen E, Whalley M (1958) Conjugated macrocycles. Part XXXI. catalytic hydrogenation of tetrazaporphins, with a note on its stereochemical course. J Chem Soc 3879–3886
Kopranenkov VN, Goncharova LS, Lukyanets EA (1979) Cyano-substituted porphyrazines. Zh Obshch Khim 49:1408–1412
Shimizu S, Haseba Y, Yamazaki M, Kumazawa G, Kobayashi N (2014) Control of chromophore symmetry by positional isomerism of peripheral substituents. Chem Eur J 20:4822–4828
(a) Mack J, Stillman MJ, Kobayashi N (2007) Application of MCD spectroscopy to porphyrinoids. Coord Chem Rev 251:429–453; (b) Mack J, Kobayashi N, Shen Z (2012) In: Kadish KM, Smith KM, Guilard R (eds) Handbook of porphyrin science, vol 23, Chap. 109. World Scientific, Singapore; (c) Kobayashi N, Muranaka A, Mack J (2012) Circular dichroism and magnetic circular dichroism spectroscopy for organic chemists. Royal Society of Chemistry, Cambridge
(a) Kaito A, Nozawa T, Yamamoto T, Hatano M, Orii Y (1977) LCAO MO SCF Π-electron calculations on the magnetic circular dichroism of porphin, protoporphyrin, and porphyrin. Chem Phys Lett 52:154–160; (b) Tajiri A, Winkler J (1983) Magnetic circular-dichroism and molecular-orbital studies on condensed thiadiazoles. Z Naturforsch A 38:1263–1269
(a) Furuyama T, Satoh K, Kushiya T, Kobayashi N (2013) Design, synthesis, and properties of phthalocyanine complexes with main-group elements showing main absorption and fluorescence beyond 1000 nm. J Am Chem Soc 136:765–776; (b) Kobayashi N, Furuyama T, Satoh K (2011) Rationally designed phthalocyanines having their main absorption band beyond 1000 nm. J Am Chem Soc 133:19642–19645
Furuyama T, Yoshida T, Hashizume D, Kobayashi N (2014) Phosphorus(v) tetraazaporphyrins: porphyrinoids showing an exceptionally strong CT band between the soret and Q bands. Chem Sci 5:2466–2474
(a) Hanack M, Dini D (2003) In: Kadish KM, Smith KM, Guilard R (eds) The porphyrin handbook, vol 18, Chap. 114. Academic Press, San Diego; (b) Weiss R, Fischer J (2003) In: Kadish KM, Smith KM, Guilard R (eds) The porphyrin handbook, vol 16, Chap. 105. Academic Press, San Diego; (c) Buchler JW, Ng DKP (2003) In: Kadish KM, Smith KM, Guilard R (eds) The porphyrin handbook, vol 3, Chap. 20. Academic Press, San Diego
(a) Marks TJ (1985) Electrically conductive metallomacrocyclic assemblies. Science 227:881–889; (b) Dirk CW, Inabe T, Schoch KF, Marks TJ (1983) Metallomacrocycles as an approach to controlling lattice architecture in low-dimensional molecular solids. chemical, structural, oxidation state, transport, magnetic, and optical properties of halogen-doped [M(phthalocyaninato)O], macromolecules, where M = Si, Ge, and Sn. J Am Chem Soc 105:1539–1550; (c) Diel BN, Inabe T, Lyding JW, Schoch KF, Kannewurf CR, Marks TJ (1983) Cofacial assembly of partially oxidized metallomacrocycles as an approach to controlling lattice architecture in low-dimensional molecular-solids - chemical and architectural properties of the face-to-face polymers [M(Phthalocyaninato)O]N, where M = Si, Ge, and Sn. J Am Chem Soc 105:1551–1567; (d) Dewulf DW, Leland JK, Wheeler BL, Bard AJ, Batzel DA, Dininny DR, Kenney ME (1987) Isolation, spectroscopic properties, and electrochemical properties of two oligomeric silicon phthalocyanines. Inorg Chem 26:266–270
(a) Ferencz A, Neher D, Schulze M, Wegner G, Viaene L, Deschryver FC (1995) Synthesis and spectroscopic properties of phthalocyanine dimers in solution. Chem Phys Lett 245:23–29; (b) OddosMarcel L, Madeore F, Bock A, Neher D, Ferencz A, Rengel H, Wagner G, Kryschi C, Trommsdorff HP (1996) Electronic states and relaxation dynamics of silicon phthalocyanine dimers. J Phys Chem 100:11850–11856
Kleinwachter J, Hanack M (1997) Rotational isomers in stacked macrocycles: synthesis and spectroscopic properties of peripherally substituted (μ-Oxo)bis(phthalocyaninatosilicon) compounds. J Am Chem Soc 119:10684–10695
(a) Ciliberto E, Doris KA, Pietro WJ, Reisner GM, Ellis DE, Fragala I, Herbstein FH, Ratner MA, Marks TJ (1984) Π-Π interactions and bandwidths in “molecular metals”. A chemical, structural, photoelectron spectroscopic, and Hartree-Fock-Slater study of monomeric and cofacially joined dimeric silicon phthalocyanines. J Am Chem Soc 106:7748–7761; (b) Li ZY, Lieberman M (2001) Axial reactivity of soluble silicon(IV) phthalocyanines. Inorg Chem 40:932–939
Kasha M (1963) Energy transfer mechanisms and the molecular exciton model for molecular aggregates. Radiat Res 20:55–70
(a) Ishikawa N, Ohno O, Kaizu Y, Kobayashi H (1992) Localized orbital study on the electronic-structure of phthalocyanine dimers. J Phys Chem 96:8832–8839; (b) Ishikawa N (2001) Electronic structures and spectral properties of double- and triple-decker phthalocyanine complexes in a localized molecular orbital view. J Porphyrins Phthalocyanines 5:87–101
Oniwa K, Shimizu S, Shiina Y, Fukuda T, Kobayashi N (2013) A μ-oxo hetero dimer of silicon phthalocyanine and naphthalocyanine. Chem Commun 49:8341–8343
Fukuda T, Biyajima T, Kobayashi N (2010) A discrete quadruple-decker phthalocyanine. J Am Chem Soc 132:6278–6279
(a) Fukuda T, Kuroda W, Ishikawa N (2011) Observation of long-range f-f interactions between two f-electronic systems in quadruple-decker phthalocyanines. Chem Commun 47:11686–11688; (b) Fukuda T, Matsumura K, Ishikawa N (2013) Influence of intramolecular f-f interactions on nuclear spin driven quantum tunneling of magnetizations in quadruple-decker phthalocyanine complexes containing two terbium or dysprosium magnetic centers. J Phys Chem A 117:10447–10454
(a) Wang H, Qian K, Wang K, Bian Y, Jiang J, Gao S (2011) Sandwich-type Tetrakis(phthalocyaninato) Dysprosium-Cadmium Quadruple-Decker SMM. Chem Commun 47:9624–9626; (b) Wang H, Kobayashi N, Jiang J (2012) New sandwich-type phthalocyaninato-metal quintuple-decker complexes. Chem Eur J 18:1047–1049; (c) Wang H, Qi D, Xie Z, Cao W, Wang K, Shang H, Jiang J (2013) A sandwich-type phthalocyaninato metal sextuple-decker complex: synthesis and NLO properties. Chem Commun 49:889–891
Fukuda T, Hata K, Ishikawa N (2012) Observation of exceptionally low-lying Π–Π* excited states in oxidized forms of quadruple-decker phthalocyanine complexes. J Am Chem Soc 134:14698–14701
Author information
Authors and Affiliations
Corresponding authors
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2015 Springer Japan
About this chapter
Cite this chapter
Shimizu, S., Kobayashi, N. (2015). Recent Advances in the Chemistry of Phthalocyanines as Functional Chromophores. In: Akasaka, T., Osuka, A., Fukuzumi, S., Kandori, H., Aso, Y. (eds) Chemical Science of π-Electron Systems. Springer, Tokyo. https://doi.org/10.1007/978-4-431-55357-1_16
Download citation
DOI: https://doi.org/10.1007/978-4-431-55357-1_16
Publisher Name: Springer, Tokyo
Print ISBN: 978-4-431-55356-4
Online ISBN: 978-4-431-55357-1
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)