Synthesis and characterization of periphery-functionalized porphyrazines containing mixed pyrrolyl and pyridylmethylamino groups

Tomasz Goslinski; Ewa Tykarska; Wojciech Szczolko; Tomasz Osmalek; Aleksandra Smigielska; Stanislaw Walorczyk; Hong Zong; Maria Gdaniec; Brian M. Hoffman; Jadwiga Mielcarek; Stanislaw Sobiak

doi:10.1142/S1088424609000309

Synthesis and characterization of periphery-functionalized porphyrazines containing mixed pyrrolyl and pyridylmethylamino groups

Tomasz Goslinski^*, Ewa Tykarska, Wojciech Szczolko, Tomasz Osmalek, Aleksandra Smigielska, Stanislaw Walorczyk, Hong Zong, Maria Gdaniec, Brian M. Hoffman, Jadwiga Mielcarek, Stanislaw Sobiak

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

13 Scopus citations

Abstract

The condensation reaction of 2-amino-3-[(3-pyridylmethyl)amino]-2(Z)- butene-1,4-dinitrile with a series of diketones led to novel dinitriles, of which 2-(2,5-dimethyl-1H-pyrrol-1-yl)-3-[methyl(3-pyridylmethylene)amino]-2(Z)- butene-1,4-dinitrile, the product of the Paal-Knorr reaction, was successfully utilized in the Linstead macrocyclization towards symmetrical and unsymmetrical porphyrazines. NMR and X-ray study revealed an almost perpendicular orientation of the pyrrolyl groups in relation to the porphyrazine platform. The newly synthesized macrocycles with different peripheral groups show interesting spectroscopic and electrochemical properties. Due to selective sensor/coordination properties they are expected to find applications as chemical sensors and electronic materials.

Original language	English (US)
Pages (from-to)	223-234
Number of pages	12
Journal	Journal of Porphyrins and Phthalocyanines
Volume	13
Issue number	2
DOIs	https://doi.org/10.1142/S1088424609000309
State	Published - Feb 2009

Keywords

Cyclic voltammetry
Diketones
Linstead macrocyclization
Porphyrazine
Spectroscopy

ASJC Scopus subject areas

Chemistry(all)

Access to Document

10.1142/S1088424609000309

Cite this

Goslinski, T., Tykarska, E., Szczolko, W., Osmalek, T., Smigielska, A., Walorczyk, S., Zong, H., Gdaniec, M., Hoffman, B. M., Mielcarek, J., & Sobiak, S. (2009). Synthesis and characterization of periphery-functionalized porphyrazines containing mixed pyrrolyl and pyridylmethylamino groups. Journal of Porphyrins and Phthalocyanines, 13(2), 223-234. https://doi.org/10.1142/S1088424609000309

@article{db193202744540f7aff1d5d0a8f613b1,

title = "Synthesis and characterization of periphery-functionalized porphyrazines containing mixed pyrrolyl and pyridylmethylamino groups",

abstract = "The condensation reaction of 2-amino-3-[(3-pyridylmethyl)amino]-2(Z)- butene-1,4-dinitrile with a series of diketones led to novel dinitriles, of which 2-(2,5-dimethyl-1H-pyrrol-1-yl)-3-[methyl(3-pyridylmethylene)amino]-2(Z)- butene-1,4-dinitrile, the product of the Paal-Knorr reaction, was successfully utilized in the Linstead macrocyclization towards symmetrical and unsymmetrical porphyrazines. NMR and X-ray study revealed an almost perpendicular orientation of the pyrrolyl groups in relation to the porphyrazine platform. The newly synthesized macrocycles with different peripheral groups show interesting spectroscopic and electrochemical properties. Due to selective sensor/coordination properties they are expected to find applications as chemical sensors and electronic materials.",

keywords = "Cyclic voltammetry, Diketones, Linstead macrocyclization, Porphyrazine, Spectroscopy",

author = "Tomasz Goslinski and Ewa Tykarska and Wojciech Szczolko and Tomasz Osmalek and Aleksandra Smigielska and Stanislaw Walorczyk and Hong Zong and Maria Gdaniec and Hoffman, {Brian M.} and Jadwiga Mielcarek and Stanislaw Sobiak",

note = "Funding Information: The Paal-Knorr reaction using 2-amino-3-[(3-py ri dyl methyl)amino]-2(Z)-butene-1,4-dinitrile and 2,5-hexa ne dione led to 2-(2,5-di methyl-1H-pyrrol-1-yl)-3-[methyl (3-pyridyl methyl) amino]-2(Z)-1,4-di nitrile, which was successfully utilized in the Lins tead macro-cyclization towards symmetrical and unsymmetrical por-phyrazines. Porphyrazine sys tems en dowed with a mixed 2,5-dimethylpyrrolyl and me thyl (3-pyridyl methyl) amino peripheral system at ta ched to the macrocycle, can be tailored to alter the phy sical properties of the porphyrazine as well as its elec tronic absorption and electrochemistry. Both optical and electrochemical characterizations of novel porphyrazines are significantly influenced by the 2,5-dimethylpyrrolyl substituent, which is in an almost perpendicular orientation to the porphyrazine ma cro-cycle. The compounds revealed electronic Q band π→π* transitions between 628–775 nm. In comparison to the previously obtained porphyrazines with symmetrical electron-donor groups in the periphery for the newly synthesized macrocycles only very weak n→π* transitions This study was supported by the Polish Ministry of Science and Higher Education Grant no N405 031 32/2052. T.G. thanks the British Council and the Po lish Ministry of Science and Higher Education for the opportunity to participate in the British-Polish Young Scientific Programme (YSP). T.G. thanks Profes sor A.G.M. Barrett from Imperial College London for supporting his studies within the YSP pro gram me. The authors thank Mrs Beata Kwiatkowska for ex cel lent technical assistance. T.G. thanks MSc D. Marek (Bruker, Poznan, Poland) for FT-IR-ATR measurements.",

year = "2009",

month = feb,

doi = "10.1142/S1088424609000309",

language = "English (US)",

volume = "13",

pages = "223--234",

journal = "Journal of Porphyrins and Phthalocyanines",

issn = "1088-4246",

publisher = "Society of Porphyrins and Phthalocyanines (SPP)",

number = "2",

}

Goslinski, T, Tykarska, E, Szczolko, W, Osmalek, T, Smigielska, A, Walorczyk, S, Zong, H, Gdaniec, M, Hoffman, BM, Mielcarek, J & Sobiak, S 2009, 'Synthesis and characterization of periphery-functionalized porphyrazines containing mixed pyrrolyl and pyridylmethylamino groups', Journal of Porphyrins and Phthalocyanines, vol. 13, no. 2, pp. 223-234. https://doi.org/10.1142/S1088424609000309

TY - JOUR

T1 - Synthesis and characterization of periphery-functionalized porphyrazines containing mixed pyrrolyl and pyridylmethylamino groups

AU - Goslinski, Tomasz

AU - Tykarska, Ewa

AU - Szczolko, Wojciech

AU - Osmalek, Tomasz

AU - Smigielska, Aleksandra

AU - Walorczyk, Stanislaw

AU - Zong, Hong

AU - Gdaniec, Maria

AU - Hoffman, Brian M.

AU - Mielcarek, Jadwiga

AU - Sobiak, Stanislaw

N1 - Funding Information: The Paal-Knorr reaction using 2-amino-3-[(3-py ri dyl methyl)amino]-2(Z)-butene-1,4-dinitrile and 2,5-hexa ne dione led to 2-(2,5-di methyl-1H-pyrrol-1-yl)-3-[methyl (3-pyridyl methyl) amino]-2(Z)-1,4-di nitrile, which was successfully utilized in the Lins tead macro-cyclization towards symmetrical and unsymmetrical por-phyrazines. Porphyrazine sys tems en dowed with a mixed 2,5-dimethylpyrrolyl and me thyl (3-pyridyl methyl) amino peripheral system at ta ched to the macrocycle, can be tailored to alter the phy sical properties of the porphyrazine as well as its elec tronic absorption and electrochemistry. Both optical and electrochemical characterizations of novel porphyrazines are significantly influenced by the 2,5-dimethylpyrrolyl substituent, which is in an almost perpendicular orientation to the porphyrazine ma cro-cycle. The compounds revealed electronic Q band π→π* transitions between 628–775 nm. In comparison to the previously obtained porphyrazines with symmetrical electron-donor groups in the periphery for the newly synthesized macrocycles only very weak n→π* transitions This study was supported by the Polish Ministry of Science and Higher Education Grant no N405 031 32/2052. T.G. thanks the British Council and the Po lish Ministry of Science and Higher Education for the opportunity to participate in the British-Polish Young Scientific Programme (YSP). T.G. thanks Profes sor A.G.M. Barrett from Imperial College London for supporting his studies within the YSP pro gram me. The authors thank Mrs Beata Kwiatkowska for ex cel lent technical assistance. T.G. thanks MSc D. Marek (Bruker, Poznan, Poland) for FT-IR-ATR measurements.

PY - 2009/2

Y1 - 2009/2

N2 - The condensation reaction of 2-amino-3-[(3-pyridylmethyl)amino]-2(Z)- butene-1,4-dinitrile with a series of diketones led to novel dinitriles, of which 2-(2,5-dimethyl-1H-pyrrol-1-yl)-3-[methyl(3-pyridylmethylene)amino]-2(Z)- butene-1,4-dinitrile, the product of the Paal-Knorr reaction, was successfully utilized in the Linstead macrocyclization towards symmetrical and unsymmetrical porphyrazines. NMR and X-ray study revealed an almost perpendicular orientation of the pyrrolyl groups in relation to the porphyrazine platform. The newly synthesized macrocycles with different peripheral groups show interesting spectroscopic and electrochemical properties. Due to selective sensor/coordination properties they are expected to find applications as chemical sensors and electronic materials.

AB - The condensation reaction of 2-amino-3-[(3-pyridylmethyl)amino]-2(Z)- butene-1,4-dinitrile with a series of diketones led to novel dinitriles, of which 2-(2,5-dimethyl-1H-pyrrol-1-yl)-3-[methyl(3-pyridylmethylene)amino]-2(Z)- butene-1,4-dinitrile, the product of the Paal-Knorr reaction, was successfully utilized in the Linstead macrocyclization towards symmetrical and unsymmetrical porphyrazines. NMR and X-ray study revealed an almost perpendicular orientation of the pyrrolyl groups in relation to the porphyrazine platform. The newly synthesized macrocycles with different peripheral groups show interesting spectroscopic and electrochemical properties. Due to selective sensor/coordination properties they are expected to find applications as chemical sensors and electronic materials.

KW - Cyclic voltammetry

KW - Diketones

KW - Linstead macrocyclization

KW - Porphyrazine

KW - Spectroscopy

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UR - http://www.scopus.com/inward/citedby.url?scp=68349163207&partnerID=8YFLogxK

U2 - 10.1142/S1088424609000309

DO - 10.1142/S1088424609000309

M3 - Article

AN - SCOPUS:68349163207

SN - 1088-4246

VL - 13

SP - 223

EP - 234

JO - Journal of Porphyrins and Phthalocyanines

JF - Journal of Porphyrins and Phthalocyanines

IS - 2

ER -

Synthesis and characterization of periphery-functionalized porphyrazines containing mixed pyrrolyl and pyridylmethylamino groups

Abstract

Keywords

ASJC Scopus subject areas

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CCDC 685050: Experimental Crystal Structure Determination

CCDC 685051: Experimental Crystal Structure Determination

CCDC 685049: Experimental Crystal Structure Determination

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Synthesis and characterization of periphery-functionalized porphyrazines containing mixed pyrrolyl and pyridylmethylamino groups

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 685050: Experimental Crystal Structure Determination

CCDC 685051: Experimental Crystal Structure Determination

CCDC 685049: Experimental Crystal Structure Determination

Cite this