Evaluation of the Intramolecular Charge-Transfer Properties in Solvatochromic and Electrochromic Zinc Octa(carbazolyl)phthalocyanines

Shereen A. Majeed; Basma Ghazal; Dustin E. Nevonen; Philip C. Goff; David A Blank; Victor N. Nemykin; Saad Makhseed

doi:10.1021/acs.inorgchem.7b01570

Evaluation of the Intramolecular Charge-Transfer Properties in Solvatochromic and Electrochromic Zinc Octa(carbazolyl)phthalocyanines

Shereen A. Majeed, Basma Ghazal, Dustin E. Nevonen, Philip C. Goff, David A Blank, Victor N. Nemykin, Saad Makhseed

Chemistry (Twin Cities)

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

49 Scopus citations

Abstract

2,3,9,10,16,17,23·24-Octakis-(9H-carbazol-9-yl) phthalocyaninato zinc(II) (3) and 2,3,9,10,16,17,23·24-octakis-(3,6-di-tert-butyl-9H-carbazole) phthalocyaninato zinc(II) (4) complexes were prepared and characterized by NMR and UV-vis spectroscopies, magnetic circular dichroism (MCD), matrix-assisted laser desorption ionization mass spectrometry, and X-ray crystallography. UV-vis and MCD data are indicative of the interligand charge-transfer nature of the broad band observed in 450-500 nm range for 3 and 4. The redox properties of 3 and 4 were probed by electrochemical and spectro-electrochemical methods, which are suggestive of phthalocyanine-centered first oxidation and reduction processes. Photophysics of 3 and 4 were investigated by steady-state fluorescence and time-resolved transient absorption spectroscopy demonstrating the influence of the carbazole substituents on deactivation from the first excited state in 3 and 4. Protonation of the meso-nitrogen atoms in 3 results in much faster deactivation kinetics from the first excited state. Spectroscopic data were correlated with density functional theory (DFT) and time-dependent DFT calculations on 3 and 4.

Original language	English (US)
Pages (from-to)	11640-11653
Number of pages	14
Journal	Inorganic chemistry
Volume	56
Issue number	19
DOIs	https://doi.org/10.1021/acs.inorgchem.7b01570
State	Published - Oct 2 2017

Bibliographical note

Funding Information:
The authors gratefully acknowledge the support of Graduate Studies at Kuwait Univ. for a Ph.D. candidacy. This research is also supported by the Kuwait Univ. Research administration-RSP unit general facilities of the Faculty of Science GFS (GS 01/01, GS 02/01, GS 03/01, GS 01/03, GS 01/05, GS02/13) and the Kuwait Foundation for the Advancement of Science-KFAS (Grant No. P114-14-SC01). V.N.N. would like to acknowledge support from NSERC, CFI, WestGrid, and the Univ. of Manitoba. V.N.N. wishes to thank Ms. S. Doble for help with collecting MCD spectra.

Publisher Copyright:
© 2017 American Chemical Society.

Copyright:
Copyright 2017 Elsevier B.V., All rights reserved.

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title = "Evaluation of the Intramolecular Charge-Transfer Properties in Solvatochromic and Electrochromic Zinc Octa(carbazolyl)phthalocyanines",

abstract = "2,3,9,10,16,17,23·24-Octakis-(9H-carbazol-9-yl) phthalocyaninato zinc(II) (3) and 2,3,9,10,16,17,23·24-octakis-(3,6-di-tert-butyl-9H-carbazole) phthalocyaninato zinc(II) (4) complexes were prepared and characterized by NMR and UV-vis spectroscopies, magnetic circular dichroism (MCD), matrix-assisted laser desorption ionization mass spectrometry, and X-ray crystallography. UV-vis and MCD data are indicative of the interligand charge-transfer nature of the broad band observed in 450-500 nm range for 3 and 4. The redox properties of 3 and 4 were probed by electrochemical and spectro-electrochemical methods, which are suggestive of phthalocyanine-centered first oxidation and reduction processes. Photophysics of 3 and 4 were investigated by steady-state fluorescence and time-resolved transient absorption spectroscopy demonstrating the influence of the carbazole substituents on deactivation from the first excited state in 3 and 4. Protonation of the meso-nitrogen atoms in 3 results in much faster deactivation kinetics from the first excited state. Spectroscopic data were correlated with density functional theory (DFT) and time-dependent DFT calculations on 3 and 4.",

author = "Majeed, {Shereen A.} and Basma Ghazal and Nevonen, {Dustin E.} and Goff, {Philip C.} and Blank, {David A} and Nemykin, {Victor N.} and Saad Makhseed",

note = "Funding Information: The authors gratefully acknowledge the support of Graduate Studies at Kuwait Univ. for a Ph.D. candidacy. This research is also supported by the Kuwait Univ. Research administration-RSP unit general facilities of the Faculty of Science GFS (GS 01/01, GS 02/01, GS 03/01, GS 01/03, GS 01/05, GS02/13) and the Kuwait Foundation for the Advancement of Science-KFAS (Grant No. P114-14-SC01). V.N.N. would like to acknowledge support from NSERC, CFI, WestGrid, and the Univ. of Manitoba. V.N.N. wishes to thank Ms. S. Doble for help with collecting MCD spectra. Publisher Copyright: {\textcopyright} 2017 American Chemical Society. Copyright: Copyright 2017 Elsevier B.V., All rights reserved.",

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T1 - Evaluation of the Intramolecular Charge-Transfer Properties in Solvatochromic and Electrochromic Zinc Octa(carbazolyl)phthalocyanines

AU - Majeed, Shereen A.

AU - Ghazal, Basma

AU - Nevonen, Dustin E.

AU - Goff, Philip C.

AU - Blank, David A

AU - Nemykin, Victor N.

AU - Makhseed, Saad

N1 - Funding Information: The authors gratefully acknowledge the support of Graduate Studies at Kuwait Univ. for a Ph.D. candidacy. This research is also supported by the Kuwait Univ. Research administration-RSP unit general facilities of the Faculty of Science GFS (GS 01/01, GS 02/01, GS 03/01, GS 01/03, GS 01/05, GS02/13) and the Kuwait Foundation for the Advancement of Science-KFAS (Grant No. P114-14-SC01). V.N.N. would like to acknowledge support from NSERC, CFI, WestGrid, and the Univ. of Manitoba. V.N.N. wishes to thank Ms. S. Doble for help with collecting MCD spectra. Publisher Copyright: © 2017 American Chemical Society. Copyright: Copyright 2017 Elsevier B.V., All rights reserved.

PY - 2017/10/2

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Evaluation of the Intramolecular Charge-Transfer Properties in Solvatochromic and Electrochromic Zinc Octa(carbazolyl)phthalocyanines

Abstract

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