Effect of carbazole and pyrrolidine functionalization of phenanthroline ligand on ground- and excited-state properties of rhenium(I) complexes. Interplay between 3MLCT and 3IL/3ILCT

Joanna Palion-Gazda; Barbara Machura; Agata Szłapa-Kula; Anna M. Maroń; Jacek E. Nycz; Przemyslaw Ledwon; Ewa Schab-Balcerzak; Mariola Siwy; Justyna Grzelak; Sebastian Maćkowski

doi:10.1016/j.dyepig.2022.110113

Effect of carbazole and pyrrolidine functionalization of phenanthroline ligand on ground- and excited-state properties of rhenium(I) complexes. Interplay between ³MLCT and ³IL/³ILCT

Joanna Palion-Gazda
, Barbara Machura
, Agata Szłapa-Kula
, Anna M. Maroń
, Jacek E. Nycz
, Przemyslaw Ledwon
, Ewa Schab-Balcerzak
, Mariola Siwy
, Justyna Grzelak
, Sebastian Maćkowski

Department of Physical Chemistry and Technology of Polymers (RCH/RCH4)

University of Silesia in Katowice
Polish Academy of Sciences
Nicolaus Copernicus University in Toruń

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

5 Citations (Scopus)

Abstract

New rhenium(I) tricarbonyl complexes based on the phenanthroline ligand were designed and synthesized to investigate the role of carbazole (cbz) and pyrrolidine (pyrr) substituents in determining thermal, electrochemical and optoelectronic properties. Both pyrr and cbz are electron-releasing substituents, but they differ in the steric hindrance and electron delocalization ability. The impact of pyrr and cbz on ground- and excited-state properties of [ReCl(CO)₃(cbz₂-CH₃phen)] (1) and [ReCl(CO)₃(pyrr₂-CH₃phen)] (2) were investigated with a range of techniques including cyclic voltammetry, absorbance and emission spectroscopies, transient absorption spectroscopy, and they were discussed in comparison with the model chromophore [ReCl(CO)₃(CH₃phen)] (3). Experimental results were supported by theoretical calculations. The most striking difference between the pyrr and cbz groups was seen in their impact on the LUMO energy level. While the attached carbazole groups decreased the LUMO energy of 1, the pyrrolidine ones in 2 resulted in the rise of LUMO energy level compared to the model chromophore. For both 1 and 2, the HOMO got energetically destabilized in agreement with electro-donor abilities of pyrr and cbz substituents. Structural modification of phen backbone resulted also in changes of distribution of occupied MOs of 1 and 2 in relation to 3. Experimentally, it was manifested in noticeable changes of electrochemical and photophysical behaviour of the resulting Re(I) complexes in relation to the model chromophore.

Original language	English
Article number	110113
Journal	Dyes and Pigments
Volume	200
DOIs	https://doi.org/10.1016/j.dyepig.2022.110113
Publication status	Published - Apr 2022

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This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 13 Climate Action

ASJC Scopus subject areas

General Chemical Engineering
Process Chemistry and Technology

Access to Document

10.1016/j.dyepig.2022.110113

Cite this

Palion-Gazda, J., Machura, B., Szłapa-Kula, A., Maroń, A. M., Nycz, J. E., Ledwon, P., Schab-Balcerzak, E., Siwy, M., Grzelak, J., & Maćkowski, S. (2022). Effect of carbazole and pyrrolidine functionalization of phenanthroline ligand on ground- and excited-state properties of rhenium(I) complexes. Interplay between ³MLCT and ³IL/³ILCT. Dyes and Pigments, 200, Article 110113. https://doi.org/10.1016/j.dyepig.2022.110113

@article{45ccd727ea674b0ab1d831b58b17caa3,

title = "Effect of carbazole and pyrrolidine functionalization of phenanthroline ligand on ground- and excited-state properties of rhenium(I) complexes. Interplay between 3MLCT and 3IL/3ILCT",

abstract = "New rhenium(I) tricarbonyl complexes based on the phenanthroline ligand were designed and synthesized to investigate the role of carbazole (cbz) and pyrrolidine (pyrr) substituents in determining thermal, electrochemical and optoelectronic properties. Both pyrr and cbz are electron-releasing substituents, but they differ in the steric hindrance and electron delocalization ability. The impact of pyrr and cbz on ground- and excited-state properties of [ReCl(CO)3(cbz2-CH3phen)] (1) and [ReCl(CO)3(pyrr2-CH3phen)] (2) were investigated with a range of techniques including cyclic voltammetry, absorbance and emission spectroscopies, transient absorption spectroscopy, and they were discussed in comparison with the model chromophore [ReCl(CO)3(CH3phen)] (3). Experimental results were supported by theoretical calculations. The most striking difference between the pyrr and cbz groups was seen in their impact on the LUMO energy level. While the attached carbazole groups decreased the LUMO energy of 1, the pyrrolidine ones in 2 resulted in the rise of LUMO energy level compared to the model chromophore. For both 1 and 2, the HOMO got energetically destabilized in agreement with electro-donor abilities of pyrr and cbz substituents. Structural modification of phen backbone resulted also in changes of distribution of occupied MOs of 1 and 2 in relation to 3. Experimentally, it was manifested in noticeable changes of electrochemical and photophysical behaviour of the resulting Re(I) complexes in relation to the model chromophore.",

author = "Joanna Palion-Gazda and Barbara Machura and Agata Sz{\l}apa-Kula and Maro{\'n}, \{Anna M.\} and Nycz, \{Jacek E.\} and Przemyslaw Ledwon and Ewa Schab-Balcerzak and Mariola Siwy and Justyna Grzelak and Sebastian Ma{\'c}kowski",

note = "Publisher Copyright: {\textcopyright} 2022",

year = "2022",

month = apr,

doi = "10.1016/j.dyepig.2022.110113",

language = "English",

volume = "200",

journal = "Dyes and Pigments",

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Palion-Gazda, J, Machura, B, Szłapa-Kula, A, Maroń, AM, Nycz, JE, Ledwon, P, Schab-Balcerzak, E, Siwy, M, Grzelak, J & Maćkowski, S 2022, 'Effect of carbazole and pyrrolidine functionalization of phenanthroline ligand on ground- and excited-state properties of rhenium(I) complexes. Interplay between ³MLCT and ³IL/³ILCT', Dyes and Pigments, vol. 200, 110113. https://doi.org/10.1016/j.dyepig.2022.110113

TY - JOUR

T1 - Effect of carbazole and pyrrolidine functionalization of phenanthroline ligand on ground- and excited-state properties of rhenium(I) complexes. Interplay between 3MLCT and 3IL/3ILCT

AU - Palion-Gazda, Joanna

AU - Machura, Barbara

AU - Szłapa-Kula, Agata

AU - Maroń, Anna M.

AU - Nycz, Jacek E.

AU - Ledwon, Przemyslaw

AU - Schab-Balcerzak, Ewa

AU - Siwy, Mariola

AU - Grzelak, Justyna

AU - Maćkowski, Sebastian

PY - 2022/4

Y1 - 2022/4

N2 - New rhenium(I) tricarbonyl complexes based on the phenanthroline ligand were designed and synthesized to investigate the role of carbazole (cbz) and pyrrolidine (pyrr) substituents in determining thermal, electrochemical and optoelectronic properties. Both pyrr and cbz are electron-releasing substituents, but they differ in the steric hindrance and electron delocalization ability. The impact of pyrr and cbz on ground- and excited-state properties of [ReCl(CO)3(cbz2-CH3phen)] (1) and [ReCl(CO)3(pyrr2-CH3phen)] (2) were investigated with a range of techniques including cyclic voltammetry, absorbance and emission spectroscopies, transient absorption spectroscopy, and they were discussed in comparison with the model chromophore [ReCl(CO)3(CH3phen)] (3). Experimental results were supported by theoretical calculations. The most striking difference between the pyrr and cbz groups was seen in their impact on the LUMO energy level. While the attached carbazole groups decreased the LUMO energy of 1, the pyrrolidine ones in 2 resulted in the rise of LUMO energy level compared to the model chromophore. For both 1 and 2, the HOMO got energetically destabilized in agreement with electro-donor abilities of pyrr and cbz substituents. Structural modification of phen backbone resulted also in changes of distribution of occupied MOs of 1 and 2 in relation to 3. Experimentally, it was manifested in noticeable changes of electrochemical and photophysical behaviour of the resulting Re(I) complexes in relation to the model chromophore.

AB - New rhenium(I) tricarbonyl complexes based on the phenanthroline ligand were designed and synthesized to investigate the role of carbazole (cbz) and pyrrolidine (pyrr) substituents in determining thermal, electrochemical and optoelectronic properties. Both pyrr and cbz are electron-releasing substituents, but they differ in the steric hindrance and electron delocalization ability. The impact of pyrr and cbz on ground- and excited-state properties of [ReCl(CO)3(cbz2-CH3phen)] (1) and [ReCl(CO)3(pyrr2-CH3phen)] (2) were investigated with a range of techniques including cyclic voltammetry, absorbance and emission spectroscopies, transient absorption spectroscopy, and they were discussed in comparison with the model chromophore [ReCl(CO)3(CH3phen)] (3). Experimental results were supported by theoretical calculations. The most striking difference between the pyrr and cbz groups was seen in their impact on the LUMO energy level. While the attached carbazole groups decreased the LUMO energy of 1, the pyrrolidine ones in 2 resulted in the rise of LUMO energy level compared to the model chromophore. For both 1 and 2, the HOMO got energetically destabilized in agreement with electro-donor abilities of pyrr and cbz substituents. Structural modification of phen backbone resulted also in changes of distribution of occupied MOs of 1 and 2 in relation to 3. Experimentally, it was manifested in noticeable changes of electrochemical and photophysical behaviour of the resulting Re(I) complexes in relation to the model chromophore.

UR - https://www.scopus.com/pages/publications/85123682677

U2 - 10.1016/j.dyepig.2022.110113

DO - 10.1016/j.dyepig.2022.110113

M3 - Article

AN - SCOPUS:85123682677

SN - 0143-7208

VL - 200

JO - Dyes and Pigments

JF - Dyes and Pigments

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