Effect of Substituents on Electronic Structure and Photophysical Properties of Re(I)(CO)<sub>3</sub>Cl(R-2, 2’-Bipyridine) Complex: DFT/TDDFT Study

Dereje Fedasa; Dunkana Negussa; Alemu Talema

doi:doi:10.11648/j.ijctc.20200802.11

| Peer-Reviewed

Effect of Substituents on Electronic Structure and Photophysical Properties of Re(I)(CO)₃Cl(R-2, 2’-Bipyridine) Complex: DFT/TDDFT Study

Dereje Fedasa, Dunkana Negussa, Alemu Talema

Published in International Journal of Computational and Theoretical Chemistry (Volume 8, Issue 2)

Received: 5 March 2020 Accepted: 24 March 2020 Published: 11 November 2020

Views: Downloads:

Download PDF

Share This Article

Twitter
Linked In
Facebook

Abstract

The electronic structure, absorption and emission spectra, as well as phosphorescence efficiency of Re(I) tricarbonyl complexes of a general formula fac-[Re(I)(CO)₃(L)(R-N^N)](L = Cl; N^N = 2, 2’-bipyridine; R = -H, 1; -NO₂, 2; -PhNO₂, 3; -NH₂, 4; -TPA (triphenylamine), 5) were investigated by using density functional theory(DFT) and time dependents density functional theory (TDDFT) methods. The calculated results reveal that introductions of the Electron with drawing group (EWG) and Electron donating group (EDG) on the R position of 2, 2’-bipyridine ligand. When EWG (-NO₂ and -PhNO₂) are introduced into complex 2 and 3, the lowest energy absorption and emission bands are red shifted compared with that of complex 1. On the contrary, the introduction of the EDG (-NH₂ and -TPA) in complex 4 and 5 cause corresponding blue shifted. The solvent effect on absorption and emission spectrum indicates that the lowest energy absorption and emission bands have red shifts with the decrease of solvent polarity. The electronic affinity (EA), ionization potential (IP) and reorganization energy (λ) results show that complex 5 is suitable to be used as an emitter in phosphorescence organic light emitting diodes (PHOLEDs). Meanwhile the emission quantum yield of complex 5 is possibly higher than that of other complexes.

Published in	International Journal of Computational and Theoretical Chemistry (Volume 8, Issue 2)
DOI	10.11648/j.ijctc.20200802.11
Page(s)	27-39
Creative Commons	This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited.
Copyright	Copyright © The Author(s), 2020. Published by Science Publishing Group

Keywords

Electronic Structure, Internal Quantum Efficiency, Luminescence, Phosphorescence and Photophysical Properties

References

[1]	Yang, R., Li, D., Bai, Y., Zhang, L., Liu, Z., Hao, J., Wei, Q., Liao, L., Peng, R. & Ge, Z. (2018). Novel tetraarylsilane-based hosts for blue phosphorescent organic light-emitting diodes. Organic Electronics, 55, 117-125.
[2]	Naturalium, R. (n.d). Spectroscopy and photochemistry of transition metal complexes: a quantum chemical study. Dalton transactions, 39, 9505-9513.
[3]	Jia, B., Lian, H., Chen, Z., Chen, Y., Huang, J.& Dong, Q. (2017). Novel carbazole/indole/thiazole-based host materials with high thermal stability for efficient phosphorescent organic light-emitting diodes. Journal of Dyes and Pigments, 147, 552-559.
[4]	Li, X., Zhang, D., Lu, G., Xiao, G., Chi, H., Dong, Y., Zhang, Z. & Hu, Z. (2012). Synthesis and characterization of novel rhenium (I) complexes with large Stokes shift for applications in organic electroluminescent devices. Journal of Photochemistry and Photobiology A: Chemistry, 241, 1-7.
[5]	Chung, W.-K., Maggie, Ng., Zhu, N., Siu, S. K.-L. & Yam, V. W.-W. (2017). Synthesis, characterization and computational studies of luminescent rhenium(I) tricarbonyl diimine complexes with 8-hydroxyquinoline containing alkynyl ligands. Journal of Organometallic Chemistry. DOI: 10.1021/acs.inorgchem.6b02999.
[6]	Nahhas, A. E., Consani, C., Blanco, A. M, Lancaster, K. M., Braem, O., Cannizzo, A., Towrie, M., Clark, I., Zalis, S., Chergui, M. & Vlcek, A. (2011). Ultrafast ExcitedState dynamics Re(I) Photosensitizers [Re(Cl)(CO)₃(N,N)] & [Re(imidazole)(CO)₃(N,N)]ⁿ⁺: Diimine Effects. American chemical society, 50, 2932-2943.
[7]	Huang, T. T. & Li, E. Y. (2016). Enhanced spin-orbit coupling driven by state mixing in organic molecules for OLED applications. Organic Electronics, 39, 311-317.
[8]	Maisuls, I., Wolcan, E., Piro, O. E., Castellano, E. E., Petroselli, G., Erra-Balsells, R., Cabrerizo, F. M. & Ruiz, G. T. (2017). Synthesis, Structural Characterization and Biological Evaluation of Rhenium (I) Tricarbonyl Complexes with -Carboline Ligands. Inorganic chemistry, 2, 8666-8672.
[9]	Bertrand, H. C., Clede, S., Guillot, R., Lambert, F. & Policar, C. (2014). Luminescence Modulations of Rhenium Tricarbonyl Complexes Induced by Structural Variations. Inorganic chemistry.dx.doi.org/10.1021/ic5007007.
[10]	Rohman, M. A., Sutradhar, D., Sangilipandi, S., Rao, K. M., Chandra, A. & Mitra, S. (2017). Photophysical behavior of systematically substituted (di-2-pyridylaminomethyl) benzene ligands and its Re(I) complexes: A combined experimental and theoretical approach. Journal of Photochemistry and Photobiology A: Chemistry. http://dx.doi.org/10.1016/j.jphotochem.2017.03.031.
[11]	Liu, S., Li, Y., Hu, X., Liu, X. & Guan, B. (2017). DFT studies on the ligand effect on electronic and optical properties of three series of functionalized Ir(III) complexes. Journal of Molecular Structure, 1151, 49-55.
[12]	Ramos, L. D., Cruz, H. M. D. & Frin, K. P. M. (2017). Photophysical properties of Rhenium(I) complexes and photo-sensitized generation of singlet O₂. Photochemical & Photobiological Sciences, 16, 459-466.
[13]	Shillito, G. E., Hall, T. B. J., Preston, D., Traber, P., Wu, L., Reynolds, K. E. A., Horvath, R., Sun, X. Z., Lucas, N. T., Crowley, J. D., George, M. W., Kupfer, S. & Gordon, K. C. (2018). Dramatic Alteration of 3ILCT Lifetimes Using Ancillary Ligands in [Re(L)(CO)₃(phen-TPA)]ⁿ⁺ Complexes: An Integrated Spectroscopic and Theoretical Study. Journal of the American Chemical Society, 140, 4534-4542.
[14]	Garino, C. & Salassa, L. (2013). The photochemistry of transition metal complexes by density functional theory. Philosophical Transactions of Royal Society A. http://dx.doi.org/10.1098/rsta.2012.0134.
[15]	Wang, J.-X., Xia, H.-Y., Liu, W.-Q., Zhao, F.& Wang, Y.-b. (2012). Synthesis, spectroscopic and DFT studies of rhenium (I) complexes with phenanthrolineimidazo ligands containing thienyl moieties. Inorganica Chimica Acta, 394, 92-97.
[16]	Velmurugan, G., Ramamoorthi, B.& Venuvanalingam, P. (2014). Are Re(I) phenanthroline complexes suitable candidates for OLEDs? Answers from DFT and TD-DFT investigations. Royal society of chemistry. DOI: 10.1039/c4cp01135j.
[17]	Wang, M., Liu, G.-B., Guo, H. & Yao, Y. (2017). An efficient method for hybrid density functional calculation with spin-orbit coupling. Computer Physics Communications. https://doi.org/10.1016/j.cpc.2017.11.010.
[18]	Plascencia, C., Wan, J.& Wilson, A. K., (2017). Importance of the ligand basis set in ab initio thermochemical calculations of transition metal species. Chemical Physics Letters. DOI: http://dx.doi.org/10.1016/j.cplett.2017.08.003.
[19]	Ermler, C. W. & Tilson, J. L. (2012). Generally contracted valence-core/valence basis sets for use with relativistic effective core potentials and spin-orbit coupling operators. Computational and Theoretical Chemistry, 1002, 24-30.
[20]	Sangilipandi, S., Nagarajaprakash, R., Sutradhar, D., Kaminsky, W., Chandra, A. K. & Rao, K. (2015). Synthesis, molecular structural studies and DFT calculations of tricarbonyl rhenium(I) metal complexes containing nitrogen based N^N donor polypyridyl ligands. Inorganica Chimica Acta, 437, 177-187.
[21]	Yang, X.-Z., Wang, Y.-L., Guo, J.-Y, Zhang, T.-T., Jia, J.-F. & Wu, H.-S. (2016). The effect of group-substitution on structures and photophysical properties of rhenium(I) tricarbonyl complexes with pyridyltetrazole ligand: A DFT/TDDFT study. Journal of Materials Chemistry and Physics, 178, 173-181.
[22]	Zhao, F., Wang, J-x.& Wang, Y-b. (2011). DFT/TDDFT theoretical studies on electronic structures and spectral properties of rhenium(I) phenanthrolineimidazo complexes. Computational and Theoretical Chemistry, 985, 90-96.
[23]	Zhao, F., Wang, J., Liu, W.-q.& Wang, Y. (2012). Electronic structures and spectral properties of rhenium(I) tricarbonyl diimine complexes with phosphine ligands: DFT/TDDFT theoretical investigations. Computational and Theoretical Chemistry, 973, 40-46.
[24]	Vincendon, M., Lacombe, L., Dinh, P. M., Suraud, E. & Reinhard, P. G. (2017). Time dependent DFT in natural orbitals. Computational Materials Science, 138, 426-434.
[25]	Ullrich, C. A. & Yang, Z.-H. (2014). A brief compendium of time-dependent density-functional theory. Columbia, USA, 2, 1305-1388.
[26]	Tyminska, N. (2013). Modern Computational Chemistry Methods for Prediction of Ground and Excited-State Properties in Open Shell Systems. Dissertations, Master's Thesis & Master's Reports.
[27]	Han, D., Liu, J., Miao, R., Zhao, L. & Zhang, G., (2014). Theoretical design study on the electronic structure and photophysical properties of a series of osmium(II) complexes with different ancillary ligands. Polyhedron, 85, 506-510.
[28]	Xia, H., Zhao, F., Liu, W.& Wang, Y. (2012). Electronic structures and spectral properties of rhenium (I) tricarbonyl cyclopenta[b]dipyridine complexes containing different aromatic ring groups. Journal of Organometallic Chemistry, 727, 10-18.
[29]	Świtlicka-Olszewska, A., Klemens, T., Nawrota, I., Machura, B. & Kruszynski, R. (2015). Novel Re(I) tricarbonyl coordination compound of 5-amino-1,10-phenanthroline-Synthesis, structural, photophysical and computational studies. Journal of Luminescence, 171, 166-175.
[30]	Zhang, T.-T., Jia, J.-F., Ren, Y.& Wu, H.-S. (2011). Ligand Effects on Structures and Spectroscopic Properties of Pyridine-2-aldoxime Complexes of Re(CO)₃ Theoretical Studies. Journal of physical chemistry, 115, 3174-3181.
[31]	Seminario, J. M. (2007). Molecular and Nano Electronics: Analysis, Design and Simulation. Texas, USA, 17, 24-27.
[32]	Baryshnikov, G., Minaev, B. & Agren, H. (2017). Theory and Calculation of the Phosphorescence Phenomenon. Chemical Reviews, 117, 6500-6537.
[33]	Gouralouen, C., Eng, J., Otsuka, M., Gindensperger, E.& Daniel, C. (2014). A Quantum Chemical Interpretation of Ultrafast Luminescence Decay and Intersystem Crossings in Rhenium(I) Carbonyl Bipyridine Complexes. Journal of Chemical Theory and Computation. DOI: 10.1021/ct500846n.
[34]	Kia, R.& Safari, F. (2016). Synthesis, spectral and structural characterization and computational studies of rhenium(I)-tricarbonyl nitrito complexes of 2, 2′-bipyridine and 2,9-dimethylphenanthroline ligands: π-accepting character of the diimine ligands. Inorganica Chimica Acta. DOI: http://dx.doi.org/10.1016/j.ica.2016.08.041.

Cite This Article

Plain Text BibTeX RIS

APA Style

Dereje Fedasa, Dunkana Negussa, Alemu Talema. (2020). Effect of Substituents on Electronic Structure and Photophysical Properties of Re(I)(CO)3Cl(R-2, 2’-Bipyridine) Complex: DFT/TDDFT Study. International Journal of Computational and Theoretical Chemistry, 8(2), 27-39. https://doi.org/10.11648/j.ijctc.20200802.11

Copy | Download

ACS Style

Dereje Fedasa; Dunkana Negussa; Alemu Talema. Effect of Substituents on Electronic Structure and Photophysical Properties of Re(I)(CO)3Cl(R-2, 2’-Bipyridine) Complex: DFT/TDDFT Study. Int. J. Comput. Theor. Chem. 2020, 8(2), 27-39. doi: 10.11648/j.ijctc.20200802.11

Copy | Download

AMA Style

Dereje Fedasa, Dunkana Negussa, Alemu Talema. Effect of Substituents on Electronic Structure and Photophysical Properties of Re(I)(CO)3Cl(R-2, 2’-Bipyridine) Complex: DFT/TDDFT Study. Int J Comput Theor Chem. 2020;8(2):27-39. doi: 10.11648/j.ijctc.20200802.11

Copy | Download

@article{10.11648/j.ijctc.20200802.11,
  author = {Dereje Fedasa and Dunkana Negussa and Alemu Talema},
  title = {Effect of Substituents on Electronic Structure and Photophysical Properties of Re(I)(CO)3Cl(R-2, 2’-Bipyridine) Complex: DFT/TDDFT Study},
  journal = {International Journal of Computational and Theoretical Chemistry},
  volume = {8},
  number = {2},
  pages = {27-39},
  doi = {10.11648/j.ijctc.20200802.11},
  url = {https://doi.org/10.11648/j.ijctc.20200802.11},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ijctc.20200802.11},
  abstract = {The electronic structure, absorption and emission spectra, as well as phosphorescence efficiency of Re(I) tricarbonyl complexes of a general formula fac-[Re(I)(CO)3(L)(R-N^N)](L = Cl; N^N = 2, 2’-bipyridine; R = -H, 1; -NO2, 2; -PhNO2, 3; -NH2, 4; -TPA (triphenylamine), 5) were investigated by using density functional theory(DFT) and time dependents density functional theory (TDDFT) methods. The calculated results reveal that introductions of the Electron with drawing group (EWG) and Electron donating group (EDG) on the R position of 2, 2’-bipyridine ligand. When EWG (-NO2 and -PhNO2) are introduced into complex 2 and 3, the lowest energy absorption and emission bands are red shifted compared with that of complex 1. On the contrary, the introduction of the EDG (-NH2 and -TPA) in complex 4 and 5 cause corresponding blue shifted. The solvent effect on absorption and emission spectrum indicates that the lowest energy absorption and emission bands have red shifts with the decrease of solvent polarity. The electronic affinity (EA), ionization potential (IP) and reorganization energy (λ) results show that complex 5 is suitable to be used as an emitter in phosphorescence organic light emitting diodes (PHOLEDs). Meanwhile the emission quantum yield of complex 5 is possibly higher than that of other complexes.},
 year = {2020}
}

Copy | Download

TY  - JOUR
T1  - Effect of Substituents on Electronic Structure and Photophysical Properties of Re(I)(CO)3Cl(R-2, 2’-Bipyridine) Complex: DFT/TDDFT Study
AU  - Dereje Fedasa
AU  - Dunkana Negussa
AU  - Alemu Talema
Y1  - 2020/11/11
PY  - 2020
N1  - https://doi.org/10.11648/j.ijctc.20200802.11
DO  - 10.11648/j.ijctc.20200802.11
T2  - International Journal of Computational and Theoretical Chemistry
JF  - International Journal of Computational and Theoretical Chemistry
JO  - International Journal of Computational and Theoretical Chemistry
SP  - 27
EP  - 39
PB  - Science Publishing Group
SN  - 2376-7308
UR  - https://doi.org/10.11648/j.ijctc.20200802.11
AB  - The electronic structure, absorption and emission spectra, as well as phosphorescence efficiency of Re(I) tricarbonyl complexes of a general formula fac-[Re(I)(CO)3(L)(R-N^N)](L = Cl; N^N = 2, 2’-bipyridine; R = -H, 1; -NO2, 2; -PhNO2, 3; -NH2, 4; -TPA (triphenylamine), 5) were investigated by using density functional theory(DFT) and time dependents density functional theory (TDDFT) methods. The calculated results reveal that introductions of the Electron with drawing group (EWG) and Electron donating group (EDG) on the R position of 2, 2’-bipyridine ligand. When EWG (-NO2 and -PhNO2) are introduced into complex 2 and 3, the lowest energy absorption and emission bands are red shifted compared with that of complex 1. On the contrary, the introduction of the EDG (-NH2 and -TPA) in complex 4 and 5 cause corresponding blue shifted. The solvent effect on absorption and emission spectrum indicates that the lowest energy absorption and emission bands have red shifts with the decrease of solvent polarity. The electronic affinity (EA), ionization potential (IP) and reorganization energy (λ) results show that complex 5 is suitable to be used as an emitter in phosphorescence organic light emitting diodes (PHOLEDs). Meanwhile the emission quantum yield of complex 5 is possibly higher than that of other complexes.
VL  - 8
IS  - 2
ER  -

Copy | Download

Author Information

Dereje Fedasa

Department of Chemistry, College of Natural and Computational Sciences, Injibara University, Injibara, Ethiopia
Dunkana Negussa

Department of Chemistry, College of Natural and Computational Sciences, Wollega University, Nekemte, Ethiopia
Alemu Talema

Department of Chemistry, College of Natural and Computational Sciences, Injibara University, Injibara, Ethiopia

Download PDF

Sections

Plain Text BibTeX RIS

APA Style

Dereje Fedasa, Dunkana Negussa, Alemu Talema. (2020). Effect of Substituents on Electronic Structure and Photophysical Properties of Re(I)(CO)3Cl(R-2, 2’-Bipyridine) Complex: DFT/TDDFT Study. International Journal of Computational and Theoretical Chemistry, 8(2), 27-39. https://doi.org/10.11648/j.ijctc.20200802.11

Copy | Download

ACS Style

Dereje Fedasa; Dunkana Negussa; Alemu Talema. Effect of Substituents on Electronic Structure and Photophysical Properties of Re(I)(CO)3Cl(R-2, 2’-Bipyridine) Complex: DFT/TDDFT Study. Int. J. Comput. Theor. Chem. 2020, 8(2), 27-39. doi: 10.11648/j.ijctc.20200802.11

Copy | Download

AMA Style

Dereje Fedasa, Dunkana Negussa, Alemu Talema. Effect of Substituents on Electronic Structure and Photophysical Properties of Re(I)(CO)3Cl(R-2, 2’-Bipyridine) Complex: DFT/TDDFT Study. Int J Comput Theor Chem. 2020;8(2):27-39. doi: 10.11648/j.ijctc.20200802.11

Copy | Download

@article{10.11648/j.ijctc.20200802.11,
  author = {Dereje Fedasa and Dunkana Negussa and Alemu Talema},
  title = {Effect of Substituents on Electronic Structure and Photophysical Properties of Re(I)(CO)3Cl(R-2, 2’-Bipyridine) Complex: DFT/TDDFT Study},
  journal = {International Journal of Computational and Theoretical Chemistry},
  volume = {8},
  number = {2},
  pages = {27-39},
  doi = {10.11648/j.ijctc.20200802.11},
  url = {https://doi.org/10.11648/j.ijctc.20200802.11},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ijctc.20200802.11},
  abstract = {The electronic structure, absorption and emission spectra, as well as phosphorescence efficiency of Re(I) tricarbonyl complexes of a general formula fac-[Re(I)(CO)3(L)(R-N^N)](L = Cl; N^N = 2, 2’-bipyridine; R = -H, 1; -NO2, 2; -PhNO2, 3; -NH2, 4; -TPA (triphenylamine), 5) were investigated by using density functional theory(DFT) and time dependents density functional theory (TDDFT) methods. The calculated results reveal that introductions of the Electron with drawing group (EWG) and Electron donating group (EDG) on the R position of 2, 2’-bipyridine ligand. When EWG (-NO2 and -PhNO2) are introduced into complex 2 and 3, the lowest energy absorption and emission bands are red shifted compared with that of complex 1. On the contrary, the introduction of the EDG (-NH2 and -TPA) in complex 4 and 5 cause corresponding blue shifted. The solvent effect on absorption and emission spectrum indicates that the lowest energy absorption and emission bands have red shifts with the decrease of solvent polarity. The electronic affinity (EA), ionization potential (IP) and reorganization energy (λ) results show that complex 5 is suitable to be used as an emitter in phosphorescence organic light emitting diodes (PHOLEDs). Meanwhile the emission quantum yield of complex 5 is possibly higher than that of other complexes.},
 year = {2020}
}

Copy | Download

TY  - JOUR
T1  - Effect of Substituents on Electronic Structure and Photophysical Properties of Re(I)(CO)3Cl(R-2, 2’-Bipyridine) Complex: DFT/TDDFT Study
AU  - Dereje Fedasa
AU  - Dunkana Negussa
AU  - Alemu Talema
Y1  - 2020/11/11
PY  - 2020
N1  - https://doi.org/10.11648/j.ijctc.20200802.11
DO  - 10.11648/j.ijctc.20200802.11
T2  - International Journal of Computational and Theoretical Chemistry
JF  - International Journal of Computational and Theoretical Chemistry
JO  - International Journal of Computational and Theoretical Chemistry
SP  - 27
EP  - 39
PB  - Science Publishing Group
SN  - 2376-7308
UR  - https://doi.org/10.11648/j.ijctc.20200802.11
AB  - The electronic structure, absorption and emission spectra, as well as phosphorescence efficiency of Re(I) tricarbonyl complexes of a general formula fac-[Re(I)(CO)3(L)(R-N^N)](L = Cl; N^N = 2, 2’-bipyridine; R = -H, 1; -NO2, 2; -PhNO2, 3; -NH2, 4; -TPA (triphenylamine), 5) were investigated by using density functional theory(DFT) and time dependents density functional theory (TDDFT) methods. The calculated results reveal that introductions of the Electron with drawing group (EWG) and Electron donating group (EDG) on the R position of 2, 2’-bipyridine ligand. When EWG (-NO2 and -PhNO2) are introduced into complex 2 and 3, the lowest energy absorption and emission bands are red shifted compared with that of complex 1. On the contrary, the introduction of the EDG (-NH2 and -TPA) in complex 4 and 5 cause corresponding blue shifted. The solvent effect on absorption and emission spectrum indicates that the lowest energy absorption and emission bands have red shifts with the decrease of solvent polarity. The electronic affinity (EA), ionization potential (IP) and reorganization energy (λ) results show that complex 5 is suitable to be used as an emitter in phosphorescence organic light emitting diodes (PHOLEDs). Meanwhile the emission quantum yield of complex 5 is possibly higher than that of other complexes.
VL  - 8
IS  - 2
ER  -

Copy | Download