Synthesis, characterization and relativistic DFT studies of fac-Re(CO)3(isonicotinic acid)2Cl complex

César Zúñiga; Diego P. Oyarzún; Rudy Martin-Transaco; Mauricio Yáñez-S; Alejandra Tello; Mauricio Fuentealba; Plinio Cantero-López; Ramiro Arratia-Pérez

doi:10.1016/j.cplett.2017.09.065

Synthesis, characterization and relativistic DFT studies of fac-Re(CO)₃(isonicotinic acid)₂Cl complex

César Zúñiga, Diego P. Oyarzún, Rudy Martin-Transaco, Mauricio Yáñez-S, Alejandra Tello, Mauricio Fuentealba, Plinio Cantero-López, Ramiro Arratia-Pérez

Exact Sciences School

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

7 Citations (Scopus)

Abstract

In this work, new fac-Re(CO)₃(PyCOOH)₂Cl from isonicotinic acid ligand has been prepared. The complex was characterized by structural (single-crystal X-ray diffraction), elemental analysis and spectroscopic (FTIR, NMR, UV-vis spectroscopy) methods. DFT and TDDFT calculations were performed to obtain the electronic transitions involved in their UV-Vis spectrum. The excitation energies agree with the experimental results. The TDDFT calculations suggest that experimental mixed absorption bands at 270 and 314[U+202F]nm could be assigned to (MLCT-LLCT)/MLCT transitions. Natural Bond Orbitals (NBO) approach has enabled studying the effects of bonding interactions. E(2) energies confirm the occurrence of ICT (Intra-molecular Charge Transfer) within the molecule.

Original language	English
Pages (from-to)	66-73
Number of pages	8
Journal	Chemical Physics Letters
Volume	688
DOIs	https://doi.org/10.1016/j.cplett.2017.09.065
Publication status	Accepted/In press - 2017

Keywords

Isonicotinic acid
Relativistic DFT calculations
Rhenium (I) complex
UV-vis spectrum

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

Access to Document

10.1016/j.cplett.2017.09.065

Cite this

@article{5eb4fd3063c84052a4e462c26c92fccc,

title = "Synthesis, characterization and relativistic DFT studies of fac-Re(CO)3(isonicotinic acid)2Cl complex",

abstract = "In this work, new fac-Re(CO)3(PyCOOH)2Cl from isonicotinic acid ligand has been prepared. The complex was characterized by structural (single-crystal X-ray diffraction), elemental analysis and spectroscopic (FTIR, NMR, UV-vis spectroscopy) methods. DFT and TDDFT calculations were performed to obtain the electronic transitions involved in their UV-Vis spectrum. The excitation energies agree with the experimental results. The TDDFT calculations suggest that experimental mixed absorption bands at 270 and 314[U+202F]nm could be assigned to (MLCT-LLCT)/MLCT transitions. Natural Bond Orbitals (NBO) approach has enabled studying the effects of bonding interactions. E(2) energies confirm the occurrence of ICT (Intra-molecular Charge Transfer) within the molecule.",

keywords = "Isonicotinic acid, Relativistic DFT calculations, Rhenium (I) complex, UV-vis spectrum",

author = "C{\'e}sar Z{\'u}{\~n}iga and Oyarz{\'u}n, {Diego P.} and Rudy Martin-Transaco and Mauricio Y{\'a}{\~n}ez-S and Alejandra Tello and Mauricio Fuentealba and Plinio Cantero-L{\'o}pez and Ramiro Arratia-P{\'e}rez",

note = "Funding Information: We are grateful to project PMI-UAB 1301 of Universidad Andres Bello for the financial support for this study, to the Iniciativa Cient{\'i}fica Milenio (ICM) RC 120001 del Ministerio de Econom{\'i}a, Fomento y Turismo del Gobierno de Chile. P.C.L. acknowledges CONICYT PCHA/Doctorado Nacional/2013-63130037 for his PhD fellowship and Andres Bello University (internal project DI-712-15/I). R. M.-T. We also thank the support from the grant FONDECYT-3150205 and M. Y.-S. thanks to DICYT-USACH Project 021541YS. A. T. thanks the Universidad de Atacama for project DIUDA 22339. ",

year = "2017",

doi = "10.1016/j.cplett.2017.09.065",

language = "English",

volume = "688",

pages = "66--73",

journal = "Chemical Physics Letters",

issn = "0009-2614",

publisher = "Elsevier",

}

TY - JOUR

T1 - Synthesis, characterization and relativistic DFT studies of fac-Re(CO)3(isonicotinic acid)2Cl complex

AU - Zúñiga, César

AU - Oyarzún, Diego P.

AU - Martin-Transaco, Rudy

AU - Yáñez-S, Mauricio

AU - Tello, Alejandra

AU - Fuentealba, Mauricio

AU - Cantero-López, Plinio

AU - Arratia-Pérez, Ramiro

N1 - Funding Information: We are grateful to project PMI-UAB 1301 of Universidad Andres Bello for the financial support for this study, to the Iniciativa Científica Milenio (ICM) RC 120001 del Ministerio de Economía, Fomento y Turismo del Gobierno de Chile. P.C.L. acknowledges CONICYT PCHA/Doctorado Nacional/2013-63130037 for his PhD fellowship and Andres Bello University (internal project DI-712-15/I). R. M.-T. We also thank the support from the grant FONDECYT-3150205 and M. Y.-S. thanks to DICYT-USACH Project 021541YS. A. T. thanks the Universidad de Atacama for project DIUDA 22339.

PY - 2017

Y1 - 2017

N2 - In this work, new fac-Re(CO)3(PyCOOH)2Cl from isonicotinic acid ligand has been prepared. The complex was characterized by structural (single-crystal X-ray diffraction), elemental analysis and spectroscopic (FTIR, NMR, UV-vis spectroscopy) methods. DFT and TDDFT calculations were performed to obtain the electronic transitions involved in their UV-Vis spectrum. The excitation energies agree with the experimental results. The TDDFT calculations suggest that experimental mixed absorption bands at 270 and 314[U+202F]nm could be assigned to (MLCT-LLCT)/MLCT transitions. Natural Bond Orbitals (NBO) approach has enabled studying the effects of bonding interactions. E(2) energies confirm the occurrence of ICT (Intra-molecular Charge Transfer) within the molecule.

AB - In this work, new fac-Re(CO)3(PyCOOH)2Cl from isonicotinic acid ligand has been prepared. The complex was characterized by structural (single-crystal X-ray diffraction), elemental analysis and spectroscopic (FTIR, NMR, UV-vis spectroscopy) methods. DFT and TDDFT calculations were performed to obtain the electronic transitions involved in their UV-Vis spectrum. The excitation energies agree with the experimental results. The TDDFT calculations suggest that experimental mixed absorption bands at 270 and 314[U+202F]nm could be assigned to (MLCT-LLCT)/MLCT transitions. Natural Bond Orbitals (NBO) approach has enabled studying the effects of bonding interactions. E(2) energies confirm the occurrence of ICT (Intra-molecular Charge Transfer) within the molecule.

KW - Isonicotinic acid

KW - Relativistic DFT calculations

KW - Rhenium (I) complex

KW - UV-vis spectrum

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DO - 10.1016/j.cplett.2017.09.065

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VL - 688

SP - 66

EP - 73

JO - Chemical Physics Letters

JF - Chemical Physics Letters

ER -