Kinetic study of the azo – Hydrazone photoinduced mechanism in complexes with a -Re(CO)3L0/+ core by flash photolysis

Maldonado, Tamara; Flores, Erick; Gómez, Alejandra; Godoy, Fernando; Mascayano, Carolina; Martí, Angel A.; Ferraudi, Guillermo

doi:10.1016/j.jphotochem.2023.114802

Kinetic study of the azo – Hydrazone photoinduced mechanism in complexes with a -Re(CO)₃L^0/+ core by flash photolysis

Journal Article · Tue Apr 25 00:00:00 EDT 2023 · Journal of Photochemistry and Photobiology. A, Chemistry

DOI:https://doi.org/10.1016/j.jphotochem.2023.114802· OSTI ID:2418858

^[1]; ^[2]; ^[2]; Godoy, Fernando ^[2]; Mascayano, Carolina ^[2]; Martí, Angel A. ^[3]; ^[4]

Pontifical Catholic University of Valparaíso (Chile); OSTI
University of Santiago (Chile)
Rice Univ., Houston, TX (United States)
University of Notre Dame, IN (United States)

The photoprocesses of three rhenium(I) tricarbonyl complexes, fac-Re(NN)(CO)₃L^0/+, bearing an azo/hydrazone ligand, NN, and L = Cl, Br or CH₃CN as axial ligand, were studied by time-resolved spectroscopic techniques. Flash irradiation of deaerated solutions of the complexes in acetonitrile photogenerated intermediates with intense optical absorptions in the UV–vis spectral region of the hydrazone ligand. The decay of the intermediates photogenerated with the Cl, Br and CH₃CN ligands in the axial position proceeds by three different mechanisms. For the fac-Re(NN)(CO)₃Cl, a three-step mechanism involving isomerization, tautomerization and rotation accounts for the spectroscopic transformations. In contrast to the flash photolysis result, the continuous photolysis of the complex in acetonitrile does not show spectroscopic changes associated with the generation of a stable product, i.e., the complex exhibits a photoreversible behavior. The first step observed in the flash irradiation of fac-Re(NN)(CO)₃Cl, is missing in the decay of the photogenerated intermediates with fac-Re(NN)(CO)₃Br and fac-[Re(NN)(CO)₃CH₃CN]⁺. A possible reason for this absence is that the process is too fast for the time-response of the flash photolysis set-up. Time-resolved spectra and associated reaction rate data for the Re(I) complexes are communicated and discussed. Finally, DFT calculations support a plausible E → Z mechanism with thermal back-isomerization mediated by tautomerization.

View Accepted Manuscript (DOE)

Research Organization:: University of Notre Dame, IN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: FC02-04ER15533

OSTI ID:: 2418858

Alternate ID(s):: OSTI ID: 2000216

Journal Information:: Journal of Photochemistry and Photobiology. A, Chemistry, Journal Name: Journal of Photochemistry and Photobiology. A, Chemistry Vol. 442; ISSN 1010-6030

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (34)

Kinetic and Mechanistic Observations on the Photoinduced Isomerization Reaction of Organometallic Chalcones: A Steady State and Flash Photolysis Study Maldonado, Tamara; Ferraudi, Guillermo; Lappin, A. Graham ChemPhotoChem, Vol. 2, Issue 2 https://doi.org/10.1002/cptc.201700129	journal	January 2018
Energies, structures, and electronic properties of molecules in solution with the C-PCM solvation model Cossi, Maurizio; Rega, Nadia; Scalmani, Giovanni Journal of Computational Chemistry, Vol. 24, Issue 6 https://doi.org/10.1002/jcc.10189	journal	April 2003
Multiwfn: A multifunctional wavefunction analyzer Lu, Tian; Chen, Feiwu Journal of Computational Chemistry, Vol. 33, Issue 5 https://doi.org/10.1002/jcc.22885	journal	December 2011
Perspective on "Density functional thermochemistry. III. The role of exact exchange" Raghavachari, Krishnan Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 103, Issue 3-4 https://doi.org/10.1007/s002149900065	journal	February 2000
Structural behavior of rhenium complexes in fluoride sensing: a spectroscopic and computational study Velayudham, Murugesan; Ramdass, Arumugam; Sathish, Veerasamy Structural Chemistry, Vol. 33, Issue 4 https://doi.org/10.1007/s11224-022-01904-4	journal	March 2022
Synthesis, crystal structure, DFT calculation and trans → cis isomerisation studies of bipyridyl ruthenium(II) complexes bearing 8-oxyquinolate azo ligands Patra, Roumi; Maity, Amit; Rajak, Kajal Krishna Journal of Chemical Sciences, Vol. 132, Issue 1 https://doi.org/10.1007/s12039-020-01846-6	journal	October 2020
The possible tautomerism of the potential rotary switch 2-(2-(2-Hydroxy-4-nitrophenyl)hydrazono)-1-phenylbutane-1,3-dione Hristova, Silvia; Kamounah, Fadhil S.; Molla, Nevse Dyes and Pigments, Vol. 144 https://doi.org/10.1016/j.dyepig.2017.05.021	journal	September 2017
A family of azoquinoline derivatives: Effect of the substituent at azo linkage on thermal cis-trans isomerization based on an experimental and computational approach Bujak, Karolina; Wasiak, Anna; Sobolewska, Anna Dyes and Pigments, Vol. 175 https://doi.org/10.1016/j.dyepig.2019.108151	journal	April 2020
Dihydroquinolylazotetrazole dyes: Effect of a substituent at the tetrazole fragment on spectral properties and thermal ‒ isomerization in organic solvents Nekipelova, Tatiana D.; Khodot, Evgenii N.; Deeva, Yulia S. Dyes and Pigments, Vol. 195 https://doi.org/10.1016/j.dyepig.2021.109675	journal	November 2021
Azo–hydrazone tautomerism in organometallic complexes triggered by a -Re(CO)3(L) core: A spectroscopic and theoretical study Maldonado, Tamara; Flores, Erick; Llanos, Leonel Dyes and Pigments, Vol. 197 https://doi.org/10.1016/j.dyepig.2021.109953	journal	January 2022
Photosensitized generation of singlet oxygen from rhenium(I) complexes: A review Wolcan, Ezequiel Inorganica Chimica Acta, Vol. 509 https://doi.org/10.1016/j.ica.2020.119650	journal	September 2020
Azobased iminopyridine ligands and their rhenium metal complexes: Syntheses, spectroscopic, trans-cis photoisomerization and theoretical studies Benmensour, Mohamed Ali; Ayadi, Awatef; Akdas-Kilig, Huriye Journal of Photochemistry and Photobiology A: Chemistry, Vol. 368 https://doi.org/10.1016/j.jphotochem.2018.09.023	journal	January 2019
Photo induced trans→cis isomerism studies of heteroleptic iridium complex with 8-quinolinol-5-phenylazo ligand: Photophysical and electrochemical studies and it's theoretical investigations Maity, Amit; Rajak, Kajal Krishna Journal of Molecular Structure, Vol. 1181 https://doi.org/10.1016/j.molstruc.2018.12.060	journal	April 2019
A comprehensive spectroscopic, solvatochromic and photochemical analysis of 5-hydroxyquinoline and 8-hydroxyquinoline mono-azo dyes Rashidnejad, Hamid; Ramezanitaghartapeh, Mohammad; Pesyan, Nader Noroozi Journal of Molecular Structure, Vol. 1223 https://doi.org/10.1016/j.molstruc.2020.129323	journal	January 2021
Photo-physical and structural studies of some synthesized arylazoquinoline dyes Ghanadzadeh Gilani, A.; Taghvaei, V.; Moradi Rufchahi, E. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 185 https://doi.org/10.1016/j.saa.2017.05.035	journal	October 2017
Computational Design of Rhenium(I) Carbonyl Complexes for Anticancer Photodynamic Therapy Álvarez, Daniel; Menéndez, M. Isabel; López, Ramón Inorganic Chemistry, Vol. 61, Issue 1 https://doi.org/10.1021/acs.inorgchem.1c03130	journal	December 2021
Hydrogen Bonding Promoted Tautomerism between Azo and Hydrazone Forms in Calcon with Multistimuli Responsiveness and Biocompatibility Zheng, Dong; Gu, Yuming; Li, Xiang Journal of Chemical Information and Modeling, Vol. 59, Issue 5 https://doi.org/10.1021/acs.jcim.8b00985	journal	February 2019
Rhenium(I) Tricarbonyl Complexes with Peripheral N-Coordination Sites: A Foundation for Heterotrimetallic Nonlinear Optical Chromophores Coe, Benjamin J.; Foxon, Simon P.; Pilkington, Rachel A. Organometallics, Vol. 35, Issue 17 https://doi.org/10.1021/acs.organomet.6b00536	journal	August 2016
Substituents and Cocatalyst Effect on the Catalytic Response and Overpotential of Re(I) Catalysts for CO₂ Reduction Boraghi, Mahsasadat; White, Travis A.; Pordel, Shabnam ACS Applied Energy Materials, Vol. 4, Issue 12 https://doi.org/10.1021/acsaem.1c02462	journal	December 2021
Nature of the lowest excited state in tricarbonylchloro-1,10-phenanthrolinerhenium(I) and related complexes Wrighton, Mark; Morse, David L. Journal of the American Chemical Society, Vol. 96, Issue 4 https://doi.org/10.1021/ja00811a008	journal	February 1974
Catalysis of the cis → trans Isomerization of 2-Hydroxy-5-methylazobenzene Wettermark, Gunnar; Langmuir, Margaret E.; Anderson, Daniel G. Journal of the American Chemical Society, Vol. 87, Issue 3 https://doi.org/10.1021/ja01081a014	journal	February 1965
Marked Improvement in Photoinduced Cell Death by a New Tris-heteroleptic Complex with Dual Action: Singlet Oxygen Sensitization and Ligand Dissociation Albani, Bryan A.; Peña, Bruno; Leed, Nicholas A. Journal of the American Chemical Society, Vol. 136, Issue 49 https://doi.org/10.1021/ja508272h	journal	December 2014
Excited-State Switching in Rhenium(I) Bipyridyl Complexes with Donor–Donor and Donor–Acceptor Substituents Sutton, Joshua J.; Preston, Dan; Traber, Philipp Journal of the American Chemical Society, Vol. 143, Issue 24 https://doi.org/10.1021/jacs.1c02755	journal	June 2021
Preparation and Reactivity of Pendent- --CO ₂ Rh ^III (phthalocyanine) Bound to a Poly(acrylate) Backbone. Effects of the Hypercoiled Backbone on the Association, Photochemical, and Thermal Redox Reactions of the Pendent Macrocycle Thomas, S.; Ruiz, G.; Ferraudi, G. Macromolecules, Vol. 39, Issue 19 https://doi.org/10.1021/ma061264u	journal	September 2006
Photochemical and Photophysical Reactions of f ac -Rhenium(I) Tricarbonyl Complexes. Effects from Binucleating Spectator Ligands on Excited and Ground State Processes Guerrero, J.; Piro, O. E.; Wolcan, E. Organometallics, Vol. 20, Issue 13 https://doi.org/10.1021/om000784p	journal	June 2001
Heteroaryl azo dyes as molecular photoswitches Crespi, Stefano; Simeth, Nadja A.; König, Burkhard Nature Reviews Chemistry, Vol. 3, Issue 3 https://doi.org/10.1038/s41570-019-0074-6	journal	February 2019
Synthesis, structure and spectroscopic properties of Re(i) complexes incorporating 5-arylazo-8-hydroxyquinoline: a density functional theory/time-dependent density functional theory investigation Sarkar, Rupa; Mondal, Pallab; Rajak, Kajal Krishna Dalton Trans., Vol. 43, Issue 7 https://doi.org/10.1039/C3DT52630E	journal	January 2014
Mononuclear rhenium(i) complexes incorporating 2-(arylazo)phenyl benzyl thioethers: synthesis, structure, spectral, DFT and TDDFT studies Mondal, Pallab; Sarkar, Rupa; Hens, Amar RSC Advances, Vol. 4, Issue 73 https://doi.org/10.1039/C4RA05699J	journal	August 2014
Photoswitching hydrazones based on benzoylpyridine Mravec, Bernard; Filo, Juraj; Csicsai, Klaudia Physical Chemistry Chemical Physics, Vol. 21, Issue 44 https://doi.org/10.1039/C9CP05049C	journal	January 2019
Accessing the triplet manifold of naphthalene benzimidazole–phenanthroline in rhenium(i) bichromophores Wells, Kaylee A.; Yarnell, James E.; Sheykhi, Sara Dalton Transactions, Vol. 50, Issue 37 https://doi.org/10.1039/D1DT02329B	journal	January 2021
Understanding the fast thermal isomerisation of azophenols in glassy and liquid-crystalline polymers Garcia-Amorós, Jaume; Velasco, Dolores Physical Chemistry Chemical Physics, Vol. 16, Issue 7 https://doi.org/10.1039/c3cp54519a	journal	January 2014
Optically induced azo-hydrazone tautomerism of some 2,6-dialkylphenol-based azobenzenes Markava, Elga; Gustina, Daina; Muzikante, Inta Optical Organic and Inorganic Materials https://doi.org/10.1117/12.425487	conference	April 2001
Dynamics of trans-cis photoisomerization of hetarylazo dyes Lygo, O. N.; Khodot, E. N.; Ogurtsov, V. A. High Energy Chemistry, Vol. 48, Issue 5 https://doi.org/10.1134/S0018143914050099	journal	September 2014
Photochemistry of Rhenium(I) Diimine Tricarbonyl Complexes in Biological Applications Schindler, Kevin; Zobi, Fabio CHIMIA, Vol. 75, Issue 10 https://doi.org/10.2533/chimia.2021.837	journal	October 2021

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Kinetic study of the azo – Hydrazone photoinduced mechanism in complexes with a -Re(CO)3L0/+ core by flash photolysis

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Kinetic study of the azo – Hydrazone photoinduced mechanism in complexes with a -Re(CO)₃L^0/+ core by flash photolysis