ACS Publications. Most Trusted. Most Cited. Most Read
Photochemistry of [Ru(pytz)(btz)2]2+ and Characterization of a κ1-btz Ligand-Loss Intermediate

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:Inorg. Chem. 2016, 55, 15, 7787-7796
    Article

    Photochemistry of [Ru(pytz)(btz)2]2+ and Characterization of a κ1-btz Ligand-Loss Intermediate
    Click to copy article linkArticle link copied!

    View Author Information
    Department of Chemistry, University of Huddersfield, Queensgate, Huddersfield HD1 3DH, United Kingdom
    *E-mail: [email protected]
    Other Access OptionsSupporting Information (3)

    Inorganic Chemistry

    Cite this: Inorg. Chem. 2016, 55, 15, 7787–7796
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.6b00782
    Published July 21, 2016
    Copyright © 2016 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    We report the synthesis, characterization, and photochemical reactivity of the triazole-containing complex [Ru(pytz)(btz)2]2+ (1, pytz = 1-benzyl-4-(pyrid-2-yl)-1,2,3-triazole, btz = 1,1′-dibenzyl-4,4′-bi-1,2,3-triazolyl). The UV–vis absorption spectrum of 1 exhibits pytz- and btz-centered 1MLCT bands at 365 and 300 nm, respectively. Upon photoexcitation, acetonitrile solutions of 1 undergo conversion to the ligand-loss intermediate, trans-[Ru(pytz)(κ2-btz)(κ1-btz)(NCMe)]2+ (2, Φ363 = 0.013) and ultimately to the ligand-loss product trans-[Ru(pytz)(btz)(NCMe)2]2+ (3), both of which are observed and characterized by 1H NMR spectroscopy. Time-dependent density functional theory calculations reveal that the S1 state of the complex has primarily HOMO → LUMO pytz-based 1MLCT character. Data show that the 3MLCT and 3MC states are in close energetic proximity (≤0.11 eV to 2 d.p.) and that the T1 state from a single-point triplet state calculation at the S0 geometry suggests 3MC character. Optimization of the T1 state of the complex starting from the ground state geometry leads to elongation of the two Ru–N(btz) bonds cis to the pytz ligand to 2.539 and 2.544 Å leading to a pseudo-4-coordinate 3MC state rather than the 3MLCT state. The work therefore provides additional insights into the photophysical and photochemical properties of ruthenium triazole-containing complexes and their excited state dynamics.

    Copyright © 2016 American Chemical Society

    Subjects

    what are subjects

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Supporting Information

    Click to copy section linkSection link copied!

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.6b00782.

    • Electrochemical data, mass spectrometry data, optimized geometry coordinates for S0 and T1 states of 1, and molecular orbital plots for the ground state of 1 (PDF)

    • Crystallographic data for [Ru(pytz)(btz)2][PF6]2 (CIF)

    • Crystallographic data for [Ru(p-cymene)(pytz)Cl][PF6]·MeCN (CIF)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!
    Citation Statements
    Explore this article's citation statements on scite.ai
    powered by  Scite

    This article is cited by 27 publications.

    1. Jakob Steube, Lorena Fritsch, Ayla Kruse, Olga S. Bokareva, Serhiy Demeshko, Hossam Elgabarty, Roland Schoch, Mohammad Alaraby, Hans Egold, Bastian Bracht, Lennart Schmitz, Stephan Hohloch, Thomas D. Kühne, Franc Meyer, Oliver Kühn, Stefan Lochbrunner, Matthias Bauer. Isostructural Series of a Cyclometalated Iron Complex in Three Oxidation States. Inorganic Chemistry 2024, 63 (37) , 16964-16980. https://doi.org/10.1021/acs.inorgchem.4c02576
    2. Pritha Chatterjee, Ramranjan Mishra, Sakshi Chawla, Avinash Kumar Sonkar, Arijit K. De, Ashis K. Patra. Dual Photoreactive Ternary Ruthenium(II) Terpyridyl Complexes: A Comparative Study on Visible-Light-Induced Single-Step Dissociation of Bidentate Ligands and Generation of Singlet Oxygen. Inorganic Chemistry 2024, 63 (32) , 14998-15015. https://doi.org/10.1021/acs.inorgchem.4c01727
    3. Katie Eastham, Paul A. Scattergood, Danny Chu, Rayhaan Z. Boota, Adrien Soupart, Fabienne Alary, Isabelle M. Dixon, Craig R. Rice, Samantha J. O. Hardman, Paul I. P. Elliott. Not All 3MC States Are the Same: The Role of 3MCcis States in the Photochemical N∧N Ligand Release from [Ru(bpy)2(N∧N)]2+ Complexes. Inorganic Chemistry 2022, 61 (49) , 19907-19924. https://doi.org/10.1021/acs.inorgchem.2c03146
    4. Rayhaan Z. Boota, Samantha J. O. Hardman, Gage P. Ashton, Craig R. Rice, Paul A. Scattergood, Paul I. P. Elliott. Photochemistry of Heteroleptic 1,4,5,8-Tetraazaphenanthrene- and Bi-1,2,3-triazolyl-Containing Ruthenium(II) Complexes. Inorganic Chemistry 2021, 60 (20) , 15768-15781. https://doi.org/10.1021/acs.inorgchem.1c02441
    5. Masanari Hirahara, Yasushi Umemura. A Synthetic Route to a Ruthenium Complex via Successive Photosubstitution Reactions. Inorganic Chemistry 2021, 60 (17) , 13193-13199. https://doi.org/10.1021/acs.inorgchem.1c01578
    6. Isabelle M. Dixon, Sylvestre Bonnet, Fabienne Alary, Jérôme Cuny. Photoinduced Ligand Exchange Dynamics of a Polypyridyl Ruthenium Complex in Aqueous Solution. The Journal of Physical Chemistry Letters 2021, 12 (30) , 7278-7284. https://doi.org/10.1021/acs.jpclett.1c01424
    7. Oscar A. Lenis-Rojas, Rui Cabral, Beatriz Carvalho, Sofia Friães, Catarina Roma-Rodrigues, Jhonathan A. A. Fernández, Sabela F. Vila, Laura Sanchez, Clara S. B. Gomes, Alexandra R. Fernandes, Beatriz Royo. Triazole-Based Half-Sandwich Ruthenium(II) Compounds: From In Vitro Antiproliferative Potential to In Vivo Toxicity Evaluation. Inorganic Chemistry 2021, 60 (11) , 8011-8026. https://doi.org/10.1021/acs.inorgchem.1c00527
    8. Adrien Soupart, Fabienne Alary, Jean-Louis Heully, Paul I. P. Elliott, Isabelle M. Dixon. Theoretical Study of the Full Photosolvolysis Mechanism of [Ru(bpy)3]2+: Providing a General Mechanistic Roadmap for the Photochemistry of [Ru(N^N)3]2+-Type Complexes toward Both Cis and Trans Photoproducts. Inorganic Chemistry 2020, 59 (20) , 14679-14695. https://doi.org/10.1021/acs.inorgchem.0c01843
    9. Dmytro Havrylyuk, David K. Heidary, Yang Sun, Sean Parkin, Edith C. Glazer. Photochemical and Photobiological Properties of Pyridyl-pyrazol(in)e-Based Ruthenium(II) Complexes with Sub-micromolar Cytotoxicity for Phototherapy. ACS Omega 2020, 5 (30) , 18894-18906. https://doi.org/10.1021/acsomega.0c02079
    10. Guocan Li, Matthew D. Brady, Gerald J. Meyer. Visible Light Driven Bromide Oxidation and Ligand Substitution Photochemistry of a Ru Diimine Complex. Journal of the American Chemical Society 2018, 140 (16) , 5447-5456. https://doi.org/10.1021/jacs.8b00944
    11. Duenpen Unjaroen, Juan Chen, Edwin Otten, and Wesley R. Browne . Switching Pathways for Reversible Ligand Photodissociation in Ru(II) Polypyridyl Complexes with Steric Effects. Inorganic Chemistry 2017, 56 (2) , 900-907. https://doi.org/10.1021/acs.inorgchem.6b02521
    12. Felix N. Castellano . Editorial for the ACS Select Virtual Issue on Emerging Investigators in Inorganic Photochemistry and Photophysics. Inorganic Chemistry 2016, 55 (24) , 12483-12487. https://doi.org/10.1021/acs.inorgchem.6b02830
    13. Ramranjan Mishra, Abhijit Saha, Pritha Chatterjee, Sucheta Kundu, Madhu Verma, Sabyasachi Sarkar, Sri Sivakumar, Anindya Datta, Ashis K. Patra. Unravelling the Relaxation Pathway and Excited State Dynamics of Ruthenium(II) Polypyridyl Complexes Incorporating Phosphorus‐Based Monodentate Ligands. Chemistry – A European Journal 2025, 31 (14) https://doi.org/10.1002/chem.202404231
    14. Ramranjan Mishra, Pritha Chatterjee, Ray J. Butcher, Ashis K. Patra. A serendipitous crossed aldol reaction in the ligand periphery of a Ru( ii ) polypyridyl complex in silica bed: prospects for delivering anticancer agents for photoactivated chemotherapy. Dalton Transactions 2024, 53 (46) , 18484-18493. https://doi.org/10.1039/D4DT02337D
    15. Samuel Francis, Craig R. Rice, Paul A. Scattergood, Paul I. P. Elliott. Synthesis and characterisation of group 8 tris(1-benzyl-1,2,3-triazol-4-yl)- p -anisolylmethane complexes. Dalton Transactions 2022, 51 (36) , 13692-13702. https://doi.org/10.1039/D2DT02503E
    16. Kate L. Flint, David M. Huang, Oliver M. Linder‐Patton, Christopher J. Sumby, F. Richard Keene. Synthesis of Triple‐Stranded Diruthenium(II) Compounds. European Journal of Inorganic Chemistry 2022, 2022 (25) https://doi.org/10.1002/ejic.202200225
    17. M.C. Joseph, A.J. Swarts, S.F. Mapolie. Cationic half-sandwich ruthenium (II) complexes ligated by pyridyl-triazole ligands: Transfer hydrogenation and mechanistic studies. Polyhedron 2022, 212 , 115579. https://doi.org/10.1016/j.poly.2021.115579
    18. Osman Dayan, Arife Gencer Imer, Melek Tercan, Aysegul Dere, Abdullah G. Al-Sehemi, Ahmed A. Al-Ghamdi, Fahrettin Yakuphanoglu. Dye sensitized solar cell-based optoelectronic device using novel [Ru(L1)(L2)(NCS)2] complex. Journal of Molecular Structure 2021, 1238 , 130464. https://doi.org/10.1016/j.molstruc.2021.130464
    19. Adrien Soupart, Fabienne Alary, Jean-Louis Heully, Paul I.P. Elliott, Isabelle M. Dixon. Recent progress in ligand photorelease reaction mechanisms: Theoretical insights focusing on Ru(II) 3MC states. Coordination Chemistry Reviews 2020, 408 , 213184. https://doi.org/10.1016/j.ccr.2020.213184
    20. Adrian Comia, Luke Charalambou, Salem A. E. Omar, Paul A. Scattergood, Paul I. P. Elliott, Alessandro Sinopoli. Photophysical and Electrocatalytic Properties of Rhenium(I) Triazole-Based Complexes. Inorganics 2020, 8 (3) , 22. https://doi.org/10.3390/inorganics8030022
    21. Wei-Guo Jia, Ming-Xia Cheng, Li-Li Gao, Siu Min Tan, Chao Wang, Xiaogang Liu, Richmond Lee. A ruthenium bisoxazoline complex as a photoredox catalyst for nitro compound reduction under visible light. Dalton Transactions 2019, 48 (27) , 9949-9953. https://doi.org/10.1039/C9DT00428A
    22. Masanari Hirahara, Hiroki Goto, Rei Yamamoto, Masayuki Yagi, Yasushi Umemura. Photoisomerization and thermal isomerization of ruthenium aqua complexes with chloro-substituted asymmetric bidentate ligands. RSC Advances 2019, 9 (4) , 2002-2010. https://doi.org/10.1039/C8RA08943D
    23. Paul A. Scattergood, Alessandro Sinopoli, Paul I.P. Elliott. Photophysics and photochemistry of 1,2,3-triazole-based complexes. Coordination Chemistry Reviews 2017, 350 , 136-154. https://doi.org/10.1016/j.ccr.2017.06.017
    24. Isabelle M. Dixon, Jean-Louis Heully, Fabienne Alary, Paul I. P. Elliott. Theoretical illumination of highly original photoreactive 3 MC states and the mechanism of the photochemistry of Ru( ii ) tris(bidentate) complexes. Phys. Chem. Chem. Phys. 2017, 19 (40) , 27765-27778. https://doi.org/10.1039/C7CP05532C
    25. Hyo Jin Jang, Samantha L. Hopkins, Maxime A. Siegler, Sylvestre Bonnet. Frontier orbitals of photosubstitutionally active ruthenium complexes: an experimental study of the spectator ligands’ electronic properties influence on photoreactivity. Dalton Transactions 2017, 46 (30) , 9969-9980. https://doi.org/10.1039/C7DT01540B
    26. Paul A. Scattergood, Paul I. P. Elliott. An unexpected journey from highly tunable phosphorescence to novel photochemistry of 1,2,3-triazole-based complexes. Dalton Transactions 2017, 46 (47) , 16343-16356. https://doi.org/10.1039/C7DT03836D
    27. Juan Sanz García, Fabienne Alary, Martial Boggio-Pasqua, Isabelle M. Dixon, Jean-Louis Heully. Is photoisomerization required for NO photorelease in ruthenium nitrosyl complexes?. Journal of Molecular Modeling 2016, 22 (11) https://doi.org/10.1007/s00894-016-3138-2
    Download PDF
    Go to Inorganic Chemistry
    Get e-Alerts
    Get e-Alerts

    Inorganic Chemistry

    Cite this: Inorg. Chem. 2016, 55, 15, 7787–7796
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.6b00782
    Published July 21, 2016
    Copyright © 2016 American Chemical Society
    Request reuse permissions

    Article Views

    999

    Altmetric

    -

    Citations

    27
    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.