New Ligand Design Provides Delocalization and Promotes Strong Absorption throughout the Visible Region in a Ru(II) Complex

Whittemore, Tyler J.; White, Travis A.; Turro, Claudia

doi:10.1021/jacs.7b09389

New Ligand Design Provides Delocalization and Promotes Strong Absorption throughout the Visible Region in a Ru(II) Complex

Journal Article · Wed Dec 20 00:00:00 EST 2017 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.7b09389· OSTI ID:1430217

Whittemore, Tyler J. ^[1]; ^[2]; ^[2]

The Ohio State Univ., Columbus, OH (United States). Department of Chemistry and Biochemistry; The Ohio State University
The Ohio State Univ., Columbus, OH (United States). Department of Chemistry and Biochemistry

The new Ru(II)–anthraquinone complex [Ru(bpy)₂(qdpq)](PF₆)₂ (Ru-qdpq; bpy = 2,2'-bipyridine; qdpq = 2,3-di(2-pyridyl)naphtho[2,3-f]quinoxaline-7,12-quinone) possesses a strong ¹MLCT Ru → qdpq absorption with a maximum at 546 nm that tails into the near-IR and is significantly red-shifted relative to that of the related complex [Ru(bpy)₂(qdppz)](PF₆)₂ (Ru-qdppz; qdppz = naphtho[2,3-a]dipyrido[3,2-h:2',3'-f]phenazine-5,18-dione), with λ_max = 450 nm. Ru-qdppz possesses electronically isolated proximal and distal qdppz-based excited states; the former is initially generated and decays to the latter, which repopulates the ground state with τ = 362 ps. In contrast, excitation of Ru-qdpq results in the population of a relatively long-lived (τ = 19 ns) Ru(dπ) → qdpq(π*) ³MLCT excited state where the promoted electron is delocalized throughout the qdpq ligand. Ultrafast spectroscopy, used together with steady-state absorption, electrochemistry, and DFT calculations, indicates that the unique coordination modes of the qdpq and qdppz ligands impart substantially different electronic communication throughout the quinone-containing ligand, affecting the excited state and electron transfer properties of these molecules. As a result, these observations create a pathway to synthesize complexes with red-shifted absorptions that possess long-lived, redox-active excited states that are useful for various applications, including solar energy conversion and photochemotherapy.

View Accepted Manuscript (DOE)

Research Organization:: The Ohio State Univ., Columbus, OH (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0010542

OSTI ID:: 1430217

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 1 Vol. 140; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (57)

Broadband Femtosecond Fluorescence Spectroscopy of [Ru(bpy)3]2+ Cannizzo, Andrea; van Mourik, Frank; Gawelda, Wojciech Angewandte Chemie International Edition, Vol. 45, Issue 19 https://doi.org/10.1002/anie.200600125	journal	May 2006
Photophysical Properties of Ruthenium(II) Polypyridyl DNA Intercalators: Effects of the Molecular Surroundings Investigated by Theory Véry, Thibaut; Ambrosek, David; Otsuka, Miho Chemistry - A European Journal, Vol. 20, Issue 40 https://doi.org/10.1002/chem.201402963	journal	August 2014
Quinones as Reversible Electron Relays in Artificial Photosynthesis Rodenberg, Alexander; Orazietti, Margherita; Mosberger, Mathias ChemPhysChem, Vol. 17, Issue 9 https://doi.org/10.1002/cphc.201501085	journal	February 2016
Photochemical Conversion of Solar Energy Balzani, Vincenzo; Credi, Alberto; Venturi, Margherita ChemSusChem, Vol. 1, Issue 1-2 https://doi.org/10.1002/cssc.200700087	journal	February 2008
Ab Initio Molecular Orbital Theory by W. J. Hehre, L. Radom, P. v. R. Schleyer, and J. A. Pople, John Wiley, New York, 548pp. Price: $79.95 (1986) Wiberg, Kenneth B. Journal of Computational Chemistry, Vol. 7, Issue 3 https://doi.org/10.1002/jcc.540070314	journal	June 1986
Resonance Raman spectroscopic studies of[Ru(phen)2qdppz]2+ and its interactions with calf thymus DNA Abraham, B.; Sastri, C. V.; Maiya, B. G. Journal of Raman Spectroscopy, Vol. 35, Issue 1 https://doi.org/10.1002/jrs.1072	journal	January 2004
Energy-adjustedab initio pseudopotentials for the second and third row transition elements Andrae, D.; H�u�ermann, U.; Dolg, M. Theoretica Chimica Acta, Vol. 77, Issue 2 https://doi.org/10.1007/BF01114537	journal	January 1990
Synthesis of a new phenanthroline derived ligand with acceptor properties Rosa López, B.; Bárbara Loeb, L.; Boussie, Thomas Tetrahedron Letters, Vol. 37, Issue 31 https://doi.org/10.1016/0040-4039(96)01141-0	journal	July 1996
Electron transfer reactions of rigid, cofacially compressed, π-stacked porphyrin–bridge–quinone systems Kang, Youn K.; Iovine, Peter M.; Therien, Michael J. Coordination Chemistry Reviews, Vol. 255, Issue 7-8 https://doi.org/10.1016/j.ccr.2010.12.011	journal	April 2011
Photoinduced hole injection in semiconductor-coordination compound systems Buchalska, Marta; Kuncewicz, Joanna; Świętek, Elżbieta Coordination Chemistry Reviews, Vol. 257, Issue 3-4 https://doi.org/10.1016/j.ccr.2012.09.017	journal	February 2013
Control and utilization of ruthenium and rhodium metal complex excited states for photoactivated cancer therapy Knoll, Jessica D.; Turro, Claudia Coordination Chemistry Reviews, Vol. 282-283 https://doi.org/10.1016/j.ccr.2014.05.018	journal	January 2015
Transition metal complexes with N-heterocyclic carbene ligands: From organometallic hydrogenation reactions toward water splitting Kaufhold, Simon; Petermann, Lydia; Staehle, Robert Coordination Chemistry Reviews, Vol. 304-305 https://doi.org/10.1016/j.ccr.2014.12.004	journal	December 2015
New Ru(II) Complexes for Dual Photoreactivity: Ligand Exchange and ¹ O ₂ Generation Knoll, Jessica D.; Albani, Bryan A.; Turro, Claudia Accounts of Chemical Research, Vol. 48, Issue 8 https://doi.org/10.1021/acs.accounts.5b00227	journal	July 2015
Optically Switchable Molecular Solids: Photoinduced Spin-Crossover, Photochromism, and Photoinduced Magnetization Sato, Osamu Accounts of Chemical Research, Vol. 36, Issue 9 https://doi.org/10.1021/ar020242z	journal	September 2003
Organoiridium Complexes: Anticancer Agents and Catalysts Liu, Zhe; Sadler, Peter J. Accounts of Chemical Research, Vol. 47, Issue 4 https://doi.org/10.1021/ar400266c	journal	February 2014
Excited State Dynamics and Isomerization in Ruthenium Sulfoxide Complexes King, Albert W.; Wang, Lei; Rack, Jeffrey J. Accounts of Chemical Research, Vol. 48, Issue 4 https://doi.org/10.1021/ar500396a	journal	March 2015
Molecular Photovoltaics Hagfeldt, Anders; Grätzel, Michael Accounts of Chemical Research, Vol. 33, Issue 5 https://doi.org/10.1021/ar980112j	journal	May 2000
Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis Prier, Christopher K.; Rankic, Danica A.; MacMillan, David W. C. Chemical Reviews, Vol. 113, Issue 7 https://doi.org/10.1021/cr300503r	journal	March 2013
The low-lying excited state in ligand .pi.-donor complexes of ruthenium(II): mononuclear and binuclear species Rillema, D. Paul; Mack, Kinsler B. Inorganic Chemistry, Vol. 21, Issue 10 https://doi.org/10.1021/ic00140a053	journal	October 1982
Effect of the Addition of a Fused Donor−Acceptor Ligand on a Ru(II) Complex: Synthesis, Characterization, and Photoinduced Electron Transfer Reactions of [Ru(TTF-dppz) ₂ (Aqphen)] ²⁺ Dupont, Nathalie; Ran, Ying-Fen; Jia, Hong-Peng Inorganic Chemistry, Vol. 50, Issue 8 https://doi.org/10.1021/ic101951n	journal	April 2011
Photoinduced Electron Transfer in Linear Triarylamine–Photosensitizer–Anthraquinone Triads with Ruthenium(II), Osmium(II), and Iridium(III) Hankache, Jihane; Niemi, Marja; Lemmetyinen, Helge Inorganic Chemistry, Vol. 51, Issue 11 https://doi.org/10.1021/ic300558s	journal	May 2012
Mixed phosphine 2,2'-bipyridine complexes of ruthenium Sullivan, B. P.; Salmon, D. J.; Meyer, T. J. Inorganic Chemistry, Vol. 17, Issue 12 https://doi.org/10.1021/ic50190a006	journal	December 1978
Excited-State Electron Transfer in a Chromophore−Quencher Complex. Spectroscopic Identification of a Redox-Separated State López, Rosa; Leiva, Ana M.; Zuloaga, Fernando Inorganic Chemistry, Vol. 38, Issue 12 https://doi.org/10.1021/ic981050w	journal	May 1999
“Electro-Photo Switch” and “Molecular Light Switch” Devices Based on Ruthenium(II) Complexes of Modified Dipyridophenazine Ligands: Modulation of the Photochemical Function through Ligand Design Arounaguiri, S.; Maiya, Bhaskar G. Inorganic Chemistry, Vol. 38, Issue 5 https://doi.org/10.1021/ic981109z	journal	February 1999
Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F. The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627 https://doi.org/10.1021/j100096a001	journal	November 1994
A time-resolved Raman study of the reaction of hydroxyl radicals with p-phenylenediamine Sun, Q.; Tripathi, G. N. R.; Schuler, R. H. The Journal of Physical Chemistry, Vol. 94, Issue 5 https://doi.org/10.1021/j100368a089	journal	March 1990
Proton Transfer Quenching of the MLCT Excited State of Ru(phen)2dppz2+ in Homogeneous Solution and Bound to DNA Turro, Claudia; Bossmann, Stefan H.; Jenkins, Yonchu Journal of the American Chemical Society, Vol. 117, Issue 35 https://doi.org/10.1021/ja00140a020	journal	September 1995
A molecular light switch for DNA: Ru(bpy)2(dppz)2+ Friedman, Alan E.; Chambron, Jean Claude; Sauvage, Jean Pierre Journal of the American Chemical Society, Vol. 112, Issue 12 https://doi.org/10.1021/ja00168a052	journal	June 1990
Spectroscopic and electrochemical properties of dimeric Ruthenium(II) diimine complexes and determination of their excited state redox properties Fuchs, Yael; Lofters, Sonita; Dieter, Thomas Journal of the American Chemical Society, Vol. 109, Issue 9 https://doi.org/10.1021/ja00243a023	journal	April 1987
Absorption Spectrum and Solvatochromism of the [Ru(4,4‘-COOH-2,2‘-bpy) ₂ (NCS) ₂ ] Molecular Dye by Time Dependent Density Functional Theory Fantacci, Simona; De Angelis, Filippo; Selloni, Annabella Journal of the American Chemical Society, Vol. 125, Issue 14 https://doi.org/10.1021/ja0207910	journal	April 2003
Ultrafast Fluorescence Detection in Tris(2,2‘-bipyridine)ruthenium(II) Complex in Solution: Relaxation Dynamics Involving Higher Excited States Bhasikuttan, Achikanath C.; Suzuki, Masaya; Nakashima, Satoru Journal of the American Chemical Society, Vol. 124, Issue 28 https://doi.org/10.1021/ja026135h	journal	July 2002
Photoregulated Transmembrane Charge Separation by Linked Spiropyran−Anthraquinone Molecules Zhu, Linyong; Khairutdinov, Rafail F.; Cape, Jonathan L. Journal of the American Chemical Society, Vol. 128, Issue 3 https://doi.org/10.1021/ja0545620	journal	January 2006
Early Events in the Photochemistry of Aryl Azides from Femtosecond UV/Vis Spectroscopy and Quantum Chemical Calculations Burdzinski, Gotard; Hackett, John C.; Wang, Jin Journal of the American Chemical Society, Vol. 128, Issue 41 https://doi.org/10.1021/ja061520i	journal	October 2006
Ultrafast Dynamics of the Low-Lying ³ MLCT States of [Ru(bpy) ₂ (dppp2)] ²⁺ Sun, Yujie; Liu, Yao; Turro, Claudia Journal of the American Chemical Society, Vol. 132, Issue 16 https://doi.org/10.1021/ja101703w	journal	April 2010
Strained Ruthenium Complexes Are Potent Light-Activated Anticancer Agents Howerton, Brock S.; Heidary, David K.; Glazer, Edith C. Journal of the American Chemical Society, Vol. 134, Issue 20 https://doi.org/10.1021/ja3009677	journal	May 2012
Exploitation of Long-Lived ³ IL Excited States for Metal–Organic Photodynamic Therapy: Verification in a Metastatic Melanoma Model Lincoln, Richard; Kohler, Lars; Monro, Susan Journal of the American Chemical Society, Vol. 135, Issue 45 https://doi.org/10.1021/ja408426z	journal	October 2013
Photophysical Properties of cis -Mo ₂ Quadruply Bonded Complexes and Observation of Photoinduced Electron Transfer to Titanium Dioxide Brown-Xu, Samantha E.; Chisholm, Malcolm H.; Durr, Christopher B. Journal of the American Chemical Society, Vol. 136, Issue 32 https://doi.org/10.1021/ja504944d	journal	July 2014
Ultrafast Carbene−Carbene Isomerization Wang, Jin; Burdzinski, Gotard; Kubicki, Jacek Journal of the American Chemical Society, Vol. 130, Issue 16 https://doi.org/10.1021/ja8002827	journal	March 2008
First Observation of the Key Intermediate in the “Light-Switch” Mechanism of [Ru(phen) ₂ dppz] ²⁺ Olson, E. J. C.; Hu, D.; Hörmann, A. Journal of the American Chemical Society, Vol. 119, Issue 47 https://doi.org/10.1021/ja971151d	journal	November 1997
Effects of Intraligand Electron Delocalization, Steric Tuning, and Excited-State Vibronic Coupling on the Photophysics of Aryl-Substituted Bipyridyl Complexes of Ru(II) Damrauer, Niels H.; Boussie, Thomas R.; Devenney, Martin Journal of the American Chemical Society, Vol. 119, Issue 35 https://doi.org/10.1021/ja971321m	journal	September 1997
Picosecond Time-Resolved Resonance Raman Probing of the Light-Switch States of [Ru(Phen) ₂ dppz] ²⁺ Coates, Colin G.; Olofsson, Johan; Coletti, Monica The Journal of Physical Chemistry B, Vol. 105, Issue 50 https://doi.org/10.1021/jp0127115	journal	December 2001
Resonance Raman Investigation of Ru(phen) ₂ (dppz) ²⁺ and Related Complexes in Water and in the Presence of DNA Chen, Wei; Turro, Claudia; Friedman, Lee A. The Journal of Physical Chemistry B, Vol. 101, Issue 35 https://doi.org/10.1021/jp970423w	journal	August 1997
Ultrafast Dynamics in the Metal-to-Ligand Charge Transfer Excited-State Evolution of [Ru(4,4‘-diphenyl-2,2‘-bipyridine) ₃ ] ²⁺ Damrauer, Niels H.; McCusker, James K. The Journal of Physical Chemistry A, Vol. 103, Issue 42 https://doi.org/10.1021/jp9927754	journal	October 1999
NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to the Organometallic Chemist Fulmer, Gregory R.; Miller, Alexander J. M.; Sherden, Nathaniel H. Organometallics, Vol. 29, Issue 9 https://doi.org/10.1021/om100106e	journal	May 2010
Spectral splitting photovoltaics using perovskite and wideband dye-sensitized solar cells Kinoshita, Takumi; Nonomura, Kazuteru; Joong Jeon, Nam Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9834	journal	November 2015
Combination of Ru( ii ) complexes and light: new frontiers in cancer therapy Mari, Cristina; Pierroz, Vanessa; Ferrari, Stefano Chemical Science, Vol. 6, Issue 5 https://doi.org/10.1039/C4SC03759F	journal	January 2015
Excited state investigation of a new Ru( ii ) complex for dual reactivity with low energy light Knoll, J. D.; Albani, B. A.; Turro, C. Chemical Communications, Vol. 51, Issue 42 https://doi.org/10.1039/C5CC01865J	journal	January 2015
Direct observation by time-resolved infrared spectroscopy of the bright and the dark excited states of the [Ru(phen) ₂ (dppz)] ²⁺ light-switch compound in solution and when bound to DNA Poynton, Fergus E.; Hall, James P.; Keane, Páraic M. Chemical Science, Vol. 7, Issue 5 https://doi.org/10.1039/C5SC04514B	journal	January 2016
Azadipyrromethene cyclometalation in neutral Ru ^II complexes: photosensitizers with extended near-infrared absorption for solar energy conversion applications Bessette, André; Cibian, Mihaela; Ferreira, Janaina G. Dalton Transactions, Vol. 45, Issue 26 https://doi.org/10.1039/C6DT00961A	journal	January 2016
Synthesis and study of a mixed-ligand ruthenium( II ) complex in its ground and excited states: bis(2,2′-bipyridine)(dipyrido[3,2-a : 2′,3′-c]phenazine-N ⁴ N ⁵ )ruthenium( II ) Amouyal, Edmond; Homsi, Abdulrazzak; Chambron, Jean-Claude J. Chem. Soc., Dalton Trans., Issue 6 https://doi.org/10.1039/DT9900001841	journal	January 1990
Synthesis, crystal structure, molecular orbital calculations and electronic properties of 2,3-di(2-pyridyl)naphtho[2,3-f ]quinoxaline-7,12-quinone (Aqdpp) López, Rosa; Boys, Daphne; Loeb, Bárbara Journal of the Chemical Society, Perkin Transactions 2, Issue 4 https://doi.org/10.1039/a707858g	journal	January 1998
Efficient DNA photocleavage by [Ru(bpy)2(dppn)]2+ with visible light Sun, Yujie; Joyce, Lauren E.; Dickson, Nicole M. Chemical Communications, Vol. 46, Issue 14 https://doi.org/10.1039/b925574e	journal	January 2010
Light-activated ruthenium complexes photobind DNA and are cytotoxic in the photodynamic therapy window Wachter, Erin; Heidary, David K.; Howerton, Brock S. Chemical Communications, Vol. 48, Issue 77 https://doi.org/10.1039/c2cc33359g	journal	January 2012
Molecular systems for light driven hydrogen production Eckenhoff, William T.; Eisenberg, Richard Dalton Transactions, Vol. 41, Issue 42 https://doi.org/10.1039/c2dt30823a	journal	January 2012
Shifting the Light Activation of Metallodrugs to the Red and Near-Infrared Region in Anticancer Phototherapy Bonnet, Sylvestre Comments on Inorganic Chemistry, Vol. 35, Issue 4 https://doi.org/10.1080/02603594.2014.979286	journal	October 2014
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
Circular Dichroism of Carotenoids in Bacterial Light-Harvesting Complexes: Experiments and Modeling Georgakopoulou, S.; van Grondelle, R.; van der Zwan, G. Biophysical Journal, Vol. 87, Issue 5 https://doi.org/10.1529/biophysj.104.047498	journal	November 2004

Cited By (5)

One-step synthesis of ball-shaped metal complexes with a main absorption band in the near-IR region Furuyama, Taniyuki; Shimasaki, Fumika; Saikawa, Natsumi Scientific Reports, Vol. 9, Issue 1 https://doi.org/10.1038/s41598-019-53014-7	journal	November 2019
π-Conjugated thiolate amplified spectrophotometry nitrite assay with improved sensitivity and accuracy Zhang, Lijuan; Wu, Xiaoxia; Yuan, Zhiqin Chemical Communications, Vol. 54, Issue 86 https://doi.org/10.1039/c8cc06477f	journal	January 2018
Using ultra-fast spectroscopy to probe the excited state dynamics of a reported highly efficient thermally activated delayed fluorescence chromophore Vázquez, Ricardo Javier; Kim, Hyungjun; Zimmerman, Paul M. Journal of Materials Chemistry C, Vol. 7, Issue 14 https://doi.org/10.1039/c8tc05957h	journal	January 2019
Long-lived MLCT states for Ru( ii ) complexes of ferrocene-appended 2,2′-bipyridines Barnsley, Jonathan E.; Findlay, James A.; Shillito, Georgina E. Dalton Transactions, Vol. 48, Issue 41 https://doi.org/10.1039/c9dt02025j	journal	January 2019
The odd–even effect of alkyl chain in organic room temperature phosphorescence luminogens and the corresponding in vivo imaging Yang, Jie; Gao, Heqi; Wang, Yunsheng Materials Chemistry Frontiers, Vol. 3, Issue 7 https://doi.org/10.1039/c9qm00108e	journal	January 2019

Figures / Tables (4)

Similar Records

Revealing Parallel Inter‐ and Intra‐Ligand Charge Transfer Dynamics in [Ru(L)₂(dppz)]²⁺ Molecular Lightswitch with N K‐Edge X‐Ray Absorption Spectroscopy

Journal Article · Wed Jul 09 20:00:00 EDT 2025 · Angewandte Chemie (International Edition) · OSTI ID:2583411

Application of resonance Raman spectroscopy to electronic structure in metal complex excited states. Excited-state ordering and electron delocalization in dipyrido[3,2-a: 2`,3`-c] phenazine (dppz): Complexes of Re(I) and Ru(II)

Journal Article · Tue Dec 19 23:00:00 EST 1995 · Inorganic Chemistry · OSTI ID:274010

Spectroscopic, electrochemical, and spectroelectrochemical investigations of mixed-metal osmium(II)/ruthenium(II) bimetallic complexes incorporating polypyridyl bridging ligands

Journal Article · Wed Apr 29 00:00:00 EDT 1992 · Inorganic Chemistry; (United States) · OSTI ID:6915650

Related Subjects

14 SOLAR ENERGY
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

New Ligand Design Provides Delocalization and Promotes Strong Absorption throughout the Visible Region in a Ru(II) Complex

Citation Formats

References (57)

Cited By (5)

Figures / Tables (4)

Similar Records

Related Subjects