Controlling the excited-state dynamics of low band gap, near-infrared absorbers via proquinoidal unit electronic structural modulation
Abstract
While the influence of proquinoidal character upon the linear absorption spectrum of low optical bandgap π-conjugated polymers and molecules is well understood, its impact upon excited-state relaxation pathways and dynamics remains obscure. We report the syntheses, electronic structural properties, and excited-state dynamics of a series of model highly conjugated near-infrared (NIR)-absorbing chromophores based on a (porphinato)metal(II)-proquinoidal spacer-(porphinato)metal(II) (PM-Sp-PM) structural motif. A combination of excited-state dynamical studies and time-dependent density functional theory calculations: (i) points to the cardinal role that excited-state configuration interaction (CI) plays in determining the magnitudes of S1 → S0 radiative (kr), S1 → T1 intersystem crossing (kISC), and S1 → S0 internal conversion (kIC) rate constants in these PM-Sp-PM chromophores, and (ii) suggests that a primary determinant of CI magnitude derives from the energetic alignment of the PM and Sp fragment LUMOs (ΔEL). These insights not only enable steering of excited-state relaxation dynamics of high oscillator strength NIR absorbers to realize either substantial fluorescence or long-lived triplets (τ$$_ {T_1}$$ > μs) generated at unit quantum yield (ΦISC = 100%), but also crafting of those having counter-intuitive properties: for example, while (porphinato)platinum compounds are well known to generate non-emissive triplet states (ΦISC = 100%) upon optical excitation atmore »
- Authors:
-
- Duke Univ., Durham, NC (United States). Dept. of Chemistry, French Family Science Center
- Publication Date:
- Research Org.:
- Duke Univ., Durham, NC (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institutes of Health (NIH)
- OSTI Identifier:
- 1426479
- Grant/Contract Number:
- SC0001517; GM048043
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Volume: 8; Journal Issue: 9; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Bai, Yusong, Rawson, Jeff, Roget, Sean A., Olivier, Jean-Hubert, Lin, Jiaxing, Zhang, Peng, Beratan, David N., and Therien, Michael J. Controlling the excited-state dynamics of low band gap, near-infrared absorbers via proquinoidal unit electronic structural modulation. United States: N. p., 2017.
Web. doi:10.1039/c7sc02150j.
Bai, Yusong, Rawson, Jeff, Roget, Sean A., Olivier, Jean-Hubert, Lin, Jiaxing, Zhang, Peng, Beratan, David N., & Therien, Michael J. Controlling the excited-state dynamics of low band gap, near-infrared absorbers via proquinoidal unit electronic structural modulation. United States. https://doi.org/10.1039/c7sc02150j
Bai, Yusong, Rawson, Jeff, Roget, Sean A., Olivier, Jean-Hubert, Lin, Jiaxing, Zhang, Peng, Beratan, David N., and Therien, Michael J. 2017.
"Controlling the excited-state dynamics of low band gap, near-infrared absorbers via proquinoidal unit electronic structural modulation". United States. https://doi.org/10.1039/c7sc02150j. https://www.osti.gov/servlets/purl/1426479.
@article{osti_1426479,
title = {Controlling the excited-state dynamics of low band gap, near-infrared absorbers via proquinoidal unit electronic structural modulation},
author = {Bai, Yusong and Rawson, Jeff and Roget, Sean A. and Olivier, Jean-Hubert and Lin, Jiaxing and Zhang, Peng and Beratan, David N. and Therien, Michael J.},
abstractNote = {While the influence of proquinoidal character upon the linear absorption spectrum of low optical bandgap π-conjugated polymers and molecules is well understood, its impact upon excited-state relaxation pathways and dynamics remains obscure. We report the syntheses, electronic structural properties, and excited-state dynamics of a series of model highly conjugated near-infrared (NIR)-absorbing chromophores based on a (porphinato)metal(II)-proquinoidal spacer-(porphinato)metal(II) (PM-Sp-PM) structural motif. A combination of excited-state dynamical studies and time-dependent density functional theory calculations: (i) points to the cardinal role that excited-state configuration interaction (CI) plays in determining the magnitudes of S1 → S0 radiative (kr), S1 → T1 intersystem crossing (kISC), and S1 → S0 internal conversion (kIC) rate constants in these PM-Sp-PM chromophores, and (ii) suggests that a primary determinant of CI magnitude derives from the energetic alignment of the PM and Sp fragment LUMOs (ΔEL). These insights not only enable steering of excited-state relaxation dynamics of high oscillator strength NIR absorbers to realize either substantial fluorescence or long-lived triplets (τ$_ {T_1}$ > μs) generated at unit quantum yield (ΦISC = 100%), but also crafting of those having counter-intuitive properties: for example, while (porphinato)platinum compounds are well known to generate non-emissive triplet states (ΦISC = 100%) upon optical excitation at ambient temperature, diminishing the extent of excited-state CI in these systems realizes long-wavelength absorbing heavy-metal fluorophores. In conclusion, this work highlights approaches to: (i) modulate low-lying singlet excited-state lifetime over the picosecond-to-nanosecond time domain, (ii) achieve NIR fluorescence with quantum yields up to 25%, (iii) tune the magnitude of S1–T1 ISC rate constant from 109 to 1012 s-1 and (iv) realize T1-state lifetimes that range from ~0.1 to several μs, for these model PM-Sp-PM chromophores, and renders new insights to evolve bespoke photophysical properties for low optical bandgap π-conjugated polymers and molecules based on proquinoidal conjugation motifs.},
doi = {10.1039/c7sc02150j},
url = {https://www.osti.gov/biblio/1426479},
journal = {Chemical Science},
issn = {2041-6520},
number = 9,
volume = 8,
place = {United States},
year = {Wed Jun 07 00:00:00 EDT 2017},
month = {Wed Jun 07 00:00:00 EDT 2017}
}
Web of Science
Works referenced in this record:
Low-Bandgap Near-IR Conjugated Polymers/Molecules for Organic Electronics
journal, August 2015
- Dou, Letian; Liu, Yongsheng; Hong, Ziruo
- Chemical Reviews, Vol. 115, Issue 23
Charge Transfer Absorption for π-Conjugated Polymers and Oligomers Mixed with Electron Acceptors
journal, May 2007
- Panda, Priyadarshi; Veldman, Dirk; Sweelssen, Jörgen
- The Journal of Physical Chemistry B, Vol. 111, Issue 19
Spin-orbit coupling in free-radical reactions: on the way to heavy elements
journal, January 1993
- Khudyakov, Igor V.; Serebrennikov, Yuri A.; Turro, Nicholas J.
- Chemical Reviews, Vol. 93, Issue 1
Extension of Gaussian-2 (G2) theory to molecules containing third-row atoms K and Ca
journal, October 1997
- Blaudeau, Jean-Philippe; McGrath, Mark P.; Curtiss, Larry A.
- The Journal of Chemical Physics, Vol. 107, Issue 13
Exceptional Near-Infrared Fluorescence Quantum Yields and Excited-State Absorptivity of Highly Conjugated Porphyrin Arrays
journal, July 2006
- Duncan, Timothy V.; Susumu, Kimihiro; Sinks, Louise E.
- Journal of the American Chemical Society, Vol. 128, Issue 28
Tetrabenzporphyrin complexes of iron, palladium and platinum
journal, January 1980
- Vogler, A.; Kunkely, H.; Rethwisch, B.
- Inorganica Chimica Acta, Vol. 46
Dynamic Stokes Shift and Excitation Wavelength Dependent Fluorescence of Dipolar Molecules in Room Temperature Ionic Liquids
journal, July 2006
- Samanta, Anunay
- The Journal of Physical Chemistry B, Vol. 110, Issue 28
Facile Synthesis of meso-Tetrakis(perfluoroalkyl)porphyrins: Spectroscopic Properties and X-ray Crystal Structure of Highly Electron-Deficient 5,10,15,20-Tetrakis(heptafluoropropyl)porphyrin
journal, November 1994
- DiMagno, Stephen G.; Williams, R. Allen; Therien, Michael J.
- The Journal of Organic Chemistry, Vol. 59, Issue 23
Ultrafast Dynamics of Highly Conjugated Porphyrin Arrays
journal, November 1998
- Kumble, Ranjit; Palese, Steven; Lin, Victor S. -Y.
- Journal of the American Chemical Society, Vol. 120, Issue 44
In vivo near-infrared fluorescence imaging
journal, October 2003
- Frangioni, J.
- Current Opinion in Chemical Biology, Vol. 7, Issue 5, p. 626-634
Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions
journal, January 1980
- Krishnan, R.; Binkley, J. S.; Seeger, R.
- The Journal of Chemical Physics, Vol. 72, Issue 1
Triplet photosensitizers: from molecular design to applications
journal, January 2013
- Zhao, Jianzhang; Wu, Wanhua; Sun, Jifu
- Chemical Society Reviews, Vol. 42, Issue 12
Femtosecond Studies of Solvation and Intramolecular Configurational Dynamics of Fluorophores in Liquid Solution
journal, April 2004
- Glasbeek, Max; Zhang, Hong
- Chemical Reviews, Vol. 104, Issue 4
The Role of Porphyrin-to-Porphyrin Linkage Topology in the Extensive Modulation of the Absorptive and Emissive Properties of a Series of Ethynyl- and Butadiynyl-Bridged Bis- and Tris(porphinato)zinc Chromophores
journal, December 1995
- Lin, Victor S. -Y.; Therien, Michael J.
- Chemistry - A European Journal, Vol. 1, Issue 9
Excitation of Highly Conjugated (Porphinato)palladium(II) and (Porphinato)platinum(II) Oligomers Produces Long-Lived, Triplet States at Unit Quantum Yield That Absorb Strongly over Broad Spectral Domains of the NIR †
journal, November 2010
- Duncan, Timothy V.; Frail, Paul R.; Miloradovic, Ivan R.
- The Journal of Physical Chemistry B, Vol. 114, Issue 45
Highly Conjugated (Polypyridyl)metal−(Porphinato)zinc(II) Compounds: Long-Lived, High Oscillator Strength, Excited-State Absorbers Having Exceptional Spectral Coverage of the Near-Infrared
journal, August 2004
- Duncan, Timothy V.; Rubtsov, Igor V.; Uyeda, H. Tetsuo
- Journal of the American Chemical Society, Vol. 126, Issue 31
Electronic Population Analysis on LCAO–MO Molecular Wave Functions. I
journal, October 1955
- Mulliken, R. S.
- The Journal of Chemical Physics, Vol. 23, Issue 10
Design of diethynyl porphyrin derivatives with high near infrared fluorescence quantum yields
journal, January 2015
- Susumu, Kimihiro; Therien, Michael J.
- Journal of Porphyrins and Phthalocyanines, Vol. 19, Issue 01-03
Facile elaboration of porphyrins via metal-mediated cross-coupling
journal, October 1993
- DiMagno, Stephen G.; Lin, Victor S. Y.; Therien, Michael J.
- The Journal of Organic Chemistry, Vol. 58, Issue 22
Picosecond spectroscopy of some metalloporphyrins
journal, January 1981
- Straub, K. D.; Rentzepis, P. M.; Huppert, D.
- Journal of Photochemistry, Vol. 17, Issue 2
Triplet–triplet annihilation based upconversion: from triplet sensitizers and triplet acceptors to upconversion quantum yields
journal, January 2011
- Zhao, Jianzhang; Ji, Shaomin; Guo, Huimin
- RSC Advances, Vol. 1, Issue 6
Synthesis, Structure, Electronic Spectroscopy, Photophysics, Electrochemistry, and X-ray Photoelectron Spectroscopy of Highly-Electron-Deficient [5,10,15,20-Tetrakis(perfluoroalkyl)porphinato]zinc(II) Complexes and Their Free Base Derivatives
journal, January 1996
- Goll, James G.; Moore, Kevin T.; Ghosh, Abhik
- Journal of the American Chemical Society, Vol. 118, Issue 35
Gaussian basis sets for molecular calculations. The representation of 3 d orbitals in transition‐metal atoms
journal, May 1977
- Hay, P. Jeffrey
- The Journal of Chemical Physics, Vol. 66, Issue 10
cclib: A library for package-independent computational chemistry algorithms
journal, January 2008
- O'boyle, Noel M.; Tenderholt, Adam L.; Langner, Karol M.
- Journal of Computational Chemistry, Vol. 29, Issue 5
Photophysical Properties of Near-Infrared Phosphorescent π-Extended Platinum Porphyrins
journal, December 2011
- Sommer, Jonathan R.; Shelton, Abigail H.; Parthasarathy, Anand
- Chemistry of Materials, Vol. 23, Issue 24
Far-red to near infrared analyte-responsive fluorescent probes based on organic fluorophore platforms for fluorescence imaging
journal, January 2013
- Yuan, Lin; Lin, Weiying; Zheng, Kaibo
- Chem. Soc. Rev., Vol. 42, Issue 2
Porphyrins
journal, September 1970
- Eastwood, DeLyle; Gouterman, Martin
- Journal of Molecular Spectroscopy, Vol. 35, Issue 3
Photon upconversion based on sensitized triplet–triplet annihilation
journal, November 2010
- Singh-Rachford, Tanya N.; Castellano, Felix N.
- Coordination Chemistry Reviews, Vol. 254, Issue 21-22
Porphyrins and phthalocyanines as materials for optical limiting
journal, March 2004
- Calvete, Mario; Yang, Guo Ying; Hanack, Michael
- Synthetic Metals, Vol. 141, Issue 3
Near-infrared fluorescence: application to in vivo molecular imaging
journal, February 2010
- Hilderbrand, Scott A.; Weissleder, Ralph
- Current Opinion in Chemical Biology, Vol. 14, Issue 1
Luminescence of porphyrins and metalloporphyrins. Part 3.—Heavy-atom effects
journal, January 1981
- Harriman, Anthony
- J. Chem. Soc., Faraday Trans. 2, Vol. 77, Issue 7
Extension of Gaussian‐2 theory to molecules containing third‐row atoms Ga–Kr
journal, October 1995
- Curtiss, Larry A.; McGrath, Mark P.; Blaudeau, Jean‐Philippe
- The Journal of Chemical Physics, Vol. 103, Issue 14
Molecular Engineering of Intensely Near-Infrared Absorbing Excited States in Highly Conjugated Oligo(porphinato)zinc−(Polypyridyl)metal(II) Supermolecules
journal, August 2007
- Duncan, Timothy V.; Ishizuka, Tomoya; Therien, Michael J.
- Journal of the American Chemical Society, Vol. 129, Issue 31
Singlet and Triplet Excited States of Emissive, Conjugated Bis(porphyrin) Compounds Probed by Optical and EPR Spectroscopic Methods
journal, July 2000
- Shediac, Renée; Gray, Mike H. B.; Uyeda, H. Tetsuo
- Journal of the American Chemical Society, Vol. 122, Issue 29
Recent development in the design of organic materials for optical power limiting
journal, January 1999
- Spangler, Charles W.
- Journal of Materials Chemistry, Vol. 9, Issue 9
Organometallic acetylides of PtII, AuI and HgII as new generation optical power limiting materials
journal, January 2011
- Zhou, Gui-Jiang; Wong, Wai-Yeung
- Chemical Society Reviews, Vol. 40, Issue 5
Decoupling Optical and Potentiometric Band Gaps in π-Conjugated Materials
journal, July 2002
- Susumu, Kimihiro; Therien, Michael J.
- Journal of the American Chemical Society, Vol. 124, Issue 29
Potentiometric, Electronic Structural, and Ground- and Excited-State Optical Properties of Conjugated Bis[(Porphinato)zinc(II)] Compounds Featuring Proquinoidal Spacer Units
journal, April 2005
- Susumu, Kimihiro; Duncan, Timothy V.; Therien, Michael J.
- Journal of the American Chemical Society, Vol. 127, Issue 14
Group 14 Dithienometallole-Linked Ethynylene-Conjugated Porphyrin Dimers
journal, July 2016
- Morisue, Mitsuhiko; Hoshino, Yuki; Nakamura, Masashi
- Inorganic Chemistry, Vol. 55, Issue 15
METALLOPORPHYRINS. ELECTRONIC SPECTRA AND NATURE OF PERTURBATIONS. I. TRANSITION METAL ION DERIVATIVES 1a
journal, December 1963
- Becker, Ralph S.; Allison, Jean B.
- The Journal of Physical Chemistry, Vol. 67, Issue 12
Catalytic conversion of simple haloporphyrins into alkyl-, aryl-, pyridyl-, and vinyl-substituted porphyrins
journal, March 1993
- DiMagno, Stephen G.; Lin, Victor S. Y.; Therien, Michael J.
- Journal of the American Chemical Society, Vol. 115, Issue 6
Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z=11–18
journal, May 1980
- McLean, A. D.; Chandler, G. S.
- The Journal of Chemical Physics, Vol. 72, Issue 10, p. 5639-5648
Excitonic Interactions in the Singlet and Triplet Excited States of Covalently Linked Zinc Porphyrin Dimers
journal, March 2000
- Piet, Jacob J.; Taylor, Peter N.; Anderson, Harry L.
- Journal of the American Chemical Society, Vol. 122, Issue 8
25th Anniversary Article: Recent Advances in n-Type and Ambipolar Organic Field-Effect Transistors
journal, August 2013
- Zhao, Yan; Guo, Yunlong; Liu, Yunqi
- Advanced Materials, Vol. 25, Issue 38
Preparation and Spectral, Electrochemical, and Photovoltaic Properties of Acene-Modified Zinc Porphyrins
journal, November 2009
- Lin, Ching-Yao; Wang, Yu-Chien; Hsu, Shun-Ju
- The Journal of Physical Chemistry C, Vol. 114, Issue 1
Compact contracted basis sets for third-row atoms: Ga-Kr
journal, November 1990
- Binning, R. C.; Curtiss, L. A.
- Journal of Computational Chemistry, Vol. 11, Issue 10
Highly conjugated, acetylenyl bridged porphyrins: new models for light-harvesting antenna systems
journal, May 1994
- Lin, V.; DiMagno, S.; Therien, M.
- Science, Vol. 264, Issue 5162
Tailoring Porphyrin-Based Electron Accepting Materials for Organic Photovoltaics
journal, December 2014
- Rawson, Jeff; Stuart, Andrew C.; You, Wei
- Journal of the American Chemical Society, Vol. 136, Issue 50
Dynamics and Transient Absorption Spectral Signatures of the Single-Wall Carbon Nanotube Electronically Excited Triplet State
journal, November 2011
- Park, Jaehong; Deria, Pravas; Therien, Michael J.
- Journal of the American Chemical Society, Vol. 133, Issue 43
Extension of Gaussian‐1 (G1) theory to bromine‐containing molecules
journal, January 1991
- McGrath, Mark P.; Radom, Leo
- The Journal of Chemical Physics, Vol. 94, Issue 1
Porphyrins with Exocyclic Rings. 13. 1 Synthesis and Spectroscopic Characterization of Highly Modified Porphyrin Chromophores with Fused Acenaphthylene and Benzothiadiazole Rings
journal, November 1998
- Lash, Timothy D.; Chandrasekar, Pushpa; Osuma, Augustine T.
- The Journal of Organic Chemistry, Vol. 63, Issue 23
Ultrafast Singlet Excited-State Polarization in Electronically Asymmetric Ethyne-Bridged Bis[(porphinato)zinc(II)] Complexes
journal, March 2003
- Rubtsov, Igor V.; Susumu, Kimihiro; Rubtsov, Grigorii I.
- Journal of the American Chemical Society, Vol. 125, Issue 9
ENERGY RELAXATION MECHANISM IN Ni(II), Pd(II), Pt(II) and Zn(II) PORPHYRINS
journal, May 1979
- Kobayashi, T.; Straub, K. D.; Rentzepis, P. M.
- Photochemistry and Photobiology, Vol. 29, Issue 5
Polymer solar cells
journal, February 2012
- Li, Gang; Zhu, Rui; Yang, Yang
- Nature Photonics, Vol. 6, Issue 3
Gaussian Basis Set for Molecular Wavefunctions Containing Third‐Row Atoms
journal, February 1970
- Wachters, A. J. H.
- The Journal of Chemical Physics, Vol. 52, Issue 3
Push−Pull Arylethynyl Porphyrins: New Chromophores That Exhibit Large Molecular First-Order Hyperpolarizabilities
journal, January 1996
- LeCours, Steven M.; Guan, Hann-Wen; DiMagno, Stephen G.
- Journal of the American Chemical Society, Vol. 118, Issue 6
Design of Coupled Porphyrin Chromophores with Unusually Large Hyperpolarizabilities
journal, April 2012
- Jiang, Nan; Zuber, Gérard; Keinan, Shahar
- The Journal of Physical Chemistry C, Vol. 116, Issue 17
A Convenient Synthesis of Ethynylarenes and Diethynylarenes
journal, January 1980
- Takahashi, S.; Kuroyama, Y.; Sonogashira, K.
- Synthesis, Vol. 1980, Issue 08
Structural Changes Accompanying Intramolecular Electron Transfer: Focus on Twisted Intramolecular Charge-Transfer States and Structures
journal, October 2003
- Grabowski, Zbigniew R.; Rotkiewicz, Krystyna; Rettig, Wolfgang
- Chemical Reviews, Vol. 103, Issue 10
Meso-Substituted Porphyrins for Dye-Sensitized Solar Cells
journal, November 2014
- Urbani, Maxence; Grätzel, Michael; Nazeeruddin, Mohammad Khaja
- Chemical Reviews, Vol. 114, Issue 24
Dye-sensitized solar cells with 13% efficiency achieved through the molecular engineering of porphyrin sensitizers
journal, February 2014
- Mathew, Simon; Yella, Aswani; Gao, Peng
- Nature Chemistry, Vol. 6, Issue 3
Emission color tuning of copolymers containing polyfluorene, benzothiadiazole, porphyrin derivatives
journal, August 2012
- Song, Ho Jun; Kim, Doo Hun; Lee, Tae Ho
- European Polymer Journal, Vol. 48, Issue 8
Solution processed small molecule bulk heterojunction organic photovoltaics based on a conjugated donor–acceptor porphyrin
journal, January 2012
- Huang, Yuying; Li, Lisheng; Peng, Xiaobin
- Journal of Materials Chemistry, Vol. 22, Issue 41
Improving the Accuracy of Hybrid Meta-GGA Density Functionals by Range Separation
journal, October 2011
- Peverati, Roberto; Truhlar, Donald G.
- The Journal of Physical Chemistry Letters, Vol. 2, Issue 21
Highly correlated systems. Excitation energies of first row transition metals Sc–Cu
journal, July 1989
- Raghavachari, Krishnan; Trucks, Gary W.
- The Journal of Chemical Physics, Vol. 91, Issue 2
Works referencing / citing this record:
Synthesis of C−C Bonded Two-Dimensional Conjugated Covalent Organic Framework Films by Suzuki Polymerization on a Liquid-Liquid Interface
journal, January 2019
- Zhou, Deng; Tan, Xianyang; Wu, Huimin
- Angewandte Chemie, Vol. 131, Issue 5
A Simple, Small-Bandgap Porphyrin-Based Conjugated Polymer for Application in Organic Electronics
journal, September 2018
- Yang, Fan; Li, Cheng; Wei, Yuanzhi
- Macromolecular Rapid Communications, Vol. 39, Issue 21
An elaborate route of exclusive sonogashira polycondensation to alternating BODIPY–porphyrin ethynylene‐conjugated polymer
journal, September 2019
- Morisue, Mitsuhiko; Kawanishi, Miho; Nakano, Shinya
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 57, Issue 24
Unusual near infrared (NIR) fluorescent palladium( ii ) macrocyclic complexes containing M–C bonds with bioimaging capability
journal, January 2019
- Yao, Yuhang; Hou, Chun-Liang; Yang, Zi-Shu
- Chemical Science, Vol. 10, Issue 43
Synthesis of C−C Bonded Two-Dimensional Conjugated Covalent Organic Framework Films by Suzuki Polymerization on a Liquid-Liquid Interface
journal, January 2019
- Zhou, Deng; Tan, Xianyang; Wu, Huimin
- Angewandte Chemie International Edition, Vol. 58, Issue 5