Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Excited-State Dynamics and Nonlinear Optical Properties of Hyperpolarizable Chromophores Based on Conjugated Bis(terpyridyl)Ru(II) and Palladium and Platinum Porphyrinic Components: Impact of Heavy Metals upon Supermolecular Electro-Optic Properties

Abstract

A new series of strongly coupled oscillators based upon (porphinato)Pd, (porphinato)Pt, and bis(terpyridyl)-ruthenium(II) building blocks is described. These RuPPd, RuPPt, RuPPdRu, and RuPPtRu chromophores feature bis- (terpyridyl)Ru(II) moieties connected to the (porphinato)metal unit via an ethyne linker that bridges the 4!-terpyridyl and porphyrin macrocycle meso-carbon positions. Pump–probe transient optical data demonstrate sub-picosecond excited singlet-to-triplet-state relaxation. The relaxed lowest-energy triplet (T1) excited states of these chromophores feature absorption manifolds that span the 800–1200 nm spectral region, microsecond triplet-state lifetimes, and large absorptive extinction coefficients [ε(T1 → Tn) > 4 × 104 M–1 cm–1]. Dynamic hyperpolarizability (βλ) values were determined from hyper-Rayleigh light scattering (HRS) measurements carried out at several incident irradiation wavelengths over the 800–1500 nm spectral region. Relative to benchmark RuPZn and RuPZnRu chromophores which showed large βHRS values over the 1200–1600 nm range, RuPPd, RuPPt, RuPPdRu, and RuPPtRu displayed large βHRS values over the 850–1200 nm region. Generalized Thomas–Kuhn sum (TKS) rules and experimental hyperpolarizability values were utilized to determine excited state-to-excited state transition dipole terms from experimental electronic absorption data and thus assessed frequency-dependent βλ values, including two- and three-level contributions for both βzzz and βxzx tensor components to the RuPPd, RuPPt, RuPPdRu, and RuPPtRu hyperpolarizability spectra. Furthermore,more » these analyses qualitatively rationalize how the βzzz and βxzx tensor elements influence the observed irradiation wavelength-dependent hyperpolarizability magnitudes. The TKS analysis suggests that supermolecules related to RuPPd, RuPPt, RuPPdRu, and RuPPtRu will likely feature intricate dependences of experimentally determined βHRS values as a function of irradiation wavelength that derive from substantial singlet–triplet mixing, and complex interactions among multiple different β tensor components that modulate the long wavelength regime of the nonlinear optical response.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3];  [4]; ORCiD logo [4]; ORCiD logo [3]; ORCiD logo [4]
+ Show Author Affiliations
  1. Duke Univ., Durham, NC (United States); Univ. of Pennsylvania, Philadelphia, PA (United States); Shiv Nadar Univ., Uttar Pradesh (India)
  2. Duke Univ., Durham, NC (United States); Univ. of Pennsylvania, Philadelphia, PA (United States); Ewha Womans Univ., Seoul (Korea)
  3. Univ. of Leuven (Belgium)
  4. Duke Univ., Durham, NC (United States)
Publication Date:
Research Org.:
Duke Univ., Durham, NC (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1830789
Alternate Identifier(s):
OSTI ID: 1890645
Grant/Contract Number:  
SC0001517
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 60; Journal Issue: 20; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Polarizability; Chromophores; Optical properties; Solvents; Quantum mechanics

Citation Formats

Nayak, Animesh, Park, Jaehong, De Mey, Kurt, Hu, Xiangqian, Beratan, David N., Clays, Koen, and Therien, Michael J. Excited-State Dynamics and Nonlinear Optical Properties of Hyperpolarizable Chromophores Based on Conjugated Bis(terpyridyl)Ru(II) and Palladium and Platinum Porphyrinic Components: Impact of Heavy Metals upon Supermolecular Electro-Optic Properties. United States: N. p., 2021. Web. doi:10.1021/acs.inorgchem.1c02041.
Copy to clipboard
Nayak, Animesh, Park, Jaehong, De Mey, Kurt, Hu, Xiangqian, Beratan, David N., Clays, Koen, & Therien, Michael J. Excited-State Dynamics and Nonlinear Optical Properties of Hyperpolarizable Chromophores Based on Conjugated Bis(terpyridyl)Ru(II) and Palladium and Platinum Porphyrinic Components: Impact of Heavy Metals upon Supermolecular Electro-Optic Properties. United States. https://doi.org/10.1021/acs.inorgchem.1c02041
Copy to clipboard
Nayak, Animesh, Park, Jaehong, De Mey, Kurt, Hu, Xiangqian, Beratan, David N., Clays, Koen, and Therien, Michael J. Wed . "Excited-State Dynamics and Nonlinear Optical Properties of Hyperpolarizable Chromophores Based on Conjugated Bis(terpyridyl)Ru(II) and Palladium and Platinum Porphyrinic Components: Impact of Heavy Metals upon Supermolecular Electro-Optic Properties". United States. https://doi.org/10.1021/acs.inorgchem.1c02041. https://www.osti.gov/servlets/purl/1830789.
Copy to clipboard
@article{osti_1830789,
title = {Excited-State Dynamics and Nonlinear Optical Properties of Hyperpolarizable Chromophores Based on Conjugated Bis(terpyridyl)Ru(II) and Palladium and Platinum Porphyrinic Components: Impact of Heavy Metals upon Supermolecular Electro-Optic Properties},
author = {Nayak, Animesh and Park, Jaehong and De Mey, Kurt and Hu, Xiangqian and Beratan, David N. and Clays, Koen and Therien, Michael J.},
abstractNote = {A new series of strongly coupled oscillators based upon (porphinato)Pd, (porphinato)Pt, and bis(terpyridyl)-ruthenium(II) building blocks is described. These RuPPd, RuPPt, RuPPdRu, and RuPPtRu chromophores feature bis- (terpyridyl)Ru(II) moieties connected to the (porphinato)metal unit via an ethyne linker that bridges the 4!-terpyridyl and porphyrin macrocycle meso-carbon positions. Pump–probe transient optical data demonstrate sub-picosecond excited singlet-to-triplet-state relaxation. The relaxed lowest-energy triplet (T1) excited states of these chromophores feature absorption manifolds that span the 800–1200 nm spectral region, microsecond triplet-state lifetimes, and large absorptive extinction coefficients [ε(T1 → Tn) > 4 × 104 M–1 cm–1]. Dynamic hyperpolarizability (βλ) values were determined from hyper-Rayleigh light scattering (HRS) measurements carried out at several incident irradiation wavelengths over the 800–1500 nm spectral region. Relative to benchmark RuPZn and RuPZnRu chromophores which showed large βHRS values over the 1200–1600 nm range, RuPPd, RuPPt, RuPPdRu, and RuPPtRu displayed large βHRS values over the 850–1200 nm region. Generalized Thomas–Kuhn sum (TKS) rules and experimental hyperpolarizability values were utilized to determine excited state-to-excited state transition dipole terms from experimental electronic absorption data and thus assessed frequency-dependent βλ values, including two- and three-level contributions for both βzzz and βxzx tensor components to the RuPPd, RuPPt, RuPPdRu, and RuPPtRu hyperpolarizability spectra. Furthermore, these analyses qualitatively rationalize how the βzzz and βxzx tensor elements influence the observed irradiation wavelength-dependent hyperpolarizability magnitudes. The TKS analysis suggests that supermolecules related to RuPPd, RuPPt, RuPPdRu, and RuPPtRu will likely feature intricate dependences of experimentally determined βHRS values as a function of irradiation wavelength that derive from substantial singlet–triplet mixing, and complex interactions among multiple different β tensor components that modulate the long wavelength regime of the nonlinear optical response.},
doi = {10.1021/acs.inorgchem.1c02041},
journal = {Inorganic Chemistry},
number = 20,
volume = 60,
place = {United States},
year = {Wed Sep 29 00:00:00 EDT 2021},
month = {Wed Sep 29 00:00:00 EDT 2021}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.inorgchem.1c02041
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

The Palladium-Catalyzed Cross-Coupling Reactions of Organotin Reagents with Organic Electrophiles [New Synthetic Methods(58)]
journal, June 1986

  • Stille, John K.
  • Angewandte Chemie International Edition in English, Vol. 25, Issue 6, p. 508-524
  • DOI: 10.1002/anie.198605081

Engineering opposite electronic polarization of singlet and triplet states increases the yield of high-energy photoproducts
journal, June 2019

  • Polizzi, Nicholas F.; Jiang, Ting; Beratan, David N.
  • Proceedings of the National Academy of Sciences, Vol. 116, Issue 29
  • DOI: 10.1073/pnas.1901752116

Supermolecular-Chromophore-Sensitized Near-Infrared-to-Visible Photon Upconversion
journal, October 2010

  • Singh-Rachford, Tanya N.; Nayak, Animesh; Muro-Small, Maria L.
  • Journal of the American Chemical Society, Vol. 132, Issue 40
  • DOI: 10.1021/ja105510k

Optical nonlinearities of conjugated molecules. Stilbene derivatives and highly polar aromatic compounds
journal, July 1977

  • Oudar, J. L.
  • The Journal of Chemical Physics, Vol. 67, Issue 2
  • DOI: 10.1063/1.434888

Femtosecond Absorption Spectroscopy of Transition Metal Charge-Transfer Complexes
journal, December 2003

  • McCusker, James K.
  • Accounts of Chemical Research, Vol. 36, Issue 12
  • DOI: 10.1021/ar030111d

Unusual Frequency Dispersion Effects of the Nonlinear Optical Response in Highly Conjugated (Polypyridyl)metal−(Porphinato)zinc(II) Chromophores
journal, November 2002

  • Uyeda, H. Tetsuo; Zhao, Yuxia; Wostyn, Kurt
  • Journal of the American Chemical Society, Vol. 124, Issue 46
  • DOI: 10.1021/ja020651q

Porphyrins
journal, September 1970

Second-order nonlinear optical materials: recent advances in chromophore design
journal, January 1997

  • Verbiest, Thierry; Houbrechts, Stephan; Kauranen, Martti
  • Journal of Materials Chemistry, Vol. 7, Issue 11
  • DOI: 10.1039/a703434b

Long-wavelength first hyperpolarizability measurements by hyper-Rayleigh scattering
journal, January 1996

  • Stadler, S.; Dietrich, R.; Bourhill, G.
  • Optics Letters, Vol. 21, Issue 4
  • DOI: 10.1364/ol.21.000251

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
  • DOI: 10.1021/ja0707512

Large Hyperpolarizabilities at Telecommunication-Relevant Wavelengths in Donor–Acceptor–Donor Nonlinear Optical Chromophores
journal, November 2016

Excitation energy-dependent photocurrent switching in a single-molecule photodiode
journal, July 2019

  • Shan, Bing; Nayak, Animesh; Williams, Olivia F.
  • Proceedings of the National Academy of Sciences, Vol. 116, Issue 33
  • DOI: 10.1073/pnas.1907118116

Molecular Road Map to Tuning Ground State Absorption and Excited State Dynamics of Long-Wavelength Absorbers
journal, November 2017

  • Bai, Yusong; Olivier, Jean-Hubert; Yoo, Hyejin
  • Journal of the American Chemical Society, Vol. 139, Issue 46
  • DOI: 10.1021/jacs.7b09982

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
  • DOI: 10.1021/cr00017a023

Femtosecond Dynamics of Excited-State Evolution in [Ru(bpy)3]2+
journal, January 1997

A Twist on Nonlinear Optics: Understanding the Unique Response of π-Twisted Chromophores
journal, April 2019

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
  • DOI: 10.1021/ja00059a060

Design and synthesis of chromophores and polymers for electro-optic and photorefractive applications
journal, August 1997

  • Marder, Seth R.; Kippelen, Bernard; Jen, Alex K. -Y.
  • Nature, Vol. 388, Issue 6645
  • DOI: 10.1038/42190

Near-Infrared-to-Visible Photon Upconversion Enabled by Conjugated Porphyrinic Sensitizers under Low-Power Noncoherent Illumination
journal, May 2015

  • Olivier, Jean-Hubert; Bai, Yusong; Uh, Hyounsoo
  • The Journal of Physical Chemistry A, Vol. 119, Issue 22
  • DOI: 10.1021/acs.jpca.5b03199

Recent advances of BODIPY based derivatives for optoelectronic applications
journal, October 2020

Predicting the Frequency Dispersion of Electronic Hyperpolarizabilities on the Basis of Absorption Data and Thomas−Kuhn Sum Rules
journal, January 2010

  • Hu, Xiangqian; Xiao, Dequan; Keinan, Shahar
  • The Journal of Physical Chemistry C, Vol. 114, Issue 5
  • DOI: 10.1021/jp911556x

The Roles of Molecular Structure and Effective Optical Symmetry in Evolving Dipolar Chromophoric Building Blocks to Potent Octopolar Nonlinear Optical Chromophores
journal, March 2011

  • Ishizuka, Tomoya; Sinks, Louise E.; Song, Kai
  • Journal of the American Chemical Society, Vol. 133, Issue 9
  • DOI: 10.1021/ja105004k

Palladium-catalyzed reactions of organic halides with olefins
journal, April 1979

Highly conjugated, acetylenyl bridged porphyrins: new models for light-harvesting antenna systems
journal, May 1994

Hyperpolarizabilities of the nitroanilines and their relations to the excited state dipole moment
journal, March 1977

  • Oudar, J. L.; Chemla, D. S.
  • The Journal of Chemical Physics, Vol. 66, Issue 6
  • DOI: 10.1063/1.434213

Double‐Quantum Light Scattering by Molecules
journal, November 1966

  • Bersohn, R.; Pao, Yoh‐Han; Frisch, H. L.
  • The Journal of Chemical Physics, Vol. 45, Issue 9
  • DOI: 10.1063/1.1728092

Engineering High-Potential Photo-oxidants with Panchromatic Absorption
journal, June 2017

  • Jiang, Ting; Polizzi, Nicholas F.; Rawson, Jeff
  • Journal of the American Chemical Society, Vol. 139, Issue 25
  • DOI: 10.1021/jacs.7b04400

From molecules to opto-chips: organic electro-optic materials
journal, January 1999

  • Dalton, Larry R.; Steier, William H.; Robinson, Bruce H.
  • Journal of Materials Chemistry, Vol. 9, Issue 9
  • DOI: 10.1039/a902659b

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
  • DOI: 10.1021/ja953610l

A Convenient Synthesis of Ethynylarenes and Diethynylarenes
journal, January 1980

  • Takahashi, S.; Kuroyama, Y.; Sonogashira, K.
  • Synthesis, Vol. 1980, Issue 08
  • DOI: 10.1055/s-1980-29145

The energy gap law for radiationless transitions in large molecules
journal, February 1970

Molecular Symmetry and Solution-Phase Structure Interrogated by Hyper-Rayleigh Depolarization Measurements: Elaborating Highly HyperpolarizableD2-Symmetric Chromophores
journal, April 2008

  • Duncan, Timothy V.; Song, Kai; Hung, Sheng-Ting
  • Angewandte Chemie International Edition, Vol. 47, Issue 16
  • DOI: 10.1002/anie.200703187

Ultrafast Fluorescence Detection in Tris(2,2‘-bipyridine)ruthenium(II) Complex in Solution:  Relaxation Dynamics Involving Higher Excited States
journal, July 2002

  • Bhasikuttan, Achikanath C.; Suzuki, Masaya; Nakashima, Satoru
  • Journal of the American Chemical Society, Vol. 124, Issue 28
  • DOI: 10.1021/ja026135h

Molecular first hyperpolarizabilities of retinal and its derivatives
journal, December 1997

First hyperpolarizability measurements via hyper-Rayleigh scattering at 1500 nm
journal, December 1995

Theoretical Studies of Steric Effects on Intraligand Electron Delocalization: Implications for the Temporal Evolution of MLCT Excited States
journal, April 1998

  • Damrauer, Niels H.; Weldon, Brandon T.; McCusker, James K.
  • The Journal of Physical Chemistry A, Vol. 102, Issue 19
  • DOI: 10.1021/jp9805095

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
  • DOI: 10.1021/ja0400638

Theory of Hyper‐Raman Effects (Nonlinear Inelastic Light Scattering): Selection Rules and Depolarization Ratios for the Second‐Order Polarizability
journal, December 1965

  • Cyvin, S. J.; Rauch, J. E.; Decius, J. C.
  • The Journal of Chemical Physics, Vol. 43, Issue 11
  • DOI: 10.1063/1.1696646

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
  • DOI: 10.1021/jo00074a027
    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: