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Title: Unusual solvent polarity dependent excitation relaxation dynamics of a bis[ p -ethynyldithiobenzoato]Pd-linked bis[(porphinato)zinc] complex

Abstract

A porphyrin dimer linked by a Pd(ii)-based linker displays unusual excited-state dynamics where solvent polarity steers singlet and triplet decay-channel population.

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [5]; ORCiD logo [6]
  1. Department of Molecular Engineering; Graduate School of Engineering; Kyoto University; Kyoto; Japan
  2. Department of Chemistry; University of Pennsylvania; Philadelphia; USA; Nuclear Chemistry Research Division
  3. Department of Chemistry; University of Pennsylvania; Philadelphia; USA
  4. Department of Chemistry; University of Pennsylvania; Philadelphia; USA; Department of Chemistry
  5. Department of Chemistry; Korea Advanced Institute of Science and Technology (KAIST) & Center for Catalytic Hydrocarbon Functionalizations; Institute for Basic Science (IBS); Daejeon 34141; South Korea
  6. Department of Chemistry; Duke University; French Family Science Center; Durham; USA
Publication Date:
Research Org.:
Duke Univ., Durham, NC (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1540055
DOE Contract Number:  
SC0001517
Resource Type:
Journal Article
Journal Name:
Molecular Systems Design & Engineering
Additional Journal Information:
Journal Volume: 3; Journal Issue: 1; Journal ID: ISSN 2058-9689
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
Chemistry; Engineering; Science & Technology - Other Topics; Materials Science

Citation Formats

Park, Jaehong, Park, Tae-Hong, Sinks, Louise E., Deria, Pravas, Park, Jiyong, Baik, Mu-Hyun, and Therien, Michael J. Unusual solvent polarity dependent excitation relaxation dynamics of a bis[ p -ethynyldithiobenzoato]Pd-linked bis[(porphinato)zinc] complex. United States: N. p., 2018. Web. doi:10.1039/c8me00001h.
Park, Jaehong, Park, Tae-Hong, Sinks, Louise E., Deria, Pravas, Park, Jiyong, Baik, Mu-Hyun, & Therien, Michael J. Unusual solvent polarity dependent excitation relaxation dynamics of a bis[ p -ethynyldithiobenzoato]Pd-linked bis[(porphinato)zinc] complex. United States. doi:10.1039/c8me00001h.
Park, Jaehong, Park, Tae-Hong, Sinks, Louise E., Deria, Pravas, Park, Jiyong, Baik, Mu-Hyun, and Therien, Michael J. Mon . "Unusual solvent polarity dependent excitation relaxation dynamics of a bis[ p -ethynyldithiobenzoato]Pd-linked bis[(porphinato)zinc] complex". United States. doi:10.1039/c8me00001h.
@article{osti_1540055,
title = {Unusual solvent polarity dependent excitation relaxation dynamics of a bis[ p -ethynyldithiobenzoato]Pd-linked bis[(porphinato)zinc] complex},
author = {Park, Jaehong and Park, Tae-Hong and Sinks, Louise E. and Deria, Pravas and Park, Jiyong and Baik, Mu-Hyun and Therien, Michael J.},
abstractNote = {A porphyrin dimer linked by a Pd(ii)-based linker displays unusual excited-state dynamics where solvent polarity steers singlet and triplet decay-channel population.},
doi = {10.1039/c8me00001h},
journal = {Molecular Systems Design & Engineering},
issn = {2058-9689},
number = 1,
volume = 3,
place = {United States},
year = {2018},
month = {1}
}

Works referenced in this record:

Molecular engineering of cocktail co-sensitization for efficient panchromatic porphyrin-sensitized solar cells
journal, January 2012

  • Wu, Hui-Ping; Ou, Zih-Wei; Pan, Tsung-Yu
  • Energy & Environmental Science, Vol. 5, Issue 12
  • DOI: 10.1039/c2ee22870j

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

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
  • DOI: 10.1039/c0cs00094a

Extended π-conjugated ruthenium zinc–porphyrin complexes with enhanced nonlinear-optical properties
journal, January 2015

  • de Torres, Miriam; Semin, Sergey; Razdolski, Ilya
  • Chemical Communications, Vol. 51, Issue 14
  • DOI: 10.1039/C4CC09592H

“Closer is Better and Two is Superior to One”: Third-Order Optical Nonlinearities of a Family of Porphyrin–Anderson Type Polyoxometalate Hybrid Compounds
journal, November 2016

  • Hassan, Sadaf ul; Asif, Hafiz Muhammad; Zhou, Yunshan
  • The Journal of Physical Chemistry C, Vol. 120, Issue 48
  • DOI: 10.1021/acs.jpcc.6b09951

Porphyrin Arch-Tapes: Synthesis, Contorted Structures, and Full Conjugation
journal, June 2017

  • Fukui, Norihito; Kim, Taeyeon; Kim, Dongho
  • Journal of the American Chemical Society, Vol. 139, Issue 26
  • DOI: 10.1021/jacs.7b05332

Quasi-Ohmic Single Molecule Charge Transport through Highly Conjugated meso -to- meso Ethyne-Bridged Porphyrin Wires
journal, May 2012

  • Li, Zhihai; Park, Tae-Hong; Rawson, Jeff
  • Nano Letters, Vol. 12, Issue 6
  • DOI: 10.1021/nl2043216

High-performance thermoelectricity in edge-over-edge zinc-porphyrin molecular wires
journal, January 2017

  • Noori, Mohammed; Sadeghi, Hatef; Lambert, Colin J.
  • Nanoscale, Vol. 9, Issue 16
  • DOI: 10.1039/C6NR09598D

Electronic Delocalization in the Radical Cations of Porphyrin Oligomer Molecular Wires
journal, July 2017

  • Peeks, Martin D.; Tait, Claudia E.; Neuhaus, Patrik
  • Journal of the American Chemical Society, Vol. 139, Issue 30
  • DOI: 10.1021/jacs.7b05386

Near-infrared-emissive polymersomes: Self-assembled soft matter for in vivo optical imaging
journal, February 2005

  • Ghoroghchian, P. P.; Frail, P. R.; Susumu, K.
  • Proceedings of the National Academy of Sciences, Vol. 102, Issue 8
  • DOI: 10.1073/pnas.0409394102

Single-Particle Two-Photon Absorption Imaging and Enhancement Determination for Organic Nanoparticles
journal, January 2011

  • Raymond, Jeffery E.; Goodson, Theodore
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 4
  • DOI: 10.1021/jz1016558

Carbohydrate-Porphyrin Conjugates with Two-Photon Absorption Properties as Potential Photosensitizing Agents for Photodynamic Therapy
journal, January 2011

  • Achelle, Sylvain; Couleaud, Pierre; Baldeck, Patrice
  • European Journal of Organic Chemistry, Vol. 2011, Issue 7
  • DOI: 10.1002/ejoc.201001209

Two-Dimensional Fully Conjugated Polymeric Photosensitizers for Advanced Photodynamic Therapy
journal, November 2016


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


Conjugated porphyrin arrays: synthesis, properties and applications for functional materials
journal, January 2015

  • Tanaka, Takayuki; Osuka, Atsuhiro
  • Chemical Society Reviews, Vol. 44, Issue 4
  • DOI: 10.1039/C3CS60443H

EPR Spectroscopy and Photophysics of the Lowest Photoactivated Triplet State of a Series of Highly Conjugated (Porphinato)Zn Arrays
journal, December 1995

  • Angiolillo, P. J.; Lin, Victor S. -Y.; Vanderkooi, J. M.
  • Journal of the American Chemical Society, Vol. 117, Issue 50
  • DOI: 10.1021/ja00155a015

Building molecular wires from the colours of life: conjugated porphyrin oligomers
journal, January 1999


Photochemistry of covalently-linked multi-porphyrinic systems
journal, June 2002

  • Aratani, Naoki; Osuka, Atsuhiro; Cho, Hyun Sun
  • Journal of Photochemistry and Photobiology C: Photochemistry Reviews, Vol. 3, Issue 1
  • DOI: 10.1016/S1389-5567(02)00003-5

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
  • DOI: 10.1021/ja021157p

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
  • DOI: 10.1021/ja040243h

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
  • DOI: 10.1021/ja061897o

Discrete Cyclic Porphyrin Arrays as Artificial Light-Harvesting Antenna
journal, December 2009

  • Aratani, Naoki; Kim, Dongho; Osuka, Atsuhiro
  • Accounts of Chemical Research, Vol. 42, Issue 12
  • DOI: 10.1021/ar9001697

Ethynyl porphyrins bridging bis(phosphine)platinum(II) centers: molecular models for conjugated organometallic porphyrin polymers
journal, January 1998

  • Ferri, Angelica; Polzonetti, Giovanni; Licoccia, Silvia
  • Journal of the Chemical Society, Dalton Transactions, Issue 23
  • DOI: 10.1039/a805728a

Syntheses and Optical and Electrochemical Properties of Porphyrin Dimers Linked by Metal Ions
journal, May 2002

  • Richeter, Sébastien; Jeandon, Christophe; Gisselbrecht, Jean-Paul
  • Journal of the American Chemical Society, Vol. 124, Issue 21
  • DOI: 10.1021/ja017531n

Excited-State Energy-Transfer Dynamics in Self-Assembled Triads Composed of Two Porphyrins and an Intervening Bis(dipyrrinato)metal Complex
journal, October 2003

  • Yu, Lianhe; Muthukumaran, Kannan; Sazanovich, Igor V.
  • Inorganic Chemistry, Vol. 42, Issue 21
  • DOI: 10.1021/ic034559m

Peripherally η 1 -Platinated Organometallic Porphyrins as Building Blocks for Multiporphyrin Arrays
journal, February 2004

  • Hartnell, Regan D.; Arnold, Dennis P.
  • Organometallics, Vol. 23, Issue 3
  • DOI: 10.1021/om0305869

Porphyrin dimers bridged by a platinum–diacetylide unit
journal, January 2006

  • Chen, Yi-Jen; Chen, Szu-Shuo; Lo, Shang-Shih
  • Chemical Communications, Issue 9
  • DOI: 10.1039/b513921j

Energy Transfers in Monomers, Dimers, and Trimers of Zinc(II) and Palladium(II) Porphyrins Bridged by Rigid Pt-Containing Conjugated Organometallic Spacers
journal, August 2009

  • Bellows, Diana; Aly, Shawkat M.; Gros, Claude P.
  • Inorganic Chemistry, Vol. 48, Issue 16
  • DOI: 10.1021/ic900840w

Helical Bis(N-Confused Porphyrins) with Subunits Fused by Double Orthometalation with Platinum: Adaptability of an Apparently Rigid System
journal, November 2009

  • Chmielewski, Piotr J.; Durlej, Bartosz; Siczek, Marta
  • Angewandte Chemie International Edition, Vol. 48, Issue 46
  • DOI: 10.1002/anie.200904289

Effects of Carbon–Metal–Carbon Linkages on the Optical, Photophysical, and Electrochemical Properties of Phosphametallacycle-Linked Coplanar Porphyrin Dimers
journal, January 2012

  • Matano, Yoshihiro; Matsumoto, Kazuaki; Hayashi, Hironobu
  • Journal of the American Chemical Society, Vol. 134, Issue 3
  • DOI: 10.1021/ja210205v

Unexpected Drastic Decrease in the Excited-State Electronic Communication between Porphyrin Chromophores Covalently Linked by a Palladium(II) Bridge
journal, August 2014

  • Abdelhameed, Mohammed; Karsenti, Paul-Ludovic; Langlois, Adam
  • Chemistry - A European Journal, Vol. 20, Issue 40
  • DOI: 10.1002/chem.201403146

Ultrafast energy transfer in a Pd( ii )-bridged bisporphyrin dyad
journal, January 2014

  • Abdelhameed, Mohammed; Langlois, Adam; Karsenti, Paul-Ludovic
  • Chem. Commun., Vol. 50, Issue 93
  • DOI: 10.1039/C4CC05898D

Synthesis and Electrochemical Studies of Porphyrin Dimers Linked by Metallocarbenes
journal, May 2014

  • Haumesser, Julien; Gisselbrecht, Jean-Paul; Karmazin-Brelot, Lydia
  • Organometallics, Vol. 33, Issue 18
  • DOI: 10.1021/om5002099

Singly and doubly β-to-β platinum-bridged porphyrin dimers and their reductive eliminations
journal, January 2015

  • Jiang, Hua-Wei; Tanaka, Takayuki; Osuka, Atsuhiro
  • Chemical Science, Vol. 6, Issue 11
  • DOI: 10.1039/C5SC02553B

meso-to-meso Pt II -bridged Ni II -porphyrin dimers
journal, January 2017

  • Fukui, Norihito; Jiang, Hua-Wei; Osuka, Atsuhiro
  • Organic Chemistry Frontiers, Vol. 4, Issue 5
  • DOI: 10.1039/C7QO00093F

The electroluminescence of organic materials
journal, January 2000

  • Mitschke, Ullrich; Bäuerle, Peter
  • Journal of Materials Chemistry, Vol. 10, Issue 7
  • DOI: 10.1039/a908713c

Metallopolymers: New Multifunctional Materials
journal, November 2007


New Trends in the Use of Transition Metal-Ligand Complexes for Applications in Electroluminescent Devices
journal, May 2005

  • Holder, E.; Langeveld, B. M. W.; Schubert, U. S.
  • Advanced Materials, Vol. 17, Issue 9
  • DOI: 10.1002/adma.200400284

Functional soft materials from metallopolymers and metallosupramolecular polymers
journal, February 2011

  • Whittell, George R.; Hager, Martin D.; Schubert, Ulrich S.
  • Nature Materials, Vol. 10, Issue 3
  • DOI: 10.1038/nmat2966

Organometallic Photovoltaics: A New and Versatile Approach for Harvesting Solar Energy Using Conjugated Polymetallaynes
journal, September 2010

  • Wong, Wai-Yeung; Ho, Cheuk-Lam
  • Accounts of Chemical Research, Vol. 43, Issue 9
  • DOI: 10.1021/ar1000378

Finding the Way to Solar Fuels with Dye-Sensitized Photoelectrosynthesis Cells
journal, September 2016

  • Brennaman, M. Kyle; Dillon, Robert J.; Alibabaei, Leila
  • Journal of the American Chemical Society, Vol. 138, Issue 40
  • DOI: 10.1021/jacs.6b06466

Metal alkynyl complexes as switchable NLO systems
journal, November 2011

  • Green, Katy A.; Cifuentes, Marie P.; Samoc, Marek
  • Coordination Chemistry Reviews, Vol. 255, Issue 21-22
  • DOI: 10.1016/j.ccr.2011.02.021

Electron Spin Relaxation of Hole and Electron Polarons in π-Conjugated Porphyrin Arrays: Spintronic Implications
journal, December 2014

  • Rawson, Jeff; Angiolillo, Paul J.; Frail, Paul R.
  • The Journal of Physical Chemistry B, Vol. 119, Issue 24
  • DOI: 10.1021/jp5122728

Alkyne-Bridged Multi[Copper(II) Porphyrin] Structures: Nuances of Orbital Symmetry in Long-Range, Through-Bond Mediated, Isotropic Spin Exchange Interactions
journal, July 2017

  • Wang, Ruobing; Brugh, Alexander M.; Rawson, Jeff
  • Journal of the American Chemical Society, Vol. 139, Issue 29
  • DOI: 10.1021/jacs.7b03252

Supramolecular coordination chemistry of aromatic polyoxalamide ligands: A metallosupramolecular approach toward functional magnetic materials
journal, October 2010

  • Dul, Marie-Claire; Pardo, Emilio; Lescouëzec, Rodrigue
  • Coordination Chemistry Reviews, Vol. 254, Issue 19-20
  • DOI: 10.1016/j.ccr.2010.03.003

Structural studies of metal complexes with sulphur-containing bidentate ligands. Part I. Crystal and molecular structures of trimeric bis-(dithiobenzoato)-nickel(II) and -palladium(II)
journal, January 1975

  • Bonamico, Mario; Dessy, Giulia; Fares, Vincenzo
  • Journal of the Chemical Society, Dalton Transactions, Issue 21
  • DOI: 10.1039/dt9750002250

Complexes of dithiocarboxylic acids
journal, August 1968


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
  • DOI: 10.1021/ja9939587

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

Carbodithioate-Terminated Oligo(phenyleneethynylene)s:  Synthesis and Surface Functionalization of Gold Nanoparticles
journal, July 2007

  • Park, Tae-Hong; Therien, Michael J.
  • Organic Letters, Vol. 9, Issue 15
  • DOI: 10.1021/ol070789j

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
  • DOI: 10.1021/ja0203925

Optical properties of metalloporphyrin excited states
journal, August 1989

  • Rodriguez, Juan; Kirmaier, Christine; Holten, Dewey
  • Journal of the American Chemical Society, Vol. 111, Issue 17
  • DOI: 10.1021/ja00199a004

Intramolecular Energy Transfer in S 1 - and S 2 -States of Porphyrin Trimers
journal, May 2001

  • Nakano, Aiko; Yasuda, Yuzo; Yamazaki, Tomoko
  • The Journal of Physical Chemistry A, Vol. 105, Issue 20
  • DOI: 10.1021/jp010596s

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
  • DOI: 10.1021/ja981811u

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

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

Ethyne-Bridged (Porphinato)Zinc(II)−(Porphinato)Iron(III) Complexes:  Phenomenological Dependence of Excited-State Dynamics upon (Porphinato)Iron Electronic Structure
journal, August 2006

  • Duncan, Timothy V.; Wu, Sophia P.; Therien, Michael J.
  • Journal of the American Chemical Society, Vol. 128, Issue 32
  • DOI: 10.1021/ja061388m

Effect of the Solvent Environment on the Spectroscopic Properties and Dynamics of the Lowest Excited States of Carotenoids
journal, May 2000

  • Frank, Harry A.; Bautista, James A.; Josue, Jesusa
  • The Journal of Physical Chemistry B, Vol. 104, Issue 18
  • DOI: 10.1021/jp000079u

Spectroscopic and Dynamic Properties of the Peridinin Lowest Singlet Excited States
journal, November 2001

  • Zigmantas, Donatas; Polívka, Tomáš; Hiller, Roger G.
  • The Journal of Physical Chemistry A, Vol. 105, Issue 45
  • DOI: 10.1021/jp010022n

Carotenoid to chlorophyll energy transfer in the peridinin-chlorophyll-a-protein complex involves an intramolecular charge transfer state
journal, December 2002

  • Zigmantas, D.; Hiller, R. G.; Sundstrom, V.
  • Proceedings of the National Academy of Sciences, Vol. 99, Issue 26
  • DOI: 10.1073/pnas.262537599

Excited-State Dynamics in Polar Solvents of Push−Pull Polyenes Designed for Nonlinear Optics
journal, March 2000

  • Plaza, Pascal; Laage, Damien; Martin, Monique M.
  • The Journal of Physical Chemistry A, Vol. 104, Issue 11
  • DOI: 10.1021/jp992282z

Femtosecond transient photoinduced transmission measurements on a novel conjugated zinc porphyrin system
journal, January 1996

  • O’Keefe, G. E.; Denton, G. J.; Harvey, E. J.
  • The Journal of Chemical Physics, Vol. 104, Issue 3
  • DOI: 10.1063/1.470805

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
  • DOI: 10.1021/ja2079477

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


Prediction of Dielectric Constants of Binary Solvents at Various Temperatures
journal, September 2010

  • Jouyban, Abolghasem; Soltanpour, Shahla
  • Journal of Chemical & Engineering Data, Vol. 55, Issue 9
  • DOI: 10.1021/je1000632