Visible-Light-Driven Triplet Sensitization of Polycyclic Aromatic Hydrocarbons Using Thionated Perinones

Palmer, Jonathan R.; Wells, Kaylee A.; Yarnell, James E.; Favale, Joseph M.; Castellano, Felix N.

doi:10.1021/acs.jpclett.0c01634

Visible-Light-Driven Triplet Sensitization of Polycyclic Aromatic Hydrocarbons Using Thionated Perinones

Journal Article · Tue Jun 09 00:00:00 EDT 2020 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.0c01634· OSTI ID:1633647

Palmer, Jonathan R. ^[1]; ^[2]; ^[3]; Favale, Joseph M. ^[2]; ^[2]

North Carolina State Univ., Raleigh, NC (United States); NC State University
North Carolina State Univ., Raleigh, NC (United States)
North Carolina State Univ., Raleigh, NC (United States); United States Air Force Academy, Colorado Springs, CO (United States)

Metal-free chromophores that efficiently generate triplet excited states represent enticing alternatives with respect to transition metal-containing photosensitizers, such as those featuring metal-to-ligand charge transfer excited states. Yet, such molecular constructs have remained underexplored due to the unclear relationship(s) between molecular structure and efficient/rapid intersystem crossing. In this regard, we present a series of three thionated perinone chromophores serving as a newly conceived class of heavy metal-free triplet photosensitizers. We demonstrate that thionation of the lone C=O substituent in each highly fluorescent perinone imparts red-shifted absorbance bands that maintain intense extinction coefficients across the visible spectrum, as well as unusually efficient triplet excited state formation as inferred from the measured singlet O₂ quantum yields at 1270 nm (Φ_Δ = 0.78–1.0). Electronic structure calculations revealed the emergence of a low energy S₁ (n → π*) excited state in the proximity of a slightly higher energy S₂ (π → π*) excited state. The distinct character in each of the two lowest-lying singlet state manifolds resulted in the energetic inversion of the corresponding triplet excited states due to differences in electron exchange interactions. Rapid S₁ → T₁ intersystem crossing was thereby facilitated in this manner through spin–orbit coupling as predicted by the El Sayed rules. The lifetimes of the resultant triplet excited states persisted into the microsecond time regime, as measured by transient absorbance spectroscopy, enabling effective bimolecular triplet sensitization of some common polycyclic aromatic hydrocarbons. The synthetically facile interchange of a single O atom to an S atom in the investigated perinones resulted in marked changes to their photophysical properties, namely, conversion of dominant singlet state fluorescence in the former to long-lived triplet excited states in the latter. The combined results suggest a general strategy for accessing long-lived triplet excited states in organic chromophores featuring a lone C=O moiety residing within its structure, valuable for the design of metal-free triplet photosensitizers.

View Accepted Manuscript (DOE)

Research Organization:: North Carolina State Univ., Raleigh, NC (United States)

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

Contributing Organization:: Air Force Institute of Technology (AFIT)

Grant/Contract Number:: SC0011979

OSTI ID:: 1633647

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 13 Vol. 11; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (63)

New Bichromophoric Triplet Photosensitizer Designs and Their Application in Triplet-Triplet Annihilation Upconversion Guo, Xinyan; Liu, Yiming; Chen, Qi Advanced Optical Materials, Vol. 6, Issue 4 https://doi.org/10.1002/adom.201700981	journal	January 2018
Photochemical Upconversion: Anthracene Dimerization Sensitized to Visible Light by a RuII Chromophore Islangulov, Radiy R.; Castellano, Felix N. Angewandte Chemie International Edition, Vol. 45, Issue 36 https://doi.org/10.1002/anie.200601615	journal	September 2006
Sensitization-Initiated Electron Transfer for Photoredox Catalysis Ghosh, Indrajit; Shaikh, Rizwan S.; König, Burkhard Angewandte Chemie International Edition, Vol. 56, Issue 29 https://doi.org/10.1002/anie.201703004	journal	May 2017
Blue-Emissive Cobalt(III) Complexes and Their Use in the Photocatalytic Trifluoromethylation of Polycyclic Aromatic Hydrocarbons Pal, Amlan K.; Li, Chenfei; Hanan, Garry S. Angewandte Chemie International Edition, Vol. 57, Issue 27 https://doi.org/10.1002/anie.201802532	journal	June 2018
Benzimidazole Derivatives: Synthesis, Physical Properties, and n-Type Semiconducting Properties Mamada, Masashi; Pérez-Bolívar, César; Kumaki, Daisuke Chemistry - A European Journal, Vol. 20, Issue 37 https://doi.org/10.1002/chem.201403058	journal	July 2014
Efficient Phosphorescence from Naphthalenebenzimidizole‐Coordinated Iridium(III) Chromophores Yarnell, James E.; De La Torre, Patricia; Castellano, Felix N. European Journal of Inorganic Chemistry, Vol. 2017, Issue 44 https://doi.org/10.1002/ejic.201700669	journal	September 2017
Structure and decay dynamics of electronic excited states of thiocarbonyl compounds Steer, R. P. Reviews of Chemical Intermediates, Vol. 4, Issue 1-4 https://doi.org/10.1007/BF03052411	journal	May 1981
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals Zhao, Yan; Truhlar, Donald G. Theoretical Chemistry Accounts, Vol. 120, Issue 1-3 https://doi.org/10.1007/s00214-007-0310-x	journal	July 2007
New aroyleneimidazoles as dyes for thermoplastic polymeric materials Kobrakov, K. I.; Zubkova, N. S.; Stankevich, G. S. Fibre Chemistry, Vol. 38, Issue 3 https://doi.org/10.1007/s10692-006-0066-4	journal	May 2006
T1–T2 inversion in aromatic thiones Maciejewski, A.; Szymanski, M.; Steer, R. P. Chemical Physics Letters, Vol. 143, Issue 6 https://doi.org/10.1016/0009-2614(88)87066-0	journal	February 1988
Organic photoconductive (OPC) devices incorporating bisarylimidazole perinone pigments Loutfy, R. Dyes and Pigments, Vol. 15, Issue 2 https://doi.org/10.1016/0143-7208(91)87013-D	journal	January 1991
Photophysics of thione triplets in solution: Factors controlling the rates of radiationless decay Szymański, M.; Maciejewski, A.; Steer, R. P. Chemical Physics, Vol. 124, Issue 1 https://doi.org/10.1016/0301-0104(88)85090-0	journal	August 1988
Concerning apparent intersystem crossing efficiencies in molecules with small S1T1 energy gaps Szymanski, M.; Maciejewski, A.; Steer, R. P. Journal of Photochemistry and Photobiology A: Chemistry, Vol. 57, Issue 1-3 https://doi.org/10.1016/1010-6030(91)85033-D	journal	April 1991
The photochemistry of thiocarbonyl compounds Coyle, John D. Tetrahedron, Vol. 41, Issue 23 https://doi.org/10.1016/S0040-4020(01)91341-9	journal	January 1985
Synthesis and properties of perylene pigments Nagao, Yukinori Progress in Organic Coatings, Vol. 31, Issue 1-2 https://doi.org/10.1016/S0300-9440(97)00017-9	journal	May 1997
Photon upconversion based on sensitized triplet–triplet annihilation Singh-Rachford, Tanya N.; Castellano, Felix N. Coordination Chemistry Reviews, Vol. 254, Issue 21-22 https://doi.org/10.1016/j.ccr.2010.01.003	journal	November 2010
A lysosome-localized thionaphthalimide as a potential heavy-atom-free photosensitizer for selective photodynamic therapy Nguyen, Van-Nghia; Baek, Gain; Qi, Sujie Dyes and Pigments, Vol. 177 https://doi.org/10.1016/j.dyepig.2020.108265	journal	June 2020
Organic Photoredox Catalysis Romero, Nathan A.; Nicewicz, David A. Chemical Reviews, Vol. 116, Issue 17 https://doi.org/10.1021/acs.chemrev.6b00057	journal	June 2016
Microwave Synthesis of Thionated Naphthalene Diimide-Based Small Molecules and Polymers Pahlavanlu, Paniz; Tilley, Andrew J.; McAllister, Bryony T. The Journal of Organic Chemistry, Vol. 82, Issue 23 https://doi.org/10.1021/acs.joc.7b02162	journal	October 2017
Excited-State Triplet Equilibria in a Series of Re(I)-Naphthalimide Bichromophores Yarnell, James E.; Wells, Kaylee A.; Palmer, Jonathan R. The Journal of Physical Chemistry B, Vol. 123, Issue 35 https://doi.org/10.1021/acs.jpcb.9b05688	journal	August 2019
Effect of Charge-Transfer State Energy on Charge Generation Efficiency via Singlet Fission in Pentacene–Fullerene Solar Cells Willems, Robin E. M.; Meskers, Stefan C. J.; Wienk, Martijn M. The Journal of Physical Chemistry C, Vol. 123, Issue 16 https://doi.org/10.1021/acs.jpcc.9b00568	journal	April 2019
Beyond Shockley–Queisser: Molecular Approaches to High-Efficiency Photovoltaics Tayebjee, Murad J. Y.; McCamey, Dane R.; Schmidt, Timothy W. The Journal of Physical Chemistry Letters, Vol. 6, Issue 12 https://doi.org/10.1021/acs.jpclett.5b00716	journal	June 2015
Thio-bisnaphthalimides as Heavy-Atom-Free Photosensitizers with Efficient Singlet Oxygen Generation and Large Stokes Shifts: Synthesis and Properties Zhang, Lei; Huang, Zhisong; Dai, Dongdong Organic Letters, Vol. 18, Issue 21 https://doi.org/10.1021/acs.orglett.6b02902	journal	October 2016
Heavy-Atom-Free Red-to-Yellow Photon Upconversion in a Thiosquaraine Composite Pristash, Sarah R.; Corp, Kathryn L.; Rabe, Emily J. ACS Applied Energy Materials, Vol. 3, Issue 1 https://doi.org/10.1021/acsaem.9b01808	journal	November 2019
The photophysics, physical photochemistry, and related spectroscopy of thiocarbonyls Maciejewski, Andrzej.; Steer, Ronald P. Chemical Reviews, Vol. 93, Issue 1 https://doi.org/10.1021/cr00017a005	journal	January 1993
Organic photoconductive materials: recent trends and developments Law, Kock Yee. Chemical Reviews, Vol. 93, Issue 1 https://doi.org/10.1021/cr00017a020	journal	January 1993
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
New Ru(II) Chromophores with Extended Excited-State Lifetimes Tyson, Daniel S.; Luman, Charles R.; Zhou, Xiaoli Inorganic Chemistry, Vol. 40, Issue 16 https://doi.org/10.1021/ic010287g	journal	July 2001
Bidirectional “Ping-Pong” Energy Transfer and 3000-Fold Lifetime Enhancement in a Re(I) Charge Transfer Complex Yarnell, James E.; Deaton, Joseph C.; McCusker, Catherine E. Inorganic Chemistry, Vol. 50, Issue 16 https://doi.org/10.1021/ic200974h	journal	August 2011
Light-Harvesting Arrays with Coumarin Donors and MLCT Acceptors Tyson, Daniel S.; Castellano, Felix N. Inorganic Chemistry, Vol. 38, Issue 20 https://doi.org/10.1021/ic9905300	journal	September 1999
Thermally activated delayed S1 fluorescence of aromatic thiones Maciejewski, Andrzej; Szymanski, Marian; Steer, Ronald P. The Journal of Physical Chemistry, Vol. 90, Issue 23 https://doi.org/10.1021/j100281a051	journal	November 1986
Temperature-Independent Singlet Exciton Fission in Tetracene Wilson, Mark W. B.; Rao, Akshay; Johnson, Kerr Journal of the American Chemical Society, Vol. 135, Issue 44 https://doi.org/10.1021/ja408854u	journal	October 2013
Multistep Photochemical Charge Separation in Rod-like Molecules Based on Aromatic Imides and Diimides Greenfield, Scott R.; Svec, Walter A.; Gosztola, David Journal of the American Chemical Society, Vol. 118, Issue 28 https://doi.org/10.1021/ja9600789	journal	January 1996
Quantitative Intramolecular Singlet Fission in Bipentacenes Sanders, Samuel N.; Kumarasamy, Elango; Pun, Andrew B. Journal of the American Chemical Society, Vol. 137, Issue 28 https://doi.org/10.1021/jacs.5b04986	journal	July 2015
Exciton Correlations in Intramolecular Singlet Fission Sanders, Samuel N.; Kumarasamy, Elango; Pun, Andrew B. Journal of the American Chemical Society, Vol. 138, Issue 23 https://doi.org/10.1021/jacs.6b00657	journal	June 2016
An Emerging Molecular Design Approach to Heavy-Atom-Free Photosensitizers for Enhanced Photodynamic Therapy under Hypoxia Nguyen, Van-Nghia; Qi, Sujie; Kim, Sangin Journal of the American Chemical Society, Vol. 141, Issue 41 https://doi.org/10.1021/jacs.9b09220	journal	September 2019
Organic Triplet Sensitizer Library Derived from a Single Chromophore (BODIPY) with Long-Lived Triplet Excited State for Triplet–Triplet Annihilation Based Upconversion Wu, Wanhua; Guo, Huimin; Wu, Wenting The Journal of Organic Chemistry, Vol. 76, Issue 17 https://doi.org/10.1021/jo200990y	journal	September 2011
Upconverted Emission from Pyrene and Di- tert -butylpyrene Using Ir(ppy) ₃ as Triplet Sensitizer Zhao, Wei; Castellano, Felix N. The Journal of Physical Chemistry A, Vol. 110, Issue 40 https://doi.org/10.1021/jp064261s	journal	October 2006
Enhanced Intersystem Crossing Rate in Polymethine-Like Molecules: Sulfur-Containing Squaraines versus Oxygen-Containing Analogues Peceli, Davorin; Hu, Honghua; Fishman, Dmitry A. The Journal of Physical Chemistry A, Vol. 117, Issue 11 https://doi.org/10.1021/jp400276g	journal	March 2013
Ultrafast Triplet Formation in Thionated Perylene Diimides Tilley, Andrew J.; Pensack, Ryan D.; Lee, Tia S. The Journal of Physical Chemistry C, Vol. 118, Issue 19 https://doi.org/10.1021/jp503708d	journal	May 2014
Near-Unity Quantum Yields for Intersystem Crossing and Singlet Oxygen Generation in Polymethine-like Molecules: Design and Experimental Realization Webster, Scott; Peceli, Davorin; Hu, Honghua The Journal of Physical Chemistry Letters, Vol. 1, Issue 15 https://doi.org/10.1021/jz100381v	journal	July 2010
Green Synthesis of Polycyclic Benzimidazole Derivatives and Organic Semiconductors Mamada, Masashi; Pérez-Bolívar, César; Anzenbacher, Pavel Organic Letters, Vol. 13, Issue 18 https://doi.org/10.1021/ol201973w	journal	September 2011
A transferable model for singlet-fission kinetics Yost, Shane R.; Lee, Jiye; Wilson, Mark W. B. Nature Chemistry, Vol. 6, Issue 6 https://doi.org/10.1038/nchem.1945	journal	May 2014
Photoredox catalysis using infrared light via triplet fusion upconversion Ravetz, Benjamin D.; Pun, Andrew B.; Churchill, Emily M. Nature, Vol. 565, Issue 7739 https://doi.org/10.1038/s41586-018-0835-2	journal	January 2019
On the efficiency limit of triplet–triplet annihilation for photochemical upconversion Cheng, Yuen Yap; Khoury, Tony; Clady, Raphaël G. C. R. Phys. Chem. Chem. Phys., Vol. 12, Issue 1 https://doi.org/10.1039/B913243K	journal	January 2010
Transition metal complexes with strong absorption of visible light and long-lived triplet excited states: from molecular design to applications Zhao, Jianzhang; Ji, Shaomin; Wu, Wanhua RSC Adv., Vol. 2, Issue 5 https://doi.org/10.1039/C1RA00665G	journal	January 2012
Photochemical upconversion: present status and prospects for its application to solar energy conversion Schulze, Tim F.; Schmidt, Timothy W. Energy & Environmental Science, Vol. 8, Issue 1 https://doi.org/10.1039/C4EE02481H	journal	January 2015
Recent progress in heavy atom-free organic compounds showing unexpected intersystem crossing (ISC) ability Zhao, Jianzhang; Chen, Kepeng; Hou, Yuqi Organic & Biomolecular Chemistry, Vol. 16, Issue 20 https://doi.org/10.1039/C8OB00421H	journal	January 2018
Ruthenium(II) complex with a notably long excited state lifetime Tyson, Daniel S.; Bialecki, Jason; Castellano, Felix N. Chemical Communications, Vol. 0, Issue 23, p. 2355-2356 https://doi.org/10.1039/b007336i	journal	January 2000
Low power upconversion using MLCT sensitizers Islangulov, Radiy R.; Kozlov, Denis V.; Castellano, Felix N. Chemical Communications, Issue 30 https://doi.org/10.1039/b506575e	journal	January 2005
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy Weigend, Florian; Ahlrichs, Reinhart Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305 https://doi.org/10.1039/b508541a	journal	January 2005
Accurate Coulomb-fitting basis sets for H to Rn Weigend, Florian Physical Chemistry Chemical Physics, Vol. 8, Issue 9 https://doi.org/10.1039/b515623h	journal	January 2006
Reevaluation of absolute luminescence quantum yields of standard solutions using a spectrometer with an integrating sphere and a back-thinned CCD detector Suzuki, Kengo; Kobayashi, Atsushi; Kaneko, Shigeo Physical Chemistry Chemical Physics, Vol. 11, Issue 42 https://doi.org/10.1039/b912178a	journal	January 2009
Energy upconversion sensitized by a platinum(ii) terpyridyl acetylide complex Du, Pingwu; Eisenberg, Richard Chemical Science, Vol. 1, Issue 4 https://doi.org/10.1039/c0sc00244e	journal	January 2010
Improving the light-harvesting of amorphous silicon solar cells with photochemical upconversion Cheng, Yuen Yap; Fückel, Burkhard; MacQueen, Rowan W. Energy & Environmental Science, Vol. 5, Issue 5 https://doi.org/10.1039/c2ee21136j	journal	January 2012
Triplet photosensitizers: from molecular design to applications Zhao, Jianzhang; Wu, Wanhua; Sun, Jifu Chemical Society Reviews, Vol. 42, Issue 12 https://doi.org/10.1039/c3cs35531d	journal	January 2013
New developments in the polarizable continuum model for quantum mechanical and classical calculations on molecules in solution Cossi, Maurizio; Scalmani, Giovanni; Rega, Nadia The Journal of Chemical Physics, Vol. 117, Issue 1 https://doi.org/10.1063/1.1480445	journal	July 2002
Spin—Orbit Coupling and the Radiationless Processes in Nitrogen Heterocyclics El‐Sayed, M. A. The Journal of Chemical Physics, Vol. 38, Issue 12 https://doi.org/10.1063/1.1733610	journal	June 1963
High-efficiency, low-voltage phosphorescent organic light-emitting diode devices with mixed host Kondakova, Marina E.; Pawlik, Thomas D.; Young, Ralph H. Journal of Applied Physics, Vol. 104, Issue 9 https://doi.org/10.1063/1.3000046	journal	November 2008
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Quantum Yields for the Photosensitized Formation of the Lowest Electronically Excited Singlet State of Molecular Oxygen in Solution Wilkinson, Francis; Helman, W. Phillip; Ross, Alberta B. Journal of Physical and Chemical Reference Data, Vol. 22, Issue 1 https://doi.org/10.1063/1.555934	journal	January 1993
Handbook of Photochemistry Montalti, Marco; Credi, Alberto; Prodi, Luca https://doi.org/10.1201/9781420015195	book	December 2005
Promising fluorescent dye for solar energy conversion based on a perylene perinone Debije, Michael G.; Verbunt, Paul P. C.; Nadkarni, Pradeep J. Applied Optics, Vol. 50, Issue 2 https://doi.org/10.1364/AO.50.000163	journal	January 2011

Similar Records

Long-lived triplet excited state in a platinum(ii) perylene monoimide complex

Journal Article · Tue Oct 02 20:00:00 EDT 2018 · Dalton Transactions · OSTI ID:1633630

Controlling the excited-state dynamics of low band gap, near-infrared absorbers via proquinoidal unit electronic structural modulation

Journal Article · Tue Jun 06 20:00:00 EDT 2017 · Chemical Science · OSTI ID:1426479

Related Subjects

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

Visible-Light-Driven Triplet Sensitization of Polycyclic Aromatic Hydrocarbons Using Thionated Perinones

Citation Formats

References (63)

Similar Records

Related Subjects