Elucidation of complex triplet excited state dynamics in Pd(ii) biladiene tetrapyrroles

Martin, Shea M.; Repa, Gil M.; Hamburger, Robert C.; Pointer, Craig A.; Ward, Kaytlin; Pham, Trong-Nhan; Martin, Maxwell I.; Rosenthal, Joel; Fredin, Lisa A.; Young, Elizabeth R.

doi:10.1039/d2cp04572a

Elucidation of complex triplet excited state dynamics in Pd(ii) biladiene tetrapyrroles

Journal Article · Mon Jan 02 23:00:00 EST 2023 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/d2cp04572a· OSTI ID:2510459

^[1]; ^[1]; ^[1]; Pointer, Craig A. ^[1]; Ward, Kaytlin ^[2]; ^[2]; Martin, Maxwell I. ^[2]; ^[2]; ^[1]; ^[1]

Lehigh University, Bethlehem, PA (United States)
University of Delaware, Newark, DE (United States)

Pd(II) biladienes have been developed over the last five years as non-aromatic oligotetrapyrrole complexes that support a rich triplet photochemistry. In this work, we have undertaken the first detailed photophysical interrogation of three homologous Pd(II) biladienes bearing different combinations of methyl- and phenyl-substituents on the frameworks’ sp³-hybridized meso-carbon (i.e., the 10-position of the biladiene framework). These experiments have revealed unexpected excited-state dynamics that are dependent on the wavelength of light used to excite the biladiene. More specifically, transient absorption spectroscopy revealed that higher-energy excitation (λ_exc ~ 350–500 nm) led to an additional lifetime (i.e., an extra photophysical process) compared to experiments carried out following excitation into the lowest-energy excited states (λ_exc = 550 nm). Each Pd(II) biladiene complex displayed an intersystem crossing lifetime on the order of tens of ps and a triplet lifetime of ~20 μs, regardless of the excitation wavelength. However, when higher-energy light is used to excite the complexes, a new lifetime on the order of hundreds of ps is observed. The origin of the ‘extra’ lifetime observed upon higher energy excitation was revealed using density functional theory (DFT) and time-dependent DFT (TDDFT). These efforts demonstrated that excitation into higher-energy metal-mixed-charge-transfer excited states with high spin–orbit coupling to higher energy metal-mixed-charge-transfer triplet states leads to the additional excitation deactivation pathway. Furthermore, the results of this work demonstrate that Pd(II) biladienes support a unique triplet photochemistry that may be exploited for development of new photochemical schemes and applications.

View Accepted Manuscript (DOE)

Research Organization:: University of Delaware, Newark, DE (United States)

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

Grant/Contract Number:: SC0021068

OSTI ID:: 2510459

Alternate ID(s):: OSTI ID: 2419600

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 3 Vol. 25; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (39)

The Art of Fluorescence Imaging with Chemical Sensors Schäferling, Michael Angewandte Chemie International Edition, Vol. 51, Issue 15 https://doi.org/10.1002/anie.201105459	journal	March 2012
Michael Kasha: From Photochemistry and Flowers to Spectroscopy and Music Demchenko, Alexander P.; Heldt, Józef; Waluk, Jacek Angewandte Chemie International Edition, Vol. 53, Issue 52 https://doi.org/10.1002/anie.201405222	journal	October 2014
Molecular and Interfacial Calculations of Iron(II) Light Harvesters Fredin, Lisa A.; Wärnmark, Kenneth; Sundström, Villy ChemSusChem, Vol. 9, Issue 7 https://doi.org/10.1002/cssc.201600062	journal	March 2016
Template Synthesis of Alkyl-Substituted Metal Isocorroles: Template Synthesis of Alkyl-Substituted Metal Isocorroles Hoffmann, Martin; Cordes, Birte; Kleeberg, Christian European Journal of Inorganic Chemistry, Vol. 2016, Issue 19 https://doi.org/10.1002/ejic.201600419	journal	June 2016
β-Octabromo- and β-Octakis(trifluoromethyl)isocorroles: New Sterically Constrained Macrocyclic Ligands Thomas, Kolle E.; Beavers, Christine M.; Gagnon, Kevin J. ChemistryOpen, Vol. 6, Issue 3 https://doi.org/10.1002/open.201700035	journal	May 2017
Luminescent nanobeads for optical sensing and imaging of dissolved oxygen Borisov, Sergey M.; Klimant, Ingo Microchimica Acta, Vol. 164, Issue 1-2 https://doi.org/10.1007/s00604-008-0047-9	journal	May 2008
Porphyrin-based compounds and their applications in materials and medicine Shi, Yingyan; Zhang, Fuming; Linhardt, Robert J. Dyes and Pigments, Vol. 188 https://doi.org/10.1016/j.dyepig.2021.109136	journal	April 2021
The photophysics of Ni(II) meso-tetraphenylbenzoporphyrin: A combined theoretical and experimental investigation Zamyatin, Andrey V.; Soldatova, Alexandra V.; Rodgers, Michael A. J. Inorganica Chimica Acta, Vol. 360, Issue 3 https://doi.org/10.1016/j.ica.2006.06.031	journal	February 2007
Binding of palladium (II) 5, 10, 15, 20-tetrakis (4-sulfonatophenyl) porphyrin to a lectin for photosensitizer targeted delivery Bogoeva, Vanya; Petrova, Lidiya; Kubát, Pavel Journal of Photochemistry and Photobiology B: Biology, Vol. 153 https://doi.org/10.1016/j.jphotobiol.2015.10.010	journal	December 2015
Photophysical characterization of imidazolium-substituted Pd(II), In(III), and Zn(II) porphyrins as photosensitizers for photodynamic therapy Kee, Hooi Ling; Bhaumik, Jayeeta; Diers, James R. Journal of Photochemistry and Photobiology A: Chemistry, Vol. 200, Issue 2-3 https://doi.org/10.1016/j.jphotochem.2008.08.006	journal	December 2008
Stable optical oxygen sensing materials based on click-coupling of fluorinated platinum(II) and palladium(II) porphyrins—A convenient way to eliminate dye migration and leaching Koren, Klaus; Borisov, Sergey M.; Klimant, Ingo Sensors and Actuators B: Chemical, Vol. 169 https://doi.org/10.1016/j.snb.2012.04.062	journal	July 2012
Synthesis, Redox, and Spectroscopic Properties of Pd(II) 10,10-Dimethylisocorrole Complexes Prepared via Bromination of Dimethylbiladiene Oligotetrapyrroles Martin, Maxwell I.; Cai, Qiuqi; Yap, Glenn P. A. Inorganic Chemistry, Vol. 59, Issue 24 https://doi.org/10.1021/acs.inorgchem.0c02721	journal	December 2020
Synthesis, Spectroscopic, and ¹ O ₂ Sensitization Characteristics of Extended Pd(II) 10,10-Dimethylbiladiene Complexes Bearing Alkynyl–Aryl Appendages Rice, Anthony T.; Martin, Maxwell I.; Warndorf, Molly C. Inorganic Chemistry, Vol. 60, Issue 15 https://doi.org/10.1021/acs.inorgchem.1c01127	journal	July 2021
Synthesis, Electrochemistry, and Photophysics of Pd(II) Biladiene Complexes Bearing Varied Substituents at the sp ³ -Hybridized 10-Position Cai, Qiuqi; Rice, Anthony T.; Pointer, Craig A. Inorganic Chemistry, Vol. 60, Issue 20 https://doi.org/10.1021/acs.inorgchem.1c02458	journal	October 2021
Photochemotherapeutic Properties of a Linear Tetrapyrrole Palladium(II) Complex displaying an Exceptionally High Phototoxicity Index Potocny, Andrea M.; Riley, Rachel S.; O’Sullivan, Rachel K. Inorganic Chemistry, Vol. 57, Issue 17 https://doi.org/10.1021/acs.inorgchem.8b01225	journal	August 2018
Evaluation of Spin-Orbit Couplings with Linear-Response Time-Dependent Density Functional Methods Gao, Xing; Bai, Shuming; Fazzi, Daniele Journal of Chemical Theory and Computation, Vol. 13, Issue 2 https://doi.org/10.1021/acs.jctc.6b00915	journal	January 2017
Two-Step, One-Flask Synthesis of a Meso-Substituted Phlorin Kim, Dongjoon; Chun, Hao-Jung; Donnelly, Christopher C. The Journal of Organic Chemistry, Vol. 81, Issue 12 https://doi.org/10.1021/acs.joc.6b00571	journal	May 2016
Sub-100 fs Intersystem Crossing to a Metal-Centered Triplet in Ni(II)OEP Observed with M-Edge XANES Ryland, Elizabeth S.; Zhang, Kaili; Vura-Weis, Josh The Journal of Physical Chemistry A, Vol. 123, Issue 25 https://doi.org/10.1021/acs.jpca.9b03376	journal	June 2019
Q and Soret Band Photoexcitation of Isolated Palladium Porphyrin Tetraanions Leads to Delayed Emission of Nonthermal Electrons over Microsecond Time Scales Jäger, Patrick; Brendle, Katrina; Schwarz, Ulrike The Journal of Physical Chemistry Letters, Vol. 7, Issue 7 https://doi.org/10.1021/acs.jpclett.6b00407	journal	March 2016
Adjusting Interfacial Chemistry and Electronic Properties of Photovoltaics Based on a Highly Pure Sb₂S₃ Absorber by Atomic Layer Deposition Büttner, Pascal; Scheler, Florian; Pointer, Craig ACS Applied Energy Materials, Vol. 2, Issue 12 https://doi.org/10.1021/acsaem.9b01721	journal	December 2019
Gold Nanoshell-Linear Tetrapyrrole Conjugates for Near Infrared-Activated Dual Photodynamic and Photothermal Therapies Wang, Jianxin; Potocny, Andrea M.; Rosenthal, Joel ACS Omega, Vol. 5, Issue 1 https://doi.org/10.1021/acsomega.9b04150	journal	December 2019
Synthesis and Characterization of Free-Base, Copper, and Nickel Isocorroles Pomarico, Giuseppe; Xiao, Xiao; Nardis, Sara Inorganic Chemistry, Vol. 49, Issue 12 https://doi.org/10.1021/ic100730j	journal	June 2010
Porphyrins. 40. Electronic spectra and four-orbital energies of free-base, zinc, copper, and palladium tetrakis(perfluorophenyl)porphyrins Spellane, P. J.; Gouterman, M.; Antipas, A. Inorganic Chemistry, Vol. 19, Issue 2 https://doi.org/10.1021/ic50204a021	journal	February 1980
Synthesis, Electrochemistry, and Photophysics of a Family of Phlorin Macrocycles That Display Cooperative Fluoride Binding Pistner, Allen J.; Lutterman, Daniel A.; Ghidiu, Michael J. Journal of the American Chemical Society, Vol. 135, Issue 17 https://doi.org/10.1021/ja401391z	journal	April 2013
Dipyrromethane + Dipyrromethanedicarbinol Routes to an Electron Deficient meso-Substituted Phlorin with Enhanced Stability O'Brien, Anna Y.; McGann, John P.; Geier, G. Richard The Journal of Organic Chemistry, Vol. 72, Issue 11 https://doi.org/10.1021/jo070216k	journal	April 2007
Investigation of Complementary Reactions of a Dipyrromethane with a Dipyrromethanemonocarbinol Leading to a 5-Isocorrole Flint, Danette L.; Fowler, Rachel L.; LeSaulnier, Timothy D. The Journal of Organic Chemistry, Vol. 75, Issue 3 https://doi.org/10.1021/jo902452c	journal	February 2010
Ultrafast Dynamics of Porphyrins in the Condensed Phase: I. Free Base Tetraphenylporphyrin ^† Baskin, J. Spencer; Yu, Hua-Zhong; Zewail, Ahmed H. The Journal of Physical Chemistry A, Vol. 106, Issue 42 https://doi.org/10.1021/jp020398g	journal	October 2002
A Tetrapyrrole Macrocycle Displaying a Multielectron Redox Chemistry and Tunable Absorbance Profile Pistner, Allen J.; Yap, Glenn P. A.; Rosenthal, Joel The Journal of Physical Chemistry C, Vol. 116, Issue 32 https://doi.org/10.1021/jp3059382	journal	August 2012
Factors Controlling the Spectroscopic Properties and Supramolecular Chemistry of an Electron Deficient 5,5-Dimethylphlorin Architecture Pistner, Allen J.; Lutterman, Daniel A.; Ghidiu, Michael J. The Journal of Physical Chemistry C, Vol. 118, Issue 26 https://doi.org/10.1021/jp5016824	journal	June 2014
Electrochemical, Spectroscopic, and ¹ O ₂ Sensitization Characteristics of 10,10-Dimethylbiladiene Complexes of Zinc and Copper Pistner, Allen J.; Pupillo, Rachel C.; Yap, Glenn P. A. The Journal of Physical Chemistry A, Vol. 118, Issue 45 https://doi.org/10.1021/jp506412r	journal	October 2014
Triplet–Triplet Excitation Transfer in Palladium Porphyrin–Fullerene and Platinum Porphyrin–Fullerene Dyads Obondi, Christopher O.; Lim, Gary N.; D’Souza, Francis The Journal of Physical Chemistry C, Vol. 119, Issue 1 https://doi.org/10.1021/jp511310c	journal	December 2014
Effective Nuclear Charges for the First- through Third-Row Transition Metal Elements in Spin−Orbit Calculations Koseki, Shiro; Schmidt, Michael W.; Gordon, Mark S. The Journal of Physical Chemistry A, Vol. 102, Issue 50 https://doi.org/10.1021/jp983453n	journal	December 1998
Electronic state dependence of heterogeneous electron transfer: injection from the S ₁ and S ₂ state of phlorin into TiO ₂ Nieto-Pescador, Jesus; Abraham, Baxter; Pistner, Allen J. Physical Chemistry Chemical Physics, Vol. 17, Issue 12 https://doi.org/10.1039/C5CP00296F	journal	January 2015
Photostable Optical Oxygen Sensing Material: Platinum Tetrakis(pentafluorophenyl)porphyrin Immobilized in Polystyrene Lee, Sang-Kyung; Okura, Ichiro Analytical Communications, Vol. 34, Issue 6 https://doi.org/10.1039/a701130j	journal	January 1997
Structure and spectroscopic characterization of free base and metal complexes of 5,5-dimethyl-10,15-bis(pentafluorophenyl)isocorrole Costa, Roshinee; Geier III, G. Richard; Ziegler, Christopher J. Dalton Transactions, Vol. 40, Issue 17 https://doi.org/10.1039/c1dt10112a	journal	January 2011
Synthesis and spectroscopic characterization of Ni, Zn, Pd and Pt tetra(pentafluorophenyl)porpholactone with comparisons to Mg, Zn, Y, Pd and Pt metal complexes of tetra(pentafluorophenyl)porphine Khalil, Gamal; Gouterman, Martin; Ching, Stephen Journal of Porphyrins and Phthalocyanines, Vol. 06, Issue 02 https://doi.org/10.1142/S108842460200018X	journal	February 2002
Synthesis, structure, electronic characterization, and halogenation of gold(III) phlorin complexes Pistner, Allen J.; Martin, Maxwell I.; Yap, Glenn P. A. Journal of Porphyrins and Phthalocyanines, Vol. 25, Issue 07n08 https://doi.org/10.1142/S1088424621500565	journal	June 2021
Evaluating Nanoshells and a Potent Biladiene Photosensitizer for Dual Photothermal and Photodynamic Therapy of Triple Negative Breast Cancer Cells Riley, Rachel; O’Sullivan, Rachel; Potocny, Andrea Nanomaterials, Vol. 8, Issue 9 https://doi.org/10.3390/nano8090658	journal	August 2018
A P-61 Black Widow Inspired Palladium Biladiene Complex for Efficient Sensitization of Singlet Oxygen Using Visible Light Rice, Anthony T.; Yap, Glenn P. A.; Rosenthal, Joel Photochem, Vol. 2, Issue 1 https://doi.org/10.3390/photochem2010005	journal	January 2022

Similar Records

Elucidation of complex triplet excited state dynamics in Pd( ii ) biladiene tetrapyrroles

Journal Article · Sat Dec 31 23:00:00 EST 2022 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:2419600

Mapping the influence of ligand electronics on the spectroscopic and ¹O ₂ sensitization characteristics of Pd( ii ) biladiene complexes bearing phenyl–alkynyl groups at the 2- and 18-positions

Journal Article · Thu May 18 00:00:00 EDT 2023 · Dalton Transactions · OSTI ID:2422516

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Transient absorption spectroscopy
density functional theory
mechanistic studies
metal-centered triplet
porphyrinoid
tetrapyrrole macrocycles
triplet formation

Elucidation of complex triplet excited state dynamics in Pd(ii) biladiene tetrapyrroles

Citation Formats

References (39)

Similar Records

Related Subjects