Orbital Engineering Mediated by Cation Conjugation in Luminescent Uranyl–Organic Hybrid Materials

Raghavan, Adharsh; Cahill, Christopher L.

doi:10.1002/anie.202318161

Title: Orbital Engineering Mediated by Cation Conjugation in Luminescent Uranyl–Organic Hybrid Materials

Journal Article · 22 December 2023 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.202318161 · OSTI ID:2255187

Raghavan, Adharsh ^[1]; Cahill, Christopher L. ^[2]

George Washington University, Washington D.C. (United States); The George Washington University
George Washington University, Washington D.C. (United States)

A series of compounds of the form [HAr]2[UO2X4] is reported here, wherein Ar is systematically varied between pyridine (1-X), quinoline (2-X), acridine (3-X), 2,5-dimethylpyrazine (4-X), quinoxaline (5-X), and phenazine (6-X), and X = Cl or Br. With greater conjugation in the organic cation, a larger quenching in uranyl luminescence is observed in the solid state. Supporting our luminescence experiments with computation, we map out the potential energy diagrams for the singlet and triplet states of both the [HAr]+ cations and [UO2Cl4]2– anion in the crystalline state, and of the assembly. The distinct energy transfer pathways in each compound are discussed.

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Research Organization:: George Washington University, Washington D.C. (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: FG02-05ER15736

OSTI ID:: 2255187

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 7 Vol. 63; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (52)

A Theoretical Insight into the Photophysics of Acridine Rubio-Pons, Òscar; Serrano-Andrés, Luis; Merchán, Manuela The Journal of Physical Chemistry A, Vol. 105, Issue 42 https://doi.org/10.1021/jp013124m	journal	October 2001
Synthesis, structure and photophysical properties of [UO ₂ X ₂ (OPPh ₃ ) ₂ ] (X = Cl, Br, I) Hashem, Emtithal; McCabe, Thomas; Schulzke, Carola Dalton Trans., Vol. 43, Issue 3 https://doi.org/10.1039/C3DT52480A	journal	January 2014
Self-assembly of [UO2X4]2− (X=Cl, Br) dianions with γ substituted pyridinium cations: Structural systematics and fluorescence properties Surbella, Robert G.; Andrews, Michael B.; Cahill, Christopher L. Journal of Solid State Chemistry, Vol. 236 https://doi.org/10.1016/j.jssc.2015.09.011	journal	April 2016
Multiphoton Imaging of Spatial Distribution, Coordination and Redox Environment of Uranium under Model Biogeochemical Conditions Andrews, Michael; Jones, Debbie; Woodward, Adam https://doi.org/10.26434/chemrxiv-2023-lvvtz	preprint	September 2023
Correlation between the vibronic spectra of the uranyl ion and the geometry of its coordination Görller-Walrand, C.; De Jaegere, S. Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 28, Issue 2 https://doi.org/10.1016/0584-8539(72)80250-2	journal	February 1972
Periodic Density Functional Theory Calculations of Uranyl Tetrachloride Compounds Engaged in Uranyl–Cation and Uranyl–Hydrogen Interactions: Electronic Structure, Vibrational, and Thermodynamic Analyses Augustine, Logan J.; Rajapaksha, Harindu; Pyrch, Mikaela Mary F. Inorganic Chemistry, Vol. 62, Issue 1 https://doi.org/10.1021/acs.inorgchem.2c03476	journal	December 2022
Nearly Perfect Triplet-Triplet Energy Transfer from Wannier Excitons to Naphthalene in Organic-Inorganic Hybrid Quantum-Well Materials Ema, K.; Inomata, M.; Kato, Y. Physical Review Letters, Vol. 100, Issue 25 https://doi.org/10.1103/PhysRevLett.100.257401	journal	June 2008
Reaction and deactivation of excited acridine in ethanol Kikuchi, Koichi; Kasama, Kunihiko; Kanemoto, Akihiko The Journal of Physical Chemistry, Vol. 89, Issue 5 https://doi.org/10.1021/j100251a030	journal	February 1985
Uranyl luminescence quenching. An experiment in photochemistry and kinetics Burrows, Hugh D.; Formosinho, Sebastiao J. Journal of Chemical Education, Vol. 55, Issue 2 https://doi.org/10.1021/ed055p125	journal	February 1978
Covalency in the uranyl ion: A polarized x-ray spectroscopic study Denning, R. G.; Green, J. C.; Hutchings, T. E. The Journal of Chemical Physics, Vol. 117, Issue 17 https://doi.org/10.1063/1.1510445	journal	November 2002
Structural Variability of 4f and 5f Thiocyanate Complexes and Dissociation of Uranium(III)–Thiocyanate Bonds with Increased Ionicity Biswas, Saptarshi; Ma, Shuwen; Nuzzo, Stefano Inorganic Chemistry, Vol. 56, Issue 23 https://doi.org/10.1021/acs.inorgchem.7b01560	journal	November 2017
Quenching of the luminescent state of the uranyl ion (UO2+2) by metal ions. Evidence for an electron transfer mechanism Burrows, Hugh D.; Formosinho, Sebastião J.; Miguel, M. Da Graça Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 72, Issue 0 https://doi.org/10.1039/f19767200163	journal	January 1976
Electronic structure and spectrum of UO22+ and UO2Cl42− Pierloot, Kristine; van Besien, Els The Journal of Chemical Physics, Vol. 123, Issue 20 https://doi.org/10.1063/1.2121608	journal	November 2005
New aspects of fluorescence quenching by molecular oxygen Kikuchi, Koichi; Sato, Chika; Watabe, Masanori Journal of the American Chemical Society, Vol. 115, Issue 12 https://doi.org/10.1021/ja00065a033	journal	June 1993
Electronic spectrum of UO22+ and [UO2Cl4]2− calculated with time-dependent density functional theory Pierloot, Kristine; van Besien, Els; van Lenthe, Erik The Journal of Chemical Physics, Vol. 126, Issue 19 https://doi.org/10.1063/1.2735297	journal	May 2007
Metal–organic hybrids involving the [UO ₂ Cl ₃ (NO ₃ )] ²⁻ tecton and the role of halogen polarizability Andrews, Michael B.; Cahill, Christopher L. CrystEngComm, Vol. 15, Issue 16 https://doi.org/10.1039/C2CE26561C	journal	January 2013
Uranium(VI) solubility in carbonate-free WIPP brine Lucchini, J. F.; Borkowski, Marian; Richmann, Michael K. Radiochimica Acta, Vol. 101, Issue 6 https://doi.org/10.1524/ract.2013.2029	journal	March 2013
Solvent effects in solvo-hydrothermal synthesis of uranyl ion complexes with 1,3-adamantanediacetate Thuéry, Pierre; Harrowfield, Jack CrystEngComm, Vol. 17, Issue 21 https://doi.org/10.1039/C5CE00401B	journal	January 2015
Thermal and Photochemical Reduction and Functionalization Chemistry of the Uranyl Dication, [U ^VI O ₂ ] ²⁺ Cowie, Bradley E.; Purkis, Jamie M.; Austin, Jonathan Chemical Reviews, Vol. 119, Issue 18 https://doi.org/10.1021/acs.chemrev.9b00048	journal	August 2019
Energy Transfer Lakowicz, Joseph R. Principles of Fluorescence Spectroscopy https://doi.org/10.1007/978-0-387-46312-4_13	book	January 2006
Chemical Bonding in Cesium Uranyl Chloride Based on the Experimental Electron Density Distribution Zhurov, Vladimir V.; Zhurova, Elizabeth A.; Pinkerton, A. Alan Inorganic Chemistry, Vol. 50, Issue 13 https://doi.org/10.1021/ic200759u	journal	July 2011
Absorption and Fluorescence Studies of Acridine in Subcritical and Supercritical Water Ryan, E. Todd; Xiang, Tao; Johnston, Keith P. The Journal of Physical Chemistry A, Vol. 101, Issue 10 https://doi.org/10.1021/jp962676f	journal	March 1997
Quenching of the uranyl fluorescence by aromatic molecules Matsushima, Ryoka; Sakuraba, Shukichi Journal of the American Chemical Society, Vol. 93, Issue 26 https://doi.org/10.1021/ja00755a004	journal	December 1971
Use of Charge-Assisted Hydrogen Bonding in the Supramolecular Assembly of Hybrid Uranyl Materials de Groot, Joshua; Gojdas, Kyle; Unruh, Daniel K. Crystal Growth & Design, Vol. 14, Issue 3 https://doi.org/10.1021/cg401849r	journal	January 2014
Transuranic Hybrid Materials: Crystallographic and Computational Metrics of Supramolecular Assembly Surbella, Robert G.; Ducati, Lucas C.; Pellegrini, Kristi L. Journal of the American Chemical Society, Vol. 139, Issue 31 https://doi.org/10.1021/jacs.7b05689	journal	July 2017
Investigation of the Luminescence of [UO ₂ X ₄ ] ^2– (X = Cl, Br) Complexes in the Organic Phase Using Time-Resolved Laser-Induced Fluorescence Spectroscopy and Quantum Chemical Simulations Oher, Hanna; Réal, Florent; Vercouter, Thomas Inorganic Chemistry, Vol. 59, Issue 9 https://doi.org/10.1021/acs.inorgchem.9b03614	journal	April 2020
Evolution of formation waters in the Permian Basin, United States: Late Permian evaporated seawater to Neogene meteoric water Saller, Arthur H.; Stueber, Alan M. AAPG Bulletin, Vol. 102, Issue 03 https://doi.org/10.1306/0504171612517157	journal	March 2018
Equatorial Electronic Structure in the Uranyl Ion: Cs ₂ UO ₂ Cl ₄ and Cs ₂ UO ₂ Br ₄ Sergentu, Dumitru-Claudiu; Gendron, Frédéric; Walter, Eric D. Inorganic Chemistry, Vol. 61, Issue 9 https://doi.org/10.1021/acs.inorgchem.1c02832	journal	November 2021
The photochemistry of the uranyl ion Burrows, H. D.; Kemp, T. J. Chemical Society Reviews, Vol. 3, Issue 2 https://doi.org/10.1039/cs9740300139	journal	January 1974
Decomposition of d- and f-Shell Contributions to Uranium Bonding from the Quantum Theory of Atoms in Molecules: Application to Uranium and Uranyl Halides Tanti, Jonathan; Lincoln, Meghan; Kerridge, Andy Inorganics, Vol. 6, Issue 3 https://doi.org/10.3390/inorganics6030088	journal	August 2018
Geochemistry of the waste isolation pilot plant (WIPP) site, southestern New Mexico, U.S.A. Lambert, Steven J. Applied Geochemistry, Vol. 7, Issue 6 https://doi.org/10.1016/0883-2927(92)90068-E	journal	November 1992
Lattice Solvent and Crystal Phase Effects on the Vibrational Spectra of UO ₂ Cl ₄ ^2– Schnaars, David D.; Wilson, Richard E. Inorganic Chemistry, Vol. 53, Issue 20 https://doi.org/10.1021/ic501553m	journal	September 2014
Relaxation mechanism of excited acridine in nonreactive solvents Kasama, Kunihiko; Kikuchi, Koichi; Yamamoto, Sadaaki The Journal of Physical Chemistry, Vol. 85, Issue 10 https://doi.org/10.1021/j150610a005	journal	May 1981
Influence of Alkaline Earth Metal Ions on Structures and Luminescent Properties of Na_mM_nUO₂(CO₃)₃^{(4–m–2n)–} (M = Mg, Ca; m, n = 0–2): Time-Resolved Fluorescence Spectroscopy and Ab Initio Studies Oher, Hanna; Vercouter, Thomas; Réal, Florent Inorganic Chemistry, Vol. 59, Issue 20 https://doi.org/10.1021/acs.inorgchem.0c01986	journal	October 2020
Non-covalent interactions of uranyl complexes: a theoretical study Platts, James A.; Baker, Robert J. Physical Chemistry Chemical Physics, Vol. 20, Issue 22 https://doi.org/10.1039/C8CP02444H	journal	January 2018
The Cambridge Structural Database Groom, Colin R.; Bruno, Ian J.; Lightfoot, Matthew P. Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 72, Issue 2, p. 171-179 https://doi.org/10.1107/S2052520616003954	journal	April 2016
Characterization of Bonding in Cesium Uranyl Chloride: Topological Analysis of the Experimental Charge Density Zhurov, Vladimir V.; Zhurova, Elizabeth A.; Stash, Adam I. The Journal of Physical Chemistry A, Vol. 115, Issue 45 https://doi.org/10.1021/jp204965b	journal	November 2011
Guiding Principles for the Rational Design of Hybrid Materials: Use of DFT Methodology for Evaluating Non‐Covalent Interactions in a Uranyl Tetrahalide Model System Rajapaksha, Harindu; Augustine, Logan J.; Mason, Sara E. Angewandte Chemie International Edition, Vol. 62, Issue 33 https://doi.org/10.1002/anie.202305073	journal	June 2023
Synthesis and spectroscopic characterization of actinyl(VI) tetrahalide coordination compounds containing 2, 2′-bipyridine Pyrch, Mikaela M.; Williams, Jay M.; Kasperski, Maguire W. Inorganica Chimica Acta, Vol. 508 https://doi.org/10.1016/j.ica.2020.119628	journal	August 2020
The electronic structure of the uranyl ion: Part I. The electronic spectrum of Cs2UO2Cl4 Denning, R. G.; Snellgrove, T. R.; Woodwark, D. R. Molecular Physics, Vol. 32, Issue 2 https://doi.org/10.1080/00268977600103211	journal	August 1976
Thermochemical properties of U(VI) hybrid materials containing uranyl tetrachloride anions Cahill, Christopher L.; Deifel, Nicholas P.; Reusser, Dana The Journal of Chemical Thermodynamics, Vol. 114 https://doi.org/10.1016/j.jct.2017.05.009	journal	November 2017
Structural and Vibrational Properties of U(VI)O ₂ Cl ₄ ^2- and Pu(VI)O ₂ Cl ₄ ^2- Complexes Schnaars, David D.; Wilson, Richard E. Inorganic Chemistry, Vol. 52, Issue 24 https://doi.org/10.1021/ic401991n	journal	November 2013
Uranyl–Organic Frameworks with Polycarboxylates: Unusual Effects of a Coordinating Solvent Thuéry, Pierre; Harrowfield, Jack Crystal Growth & Design, Vol. 14, Issue 3 https://doi.org/10.1021/cg4018163	journal	January 2014
Electronic Structure and Bonding in Actinyl Ions and their Analogs Denning, Robert G. The Journal of Physical Chemistry A, Vol. 111, Issue 20 https://doi.org/10.1021/jp071061n	journal	May 2007
Tailoring of energy levels in lead chloride based layered perovskites and energy transfer between the organic and inorganic planes Braun, M.; Tuffentsammer, W.; Wachtel, H. Chemical Physics Letters, Vol. 303, Issue 1-2 https://doi.org/10.1016/S0009-2614(99)00205-5	journal	April 1999
Probing the local coordination environment and nuclearity of uranyl(vi) complexes in non-aqueous media by emission spectroscopy Redmond, Michael P.; Cornet, Stephanie M.; Woodall, Sean D. Dalton Transactions, Vol. 40, Issue 15 https://doi.org/10.1039/c0dt01464h	journal	January 2011
Emission of Acridine and its Aggregates Isolated in the Neon Matrix Prochorow, J.; Kozankiewicz, B.; Dongo Gemi, Bango Bango Acta Physica Polonica A, Vol. 94, Issue 5-6 https://doi.org/10.12693/APhysPolA.94.749	journal	November 1998
Uranium( vi ) complexes with isonicotinic acid: from monomer to 2D polymer with unique U–N bonding Zhang, Yingjie; Karatchevtseva, Inna; Price, Jason R. RSC Advances, Vol. 5, Issue 42 https://doi.org/10.1039/C5RA01272D	journal	January 2015
Mechanism of quenching of the uranyl fluorescence by organic compounds Matsushima, Ryoka Journal of the American Chemical Society, Vol. 94, Issue 17 https://doi.org/10.1021/ja00772a012	journal	August 1972
Uranyl and Uranyl–3d Block Cation Complexes with 1,3-Adamantanedicarboxylate: Crystal Structures, Luminescence, and Magnetic Properties Thuéry, Pierre; Rivière, Eric; Harrowfield, Jack Inorganic Chemistry, Vol. 54, Issue 6 https://doi.org/10.1021/ic503004j	journal	February 2015
Detection and identification of solids, surfaces, and solutions of uranium using vibrational spectroscopy Lu, Grace; Haes, Amanda J.; Forbes, Tori Z. Coordination Chemistry Reviews, Vol. 374 https://doi.org/10.1016/j.ccr.2018.07.010	journal	November 2018
Acridine: an investigation of its molecular and crystalline photophysical behaviour Williams, John O.; Clarke, Brian P. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 73, Issue 0 https://doi.org/10.1039/f19777300514	journal	January 1977

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uranyl
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CCDC 2309525: Experimental Crystal Structure Determination Adharsh, Raghavan,; L., Cahill, Christopher https://doi.org/10.5517/ccdc.csd.cc2hj7t3 The current record is supplemented by this dataset	dataset	January 2024
CCDC 2309522: Experimental Crystal Structure Determination Adharsh, Raghavan,; L., Cahill, Christopher https://doi.org/10.5517/ccdc.csd.cc2hj7q0 The current record is supplemented by this dataset	dataset	January 2024
CCDC 2309520: Experimental Crystal Structure Determination Adharsh, Raghavan,; L., Cahill, Christopher https://doi.org/10.5517/ccdc.csd.cc2hj7ny The current record is supplemented by this dataset	dataset	January 2024
CCDC 2309523: Experimental Crystal Structure Determination Adharsh, Raghavan,; L., Cahill, Christopher https://doi.org/10.5517/ccdc.csd.cc2hj7r1 The current record is supplemented by this dataset	dataset	January 2024
CCDC 2309524: Experimental Crystal Structure Determination Adharsh, Raghavan,; L., Cahill, Christopher https://doi.org/10.5517/ccdc.csd.cc2hj7s2 The current record is supplemented by this dataset	dataset	January 2024
CCDC 2309521: Experimental Crystal Structure Determination Adharsh, Raghavan,; L., Cahill, Christopher https://doi.org/10.5517/ccdc.csd.cc2hj7pz The current record is supplemented by this dataset	dataset	January 2024
CCDC 2309519: Experimental Crystal Structure Determination Adharsh, Raghavan,; L., Cahill, Christopher https://doi.org/10.5517/ccdc.csd.cc2hj7mx The current record is supplemented by this dataset	dataset	January 2024
CCDC 2309518: Experimental Crystal Structure Determination Adharsh, Raghavan,; L., Cahill, Christopher https://doi.org/10.5517/ccdc.csd.cc2hj7lw The current record is supplemented by this dataset	dataset	January 2024

Title: Orbital Engineering Mediated by Cation Conjugation in Luminescent Uranyl–Organic Hybrid Materials

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