Supramolecular Assembly of Molecular Rare-Earth–3,5-Dichlorobenzoic Acid–2,2':6',2"-Terpyridine Materials: Structural Systematics, Luminescence Properties, and Magnetic Behavior
Abstract
The syntheses and crystal structures of 16 new rare-earth (RE = La3+–Y3+)–3,5-dichlorobenzoic acid–terpyridine molecular materials characterized via single-crystal and powder X-ray diffraction are reported. These 16 complexes consist of four unique structure types ranging from molecular dimers (La3+ and Ce3+) to tetramers (Pr3+–Y3+) as one moves across the RE3+ series. This structural evolution is accompanied by subsequent changes in modes of supramolecular assembly (halogen bonding, halogen-π, halogen–halogen, and π–π interactions). Solid-state visible and near-infrared lifetime measurements were performed on complexes 6 (Sm3+), 7 (Eu3+), 9 (Tb3+), 10 (Dy3+), 11 (Ho3+), 12 (Er3+), and 14 (Yb3+), and characteristic emission was observed for all complexes except 11. Lifetime data for 11, 12, and 14 suggest sensitization by the terpy antenna does occur in near-infrared systems, although not as efficiently as in the visible region. Additionally, direct current magnetic susceptibility measurements were taken for complexes 10 (Dy3+) and 12 (Er3+) and showed dominant ferromagnetic behavior.
- Authors:
-
- George Washington Univ., Washington, DC (United States)
- Cardiff Univ.,Wales (United Kingdom)
- Univ. of Ottawa, Ontario (Canada)
- Howard Univ., Washington, DC (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1388551
- Grant/Contract Number:
- SC0001089
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 55; Journal Issue: 14; Related Information: MSA partners with University of Notre Dame (lead); University of California, Davis; Florida State University; George Washington University; University of Michigan; University of Minnesota; Oak Ridge National Laboratory; Oregon state University; Rensselaer Polytechnic Institute; Savannah River National Laboratory; 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; nuclear (including radiation effects); materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly)
Citation Formats
Carter, Korey P., Thomas, Kara E., Pope, Simon J. A., Holmberg, Rebecca J., Butcher, Ray J., Murugesu, Muralee, and Cahill, Christopher L. Supramolecular Assembly of Molecular Rare-Earth–3,5-Dichlorobenzoic Acid–2,2':6',2"-Terpyridine Materials: Structural Systematics, Luminescence Properties, and Magnetic Behavior. United States: N. p., 2016.
Web. doi:10.1021/acs.inorgchem.6b00408.
Carter, Korey P., Thomas, Kara E., Pope, Simon J. A., Holmberg, Rebecca J., Butcher, Ray J., Murugesu, Muralee, & Cahill, Christopher L. Supramolecular Assembly of Molecular Rare-Earth–3,5-Dichlorobenzoic Acid–2,2':6',2"-Terpyridine Materials: Structural Systematics, Luminescence Properties, and Magnetic Behavior. United States. https://doi.org/10.1021/acs.inorgchem.6b00408
Carter, Korey P., Thomas, Kara E., Pope, Simon J. A., Holmberg, Rebecca J., Butcher, Ray J., Murugesu, Muralee, and Cahill, Christopher L. Mon .
"Supramolecular Assembly of Molecular Rare-Earth–3,5-Dichlorobenzoic Acid–2,2':6',2"-Terpyridine Materials: Structural Systematics, Luminescence Properties, and Magnetic Behavior". United States. https://doi.org/10.1021/acs.inorgchem.6b00408. https://www.osti.gov/servlets/purl/1388551.
@article{osti_1388551,
title = {Supramolecular Assembly of Molecular Rare-Earth–3,5-Dichlorobenzoic Acid–2,2':6',2"-Terpyridine Materials: Structural Systematics, Luminescence Properties, and Magnetic Behavior},
author = {Carter, Korey P. and Thomas, Kara E. and Pope, Simon J. A. and Holmberg, Rebecca J. and Butcher, Ray J. and Murugesu, Muralee and Cahill, Christopher L.},
abstractNote = {The syntheses and crystal structures of 16 new rare-earth (RE = La3+–Y3+)–3,5-dichlorobenzoic acid–terpyridine molecular materials characterized via single-crystal and powder X-ray diffraction are reported. These 16 complexes consist of four unique structure types ranging from molecular dimers (La3+ and Ce3+) to tetramers (Pr3+–Y3+) as one moves across the RE3+ series. This structural evolution is accompanied by subsequent changes in modes of supramolecular assembly (halogen bonding, halogen-π, halogen–halogen, and π–π interactions). Solid-state visible and near-infrared lifetime measurements were performed on complexes 6 (Sm3+), 7 (Eu3+), 9 (Tb3+), 10 (Dy3+), 11 (Ho3+), 12 (Er3+), and 14 (Yb3+), and characteristic emission was observed for all complexes except 11. Lifetime data for 11, 12, and 14 suggest sensitization by the terpy antenna does occur in near-infrared systems, although not as efficiently as in the visible region. Additionally, direct current magnetic susceptibility measurements were taken for complexes 10 (Dy3+) and 12 (Er3+) and showed dominant ferromagnetic behavior.},
doi = {10.1021/acs.inorgchem.6b00408},
journal = {Inorganic Chemistry},
number = 14,
volume = 55,
place = {United States},
year = {Mon Jun 27 00:00:00 EDT 2016},
month = {Mon Jun 27 00:00:00 EDT 2016}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 53 works
Citation information provided by
Web of Science
Web of Science
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:
Lanthanide-Containing Molecular and Supramolecular Polymetallic Functional Assemblies
journal, June 2002
- Bünzli, Jean-Claude G.; Piguet, Claude
- Chemical Reviews, Vol. 102, Issue 6
Taking advantage of luminescent lanthanide ions
journal, January 2005
- Bünzli, Jean-Claude G.; Piguet, Claude
- Chemical Society Reviews, Vol. 34, Issue 12
Development of responsive visibly and NIR luminescent and supramolecular coordination self-assemblies using lanthanide ion directed synthesis
journal, August 2014
- Bradberry, Samuel J.; Savyasachi, Aramballi Jayant; Martinez-Calvo, Miguel
- Coordination Chemistry Reviews, Vol. 273-274
Aromatic N-donor ligands as chelators and sensitizers of lanthanide ion emission
journal, August 2014
- de Bettencourt-Dias, Ana; Barber, Patrick S.; Viswanathan, Subha
- Coordination Chemistry Reviews, Vol. 273-274
Lanthanide-directed synthesis of luminescent self-assembly supramolecular structures and mechanically bonded systems from acyclic coordinating organic ligands
journal, January 2016
- Barry, Dawn E.; Caffrey, David F.; Gunnlaugsson, Thorfinnur
- Chemical Society Reviews, Vol. 45, Issue 11
Lanthanide Luminescent Bioprobes (LLBs)
journal, February 2009
- Bünzli, Jean-Claude G.
- Chemistry Letters, Vol. 38, Issue 2
Visible-light sensitized luminescent europium(iii)-β-diketonate complexes: bioprobes for cellular imaging
journal, January 2013
- Reddy, M. L. P.; Divya, V.; Pavithran, Rani
- Dalton Transactions, Vol. 42, Issue 43
Charge Transport and Sensitized 1.5 μm Electroluminescence Properties of Full Solution-Processed NIR-OLED based on Novel Er(III) Fluorinated β-Diketonate Ternary Complex
journal, May 2013
- Martín-Ramos, Pablo; Coya, Carmen; Álvarez, Ángel L.
- The Journal of Physical Chemistry C, Vol. 117, Issue 19
White OLED based on a temperature sensitive Eu3+/Tb3+ β-diketonate complex
journal, March 2014
- Lima, P. P.; Paz, F. A. A.; Brites, C. D. S.
- Organic Electronics, Vol. 15, Issue 3
Lanthanide Complexes for Second Order Nonlinear Optics: Evidence for the Direct Contribution of f Electrons to the Quadratic Hyperpolarizability 1
journal, October 2005
- Tancrez, Nicolas; Feuvrie, Christophe; Ledoux, Isabelle
- Journal of the American Chemical Society, Vol. 127, Issue 39
Nonlinear optical activity in dipolar organic–lanthanide complexes
journal, January 2010
- Law, Ga-Lai; Wong, Ka-Leung; Lau, Kok-Kin
- Journal of Materials Chemistry, Vol. 20, Issue 20
Lanthanides in molecular magnetism: so fascinating, so challenging
journal, January 2012
- Luzon, Javier; Sessoli, Roberta
- Dalton Transactions, Vol. 41, Issue 44
Lanthanide Single-Molecule Magnets
journal, March 2013
- Woodruff, Daniel N.; Winpenny, Richard E. P.; Layfield, Richard A.
- Chemical Reviews, Vol. 113, Issue 7
Lessons learned from dinuclear lanthanide nano-magnets
journal, January 2013
- Habib, Fatemah; Murugesu, Muralee
- Chemical Society Reviews, Vol. 42, Issue 8
Structural Rearrangement Through Lanthanide Contraction in Dinuclear Complexes
journal, December 2013
- Hutchings, Amy-Jayne; Habib, Fatemah; Holmberg, Rebecca J.
- Inorganic Chemistry, Vol. 53, Issue 4
Review: Lanthanide coordination chemistry: from old concepts to coordination polymers
journal, September 2014
- Bünzli, Jean-Claude G.
- Journal of Coordination Chemistry, Vol. 67, Issue 23-24
Lanthanide based tuning of luminescence in MOFs and dense frameworks – from mono- and multimetal systems to sensors and films
journal, January 2014
- Meyer, L. V.; Schönfeld, F.; Müller-Buschbaum, K.
- Chemical Communications, Vol. 50, Issue 60
Magnetic Anisotropy in a Dysprosium/DOTA Single-Molecule Magnet: Beyond Simple Magneto-Structural Correlations
journal, January 2012
- Cucinotta, Giuseppe; Perfetti, Mauro; Luzon, Javier
- Angewandte Chemie International Edition, Vol. 51, Issue 7
Effect of the capping ligand on luminescent erbium(iii) β-diketonate single-ion magnets
journal, January 2014
- Silva, M. Ramos; Martín-Ramos, P.; Coutinho, J. T.
- Dalton Transactions, Vol. 43, Issue 18
A series of Ln-p-chlorobenzoic acid–terpyridine complexes: lanthanide contraction effects, supramolecular interactions and luminescent behavior
journal, January 2014
- Carter, Korey P.; Pope, Simon J. A.; Cahill, Christopher L.
- CrystEngComm, Vol. 16, Issue 10
Exploring supramolecular assembly and luminescent behavior in a series of RE-p-chlorobenzoic acid-1,10-phenanthroline complexes
journal, January 2014
- Carter, Korey P.; Zulato, Cecília H. F.; Cahill, Christopher L.
- CrystEngComm, Vol. 16, Issue 44
Controlling dimensionality via a dual ligand strategy in Ln-thiophene-2,5-dicarboxylic acid-terpyridine coordination polymers
journal, January 2015
- Carter, Korey P.; Zulato, Cecília H. F.; Rodrigues, Emille M.
- Dalton Transactions, Vol. 44, Issue 36
2,2′:6′,2″-Terpyridines: From chemical obscurity to common supramolecular motifs
journal, January 2007
- Constable, Edwin C.
- Chem. Soc. Rev., Vol. 36, Issue 2
Combining coordination and supramolecular chemistry to explore uranyl assembly in the solid state
journal, January 2015
- Carter, Korey P.; Cahill, Christopher L.
- Inorganic Chemistry Frontiers, Vol. 2, Issue 2
Probing the Influence of N-Donor Capping Ligands on Supramolecular Assembly in Molecular Uranyl Materials
journal, December 2015
- Carter, Korey P.; Kalaj, Mark; Cahill, Christopher L.
- European Journal of Inorganic Chemistry, Vol. 2016, Issue 1
Comparison of silver and molybdenum microfocus X-ray sources for single-crystal structure determination
journal, January 2015
- Krause, Lennard; Herbst-Irmer, Regine; Sheldrick, George M.
- Journal of Applied Crystallography, Vol. 48, Issue 1
SIR 92 – a program for automatic solution of crystal structures by direct methods
journal, June 1994
- Altomare, A.; Cascarano, G.; Giacovazzo, C.
- Journal of Applied Crystallography, Vol. 27, Issue 3
A short history of SHELX
journal, December 2007
- Sheldrick, George M.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
WinGX and ORTEP for Windows : an update
journal, July 2012
- Farrugia, Louis J.
- Journal of Applied Crystallography, Vol. 45, Issue 4
The nature of halogen.cntdot..cntdot..cntdot.halogen interactions: are short halogen contacts due to specific attractive forces or due to close packing of nonspherical atoms?
journal, November 1989
- Desiraju, Gautam R.; Parthasarathy, R.
- Journal of the American Chemical Society, Vol. 111, Issue 23
Halogen Bonds in Crystal Engineering: Like Hydrogen Bonds yet Different
journal, May 2014
- Mukherjee, Arijit; Tothadi, Srinu; Desiraju, Gautam R.
- Accounts of Chemical Research, Vol. 47, Issue 8
OH–π and halogen–π interactions as driving forces in the crystal organisations of tri-bromo and tri-iodo trityl alcohols
journal, January 2008
- Schollmeyer, Dieter; Shishkin, Oleg V.; Rühl, Thomas
- CrystEngComm, Vol. 10, Issue 6
Lone pair–π interactions: a new supramolecular bond?
journal, January 2008
- Mooibroek, Tiddo J.; Gamez, Patrick; Reedijk, Jan
- CrystEngComm, Vol. 10, Issue 11
A critical account on π–π stacking in metal complexes with aromatic nitrogen-containing ligands †
journal, January 2000
- Janiak, Christoph
- Journal of the Chemical Society, Dalton Transactions, Issue 21
The exploration of supramolecular interactions stemming from the [UO 2 (NCS) 4 (H 2 O)] 2− tecton and substituted pyridinium cations
journal, January 2014
- Surbella III, Robert G.; Cahill, Christopher L.
- CrystEngComm, Vol. 16, Issue 12
Combining coordination and supramolecular chemistry for the formation of uranyl-organic hybrid materials
journal, January 2011
- Deifel, Nicholas P.; Cahill, Christopher L.
- Chemical Communications, Vol. 47, Issue 21
Utilizing hydrogen bonds and halogen–halogen interactions in the design of uranyl hybrid materials
journal, January 2012
- Andrews, Michael B.; Cahill, Christopher L.
- Dalton Trans., Vol. 41, Issue 14
Uranyl Bearing Hybrid Materials: Synthesis, Speciation, and Solid-State Structures
journal, August 2012
- Andrews, Michael B.; Cahill, Christopher L.
- Chemical Reviews, Vol. 113, Issue 2
Syntheses, structures and characterizations of two Ln(III)-3,5-dichlorobenzoate coordination polymers
journal, September 2013
- Tan, Xin; Che, Yun-Xia; Zheng, Ji-Min
- Inorganic Chemistry Communications, Vol. 35
Synthesis, Structure, and Magnetic Properties of Dy 2 Co 2 L 10 (bipy) 2 and Ln 2 Ni 2 L 10 (bipy) 2 , Ln = La, Gd, Tb, Dy, and Ho: Slow Magnetic Relaxation in Dy 2 Co 2 L 10 (bipy) 2 and Dy 2 Ni 2 L 10 (bipy) 2
journal, August 2014
- Zhao, Fang-Hua; Li, Hui; Che, Yun-Xia
- Inorganic Chemistry, Vol. 53, Issue 18
A new tetrakis β-diketone ligand for NIR emitting LnIII ions: luminescent doped PMMA films and flexible resins for advanced photonic applications
journal, January 2013
- Biju, Silvanose; Eom, Yu Kyung; Bünzli, Jean-Claude G.
- Journal of Materials Chemistry C, Vol. 1, Issue 42
Theoretical and Experimental Studies of the Photoluminescent Properties of the Coordination Polymer [Eu(DPA)(HDPA)(H 2 O) 2 ]·4H 2 O
journal, April 2008
- Rodrigues, Marcelo O.; da Costa Júnior, Nivan B.; de Simone, Carlos A.
- The Journal of Physical Chemistry B, Vol. 112, Issue 14
Benzothiazole- and Benzoxazole-Substituted Pyridine-2-Carboxylates as Efficient Sensitizers of Europium Luminescence
journal, July 2009
- Shavaleev, Nail M.; Scopelliti, Rosario; Gumy, Frédéric
- Inorganic Chemistry, Vol. 48, Issue 13
Effect of Lanthanide Contraction on Crystal Structures of Three-Dimensional Lanthanide Based Metal–Organic Frameworks with Thiophene-2,5-Dicarboxylate and Oxalate
journal, June 2011
- Xu, Jing; Cheng, Jianwen; Su, Weiping
- Crystal Growth & Design, Vol. 11, Issue 6
Sensitization of Visible and NIR Emitting Lanthanide(III) Ions in Noncentrosymmetric Complexes of Hexafluoroacetylacetone and Unsubstituted Monodentate Pyrazole
journal, October 2013
- Ahmed, Zubair; Iftikhar, K.
- The Journal of Physical Chemistry A, Vol. 117, Issue 44
Slow Magnetic Relaxation in a Redox-Active Tetrathiafulvalene-Based Ferromagnetic Dysprosium Complex: Slow Magnetic Relaxation in a Ferromagnetic Dysprosium Complex
journal, May 2014
- Pointillart, Fabrice; Golhen, Stéphane; Cador, Olivier
- European Journal of Inorganic Chemistry, Vol. 2014, Issue 27
Direct measurement of dysprosium(III)˙˙˙dysprosium(III) interactions in a single-molecule magnet
journal, October 2014
- Moreno Pineda, Eufemio; Chilton, Nicholas F.; Marx, Raphael
- Nature Communications, Vol. 5, Issue 1
Works referencing / citing this record:
Synthesis, crystal structures, luminescence and thermal properties of lanthanide complexes containing 2,5-dichlorobenzoic acid and 2,2:6′,2″-terpyridine
journal, August 2017
- Zhao, Qing-Qing; Wu, Xiao-Hui; Ren, Ning
- Journal of Thermal Analysis and Calorimetry, Vol. 131, Issue 2
Monomeric thorium chalcogenolates with bipyridine and terpyridine ligands
journal, January 2018
- Ringgold, Marissa; Wu, Wen; Stuber, Matthew
- Dalton Transactions, Vol. 47, Issue 41
Metal–Ligand Ratio Controlled Assembly Of Two Heterometallic CuEr Cluster Complexes: Syntheses, Structures and Magnetism
journal, December 2019
- Zhao, Fang-Hua; Li, Zhong-Lin; Yu, Ya-Hua
- Journal of Cluster Science
Four novel lanthanide complexes with 4-ethylbenzoic acid and 5,5′-dimethy-2,2′-bipyridine: Structures, luminescent, thermal properties and bacteriostatic activities
journal, May 2017
- Shen, Pan-Pan; Zhu, Min-Min; Ren, Ning
- Applied Organometallic Chemistry, Vol. 31, Issue 12
Syntheses, Structures, Photoluminescence, and Magnetism of a Series of Discrete Lanthanide Complexes based on 2,5-Dichlorobenzoate and 1,10-Phenanthroline: Syntheses, Structures, Photoluminescence, and Magnetism of a Series of Discrete Lanthanide Complexes based on 2,5-Dichlorobenzoate and 1,10-Phenanthro
journal, March 2019
- Zhang, Ju-Wen; Man, Yi; Ren, Yu-Ning
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 645, Issue 6-7
Similarities of Coordination Polymer and Dimeric Complex of Europium(III) with Joint and Separate Terpyridine and Benzoate
journal, June 2020
- Sedykh, Alexander E.; Sotnik, Svetlana A.; Kurth, Dirk G.
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 646, Issue 20
A Thorium Metal‐Organic Framework with Outstanding Thermal and Chemical Stability
journal, April 2019
- Carter, Korey P.; Ridenour, J. August; Kalaj, Mark
- Chemistry – A European Journal, Vol. 25, Issue 29
A series of new lanthanide complexes with 2-bromo-5-methoxybenzoic acid and 5,5′-dimethyl-2,2′-bipyridine: Crystal structures, thermal behavior, luminescent and magnetic properties: Structures, thermal behavior, luminescent and magnetic properties
journal, August 2018
- Xiao-Hui, Wu; Ning, Ren; Jian-Jun, Zhang
- Applied Organometallic Chemistry, Vol. 32, Issue 11
Synthesis, structures, thermal behaviour, luminescence and magnetic properties of lanthanide complexes constructed from 2,6‐dimethylbenzoic acid and 5,5′‐dimethyl‐2,2′‐bipyridine
journal, December 2019
- Li, Ying‐Ying; Ren, Ning; He, Shu‐Mei
- Applied Organometallic Chemistry, Vol. 34, Issue 3
Dinuclear Ln III Complexes with 9-Anthracenecarboxylate Showing Field-Induced SMM and Visible/NIR Luminescence : Dinuclear Ln
journal, August 2018
- Casanovas, Berta; Speed, Saskia; Maury, Olivier
- European Journal of Inorganic Chemistry, Vol. 2018, Issue 34
Exploring the Promotion of Synthons of Choice: Halogen Bonding in Molecular Lanthanide Complexes Characterized via X-ray Diffraction, Luminescence Spectroscopy, and Magnetic Measurements: Exploring the Promotion of Synthons of Choice: Halogen Bonding in Molecular Lanthanide Complexes Characterized via X-ray Diffraction, Luminescence Spe
journal, October 2017
- Carter, Korey P.; Pope, Simon J. A.; Kalaj, Mark
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 643, Issue 23
Supramolecular assembly of lanthanide-2,3,5,6-tetrafluoroterephthalic acid coordination polymers via fluorine⋯fluorine interactions: a platform for luminescent detection of Fe 3+ and nitroaromatic compounds
journal, January 2020
- Smith, Jermaine A.; Singh-Wilmot, Marvadeen A.; Carter, Korey P.
- New Journal of Chemistry, Vol. 44, Issue 28