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Title: Controlling dimensionality via a dual ligand strategy in Ln-thiophene-2,5-dicarboxylic acid-terpyridine coordination polymers

Abstract

Eleven new lanthanide (Ln = Nd-Lu)-thiophene-2,5-dicarboxylic acid (25-TDC)-2,2':6',2''-terpyridine (terpy) coordination polymers (1–11) which employ a dual ligand strategy have been synthesized hydrothermally and structurally characterized by single crystal and powder X-ray diffraction. Two additional members of the series (12 and 13) were made with Ce3+ and Pr3+ and characterized via powder X-ray diffraction only. The series is comprised of three similar structures wherein differences due to the lanthanide contraction manifest in Ln3+ coordination number as well as the number of bound and solvent water molecules within the crystal lattice. Structure type I (Ce3+–Sm3+) contains two nine-coordinate Ln3+ metal centers each with a bound water molecule. Structure type II (Eu3+–Ho3+) features a nine and an eight coordinate Ln3+ metal along with one bound and one solvent water molecule. Structure type III (Er3+–Lu3+) includes two eight-coordinate Ln3+ metal centers with both water molecules residing in the lattice. Assembly into supramolecular 3D networks via π–π interactions is observed for all three structure types, whereas structure types II and III also feature hydrogen-bonding interactions via the well-known C–H•••O and O–H•••O synthons. Visible and near-IR luminescence studies were performed on compounds 1, 2, 10, and 13 at room temperature. As a result characteristic near-IR luminescentmore » bands of Pr3+, Nd3+, Sm3+, and Yb3+ as well as visible bands of Sm3+ were observed.« less

Authors:
; ; ; ; ;
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) (SC-22)
OSTI Identifier:
1370890
DOE Contract Number:  
SC0001089
Resource Type:
Journal Article
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 44; Journal Issue: 36; 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 1477-9226
Publisher:
Royal Society of Chemistry
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., Zulato, Cecília H. F., Rodrigues, Emille M., Pope, Simon J. A., Sigoli, Fernando A., and Cahill, Christopher L. Controlling dimensionality via a dual ligand strategy in Ln-thiophene-2,5-dicarboxylic acid-terpyridine coordination polymers. United States: N. p., 2015. Web. doi:10.1039/c5dt02596f.
Carter, Korey P., Zulato, Cecília H. F., Rodrigues, Emille M., Pope, Simon J. A., Sigoli, Fernando A., & Cahill, Christopher L. Controlling dimensionality via a dual ligand strategy in Ln-thiophene-2,5-dicarboxylic acid-terpyridine coordination polymers. United States. doi:10.1039/c5dt02596f.
Carter, Korey P., Zulato, Cecília H. F., Rodrigues, Emille M., Pope, Simon J. A., Sigoli, Fernando A., and Cahill, Christopher L. Thu . "Controlling dimensionality via a dual ligand strategy in Ln-thiophene-2,5-dicarboxylic acid-terpyridine coordination polymers". United States. doi:10.1039/c5dt02596f.
@article{osti_1370890,
title = {Controlling dimensionality via a dual ligand strategy in Ln-thiophene-2,5-dicarboxylic acid-terpyridine coordination polymers},
author = {Carter, Korey P. and Zulato, Cecília H. F. and Rodrigues, Emille M. and Pope, Simon J. A. and Sigoli, Fernando A. and Cahill, Christopher L.},
abstractNote = {Eleven new lanthanide (Ln = Nd-Lu)-thiophene-2,5-dicarboxylic acid (25-TDC)-2,2':6',2''-terpyridine (terpy) coordination polymers (1–11) which employ a dual ligand strategy have been synthesized hydrothermally and structurally characterized by single crystal and powder X-ray diffraction. Two additional members of the series (12 and 13) were made with Ce3+ and Pr3+ and characterized via powder X-ray diffraction only. The series is comprised of three similar structures wherein differences due to the lanthanide contraction manifest in Ln3+ coordination number as well as the number of bound and solvent water molecules within the crystal lattice. Structure type I (Ce3+–Sm3+) contains two nine-coordinate Ln3+ metal centers each with a bound water molecule. Structure type II (Eu3+–Ho3+) features a nine and an eight coordinate Ln3+ metal along with one bound and one solvent water molecule. Structure type III (Er3+–Lu3+) includes two eight-coordinate Ln3+ metal centers with both water molecules residing in the lattice. Assembly into supramolecular 3D networks via π–π interactions is observed for all three structure types, whereas structure types II and III also feature hydrogen-bonding interactions via the well-known C–H•••O and O–H•••O synthons. Visible and near-IR luminescence studies were performed on compounds 1, 2, 10, and 13 at room temperature. As a result characteristic near-IR luminescent bands of Pr3+, Nd3+, Sm3+, and Yb3+ as well as visible bands of Sm3+ were observed.},
doi = {10.1039/c5dt02596f},
journal = {Dalton Transactions},
issn = {1477-9226},
number = 36,
volume = 44,
place = {United States},
year = {2015},
month = {1}
}

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