Supramolecular Assembly of Molecular Rare-Earth-3,5-Dichlorobenzoic Acid-2,2':6',2″-Terpyridine Materials: Structural Systematics, Luminescence Properties, and Magnetic Behavior

Korey P Carter; Kara E Thomas; Simon J A Pope; Rebecca J Holmberg; Ray J Butcher; Muralee Murugesu; Christopher L Cahill

doi:10.1021/acs.inorgchem.6b00408

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Supramolecular Assembly of Molecular Rare-Earth-3,5-Dichlorobenzoic Acid-2,2':6',2″-Terpyridine Materials: Structural Systematics, Luminescence Properties, and Magnetic Behavior

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Supramolecular Assembly of Molecular Rare-Earth-3,5-Dichlorobenzoic Acid-2,2':6',2″-Terpyridine Materials: Structural Systematics, Luminescence Properties, and Magnetic Behavior

Korey P Carter, Kara E Thomas, Simon J A Pope, Rebecca J Holmberg, Ray J Butcher, Muralee Murugesu and Christopher L Cahill

Inorganic chemistry, Vol.55(14), pp.6902-6915

07/18/2016

DOI: 10.1021/acs.inorgchem.6b00408

PMID: 27347607

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https://www.osti.gov/biblio/1388551View

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Abstract

The syntheses and crystal structures of 16 new rare-earth (RE = La(3+)-Y(3+))-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 (La(3+) and Ce(3+)) to tetramers (Pr(3+)-Y(3+)) as one moves across the RE(3+) 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 (Sm(3+)), 7 (Eu(3+)), 9 (Tb(3+)), 10 (Dy(3+)), 11 (Ho(3+)), 12 (Er(3+)), and 14 (Yb(3+)), 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 (Dy(3+)) and 12 (Er(3+)) and showed dominant ferromagnetic behavior.

Details

Title: Subtitle: Supramolecular Assembly of Molecular Rare-Earth-3,5-Dichlorobenzoic Acid-2,2':6',2″-Terpyridine Materials: Structural Systematics, Luminescence Properties, and Magnetic Behavior
Creators: Korey P Carter - Department of Chemistry, The George Washington University , 800 22nd Street, Northwest, Washington, D.C. 20052, United States
Kara E Thomas - Department of Chemistry, The George Washington University , 800 22nd Street, Northwest, Washington, D.C. 20052, United States
Simon J A Pope - School of Chemistry, Cardiff University , Main Building, Cardiff, Cymru/Wales CF10 3AT, U.K
Rebecca J Holmberg - Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie Curie, Ottawa, ON, Canada K1N 6N5
Ray J Butcher - Department of Chemistry, Howard University , 525 College Street, Northwest, Washington, D.C. 20059, United States
Muralee Murugesu - Department of Chemistry and Biomolecular Sciences, University of Ottawa , 10 Marie Curie, Ottawa, ON, Canada K1N 6N5
Christopher L Cahill - Department of Chemistry, The George Washington University , 800 22nd Street, Northwest, Washington, D.C. 20052, United States
Resource Type: Journal article
Publication Details: Inorganic chemistry, Vol.55(14), pp.6902-6915
DOI: 10.1021/acs.inorgchem.6b00408
PMID: 27347607
NLM abbreviation: Inorg Chem
ISSN: 0020-1669
eISSN: 1520-510X
Grant note: DOI: 10.13039/100007108, name: George Washington University; DOI: 10.13039/100006151, name: Basic Energy Sciences, award: DE-SC0001089
Language: English
Date published: 07/18/2016
Academic Unit: Chemistry
Record Identifier: 9984216614202771

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