Title: Exploring the Promotion of Synthons of Choice: Halogen Bonding in Molecular Lanthanide Complexes Characterized via X-ray Diffraction, Luminescence Spectroscopy, and Magnetic Measurements

Abstract

Promotion of a synthon of choice for the non‐covalent assembly of lanthanide tectons represents both a noteworthy challenge and opportunity within Ln ^III hybrid materials. We have developed a system, wherein some control can be exercised over supramolecular assembly and, as part of continued efforts to improve this process we have generated a family of ten new lanthanide ( Ln = Sm ³⁺ – Lu ³⁺ ) 2,4,6‐trichlorobenzoic acid‐1,10‐phenanthroline molecular complexes. Delineation of criteria for promoting assembly via halogen based interactions was introduced previously and is refined herein based on the characterization of complexes 1 – 10 via single‐crystal X‐ray diffraction. Direct comparison of means of supramolecular assembly for 1 – 10 with isostructural Ln ‐ p ‐chlorobenzoic acid‐1,10‐phenanthroline analogues verifies that increasing the number of halogen atoms at the periphery of a tecton is one route that increases the frequency of halogen bonding interactions. Additionally, solid‐state visible and near‐IR photoluminescence and luminescent lifetime data were collected for complexes 1 (Sm ³⁺ ), 2 (Eu ³⁺ ), 4 (Tb ³⁺ ), 5 (Dy ³⁺ ), 6 (Ho ³⁺ ), 7 (Er ³⁺ ), and 9 (Yb ³⁺ ) and characteristic emission was observed for all complexes except 6 . Further,more » direct current magnetic susceptibility measurements were carried out for complexes 5 (Dy ³⁺ ) and 7 (Er ³⁺ ), and two slow magnetic relaxation processes were characterized using alternating current magnetic susceptibility measurements for 5 .« less

Authors:

Carter, Korey P. ^[1]; Pope, Simon J. A. ^[2]; Kalaj, Mark ^[1]; Holmberg, Rebecca J. ^[3]; Murugesu, Muralee ^[3]; Cahill, Christopher L. ^[1]

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+ Show Author Affiliations

1. George Washington Univ., Washington, DC (United States). Dept. of Chemistry
2. Cardiff Univ., Wales (United Kingdom). School of Chemistry
3. Univ. of Ottawa, Ottawa, ON (Canada). Dept. of Chemistry and Biomolecular Sciences

Publication Date:

Fri Sep 29 00:00:00 EDT 2017

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:

1470041

Alternate Identifier(s):

OSTI ID: 1399274

Grant/Contract Number:  

SC0001089

Resource Type:

Accepted Manuscript

Journal Name:

Zeitschrift fuer Anorganische und Allgemeine Chemie

Additional Journal Information:

Journal Volume: 643; Journal Issue: 23; 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 0044-2313

Publisher:

Wiley

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; nuclear (including radiation effects); materials and chemistry by design; synthesis (novel materials), synthesis (self-assembly)