Zeitschrift für Anorganische und Allgemeine Chemie
Zeitschrift für Anorganische und Allgemeine Chemie
3 years ago

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 Spectroscopy, and Magnetic Measurements
Korey P. Carter, Mark Kalaj, Simon J. A. Pope, Muralee Murugesu, Rebecca J. Holmberg, Christopher L. Cahill
Promotion of a synthon of choice for the non-covalent assembly of lanthanide tectons represents both a noteworthy challenge and opportunity within LnIII 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 = Sm3+ – Lu3+) 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 (Sm3+), 2 (Eu3+), 4 (Tb3+), 5 (Dy3+), 6 (Ho3+), 7 (Er3+), and 9 (Yb3+) and characteristic emission was observed for all complexes except 6. Further, direct current magnetic susceptibility measurements were carried out for complexes 5 (Dy3+) and 7 (Er3+), and two slow magnetic relaxation processes were characterized using alternating current magnetic susceptibility measurements for 5.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/zaac.201700341

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