Pyridinium Salts of Dehydrated Lanthanide Polychlorides

Cramer, Roger E.; Baca, Esteban M.; Boyle, Timothy J.

doi:10.3390/molecules28010283

Pyridinium Salts of Dehydrated Lanthanide Polychlorides

Journal Article · Wed Dec 28 23:00:00 EST 2022 · Molecules

DOI:https://doi.org/10.3390/molecules28010283· OSTI ID:2469916

^[1]; Baca, Esteban M. ^[2]; ^[2]

Univ. of Hawaii at Manoa, Honolulu, HI (United States)
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

The reaction of lanthanide (Ln) chloride hydrates ([Ln(H₂O)_n(Cl)₃]) with pyridine (py) yielded a set of dehydrated pyridinium (py-H) Ln-polychloride salts. These species were crystallographically characterized as [[py-H-py][py-H]₂[LnCl₆]] (Ln-6; Ln = La, Ce, Pr, Nd, Sm, Eu, Gd) or [[py-H]₂[LnCl₅(py)]] ((Ln-5; Ln = Tb, Dy, Ho, Er, Tm, Yb, Lu). The Ln-6 metal centers adopt an octahedral (OC-6) geometry, binding six Cl ligands. The -3 charge is off-set by two py-H moieties and a di-pyridinium (py-H-py) ion. For the Ln-5 species, an OC-6 anion is formed by the Ln cation binding a single py and five Cl ligands. The remaining -2 charge is offset by two py-H⁺ cations that H-bond to the anion. Significant H-bonding occurs between the various cation/anion moieties inducing the molecular stability. The change in structure from the Ln-6 to Ln-5 is believed to be due to the Ln-contraction producing a smaller unit cell, which prevents formation of the py-H-py⁺ cation, leading to the loss of the H-bonding-induced stability. Based on this, it was determined that the Ln-5 structures only exist when the lattice energy is small. While dehydrated polychloride salts can be produced by simply mixing in pyridine, the final structures adopted result from a delicate balance of cation size, Coulombic charge, and stabilizing H-bonding.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: NA0003525

OSTI ID:: 2469916

Journal Information:: Molecules, Journal Name: Molecules Journal Issue: 1 Vol. 28; ISSN 1420-3049

Publisher:: MDPICopyright Statement

Country of Publication:: United States

Language:: English

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CCDC 2214067: Experimental Crystal Structure Determination E., Cramer, R.; M., Baca, E.; J., Boyle, T. https://doi.org/10.5517/ccdc.csd.cc2d9xj5 The current record is supplemented by this dataset	dataset	January 2023
CCDC 2214068: Experimental Crystal Structure Determination E., Cramer, R.; M., Baca, E.; J., Boyle, T. https://doi.org/10.5517/ccdc.csd.cc2d9xk6 The current record is supplemented by this dataset	dataset	January 2023
CCDC 2214069: Experimental Crystal Structure Determination E., Cramer, R.; M., Baca, E.; J., Boyle, T. https://doi.org/10.5517/ccdc.csd.cc2d9xl7 The current record is supplemented by this dataset	dataset	January 2023
CCDC 2214070: Experimental Crystal Structure Determination E., Cramer, R.; M., Baca, E.; J., Boyle, T. https://doi.org/10.5517/ccdc.csd.cc2d9xm8 The current record is supplemented by this dataset	dataset	January 2023
CCDC 2214071: Experimental Crystal Structure Determination E., Cramer, R.; M., Baca, E.; J., Boyle, T. https://doi.org/10.5517/ccdc.csd.cc2d9xn9 The current record is supplemented by this dataset	dataset	January 2023
CCDC 2214073: Experimental Crystal Structure Determination E., Cramer, R.; M., Baca, E.; J., Boyle, T. https://doi.org/10.5517/ccdc.csd.cc2d9xqc The current record is supplemented by this dataset	dataset	January 2023
CCDC 2214074: Experimental Crystal Structure Determination E., Cramer, R.; M., Baca, E.; J., Boyle, T. https://doi.org/10.5517/ccdc.csd.cc2d9xrd The current record is supplemented by this dataset	dataset	January 2023
CCDC 2214078: Experimental Crystal Structure Determination E., Cramer, R.; M., Baca, E.; J., Boyle, T. https://doi.org/10.5517/ccdc.csd.cc2d9xwj The current record is supplemented by this dataset	dataset	January 2023
CCDC 2214079: Experimental Crystal Structure Determination E., Cramer, R.; M., Baca, E.; J., Boyle, T. https://doi.org/10.5517/ccdc.csd.cc2d9xxk The current record is supplemented by this dataset	dataset	January 2023
CCDC 2214080: Experimental Crystal Structure Determination E., Cramer, R.; M., Baca, E.; J., Boyle, T. https://doi.org/10.5517/ccdc.csd.cc2d9xyl The current record is supplemented by this dataset	dataset	January 2023

Pyridinium Salts of Dehydrated Lanthanide Polychlorides

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