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Title: Transuranic Hybrid Materials: Crystallographic and Computational Metrics of Supramolecular Assembly

Abstract

A family of twelve supramolecular [AnO2Cl4]2- (An = U, Np, Pu) containing compounds assembled via hydrogen and halogen bonds donated by substituted 4-X-pyridinium cations (X = H, Cl, Br, I) is reported. These materials were prepared from a room-temperature synthesis wherein crystallization of unhydrolyzed and valence pure [An(VI)O2Cl4]2- (An = U, Np, Pu) tectons are the norm. We present a hierarchy of assembly criteria based on crystallographic observations, and subsequently quantify the strengths of the non-covalent interactions using Kohn-Sham density functional calculations. We provide, for the first time, a detailed description of the electrostatic potentials (ESPs) of the actinyl tetrahalide dianions and reconcile crystallographically observed structural motifs and non-covalent interaction (NCI) acceptor-donor pairings. Our findings indicate that the average electrostatic potential across the halogen ligands (the acceptors) changes by only ~2 kJ mol-1 across the AnO22+ series, indicating the magnitude of the potential is independent of the metal center. The role of the cation is therefore critical in directing structural motifs and dictating the resulting hydrogen and halogen bond strengths, the former being stronger due to the positive charge centralized on the pyridyl nitrogen N-H+. Subsequent analyses using the Quantum theory of atoms in molecules (QTAIM) and natural bond orbitalmore » (NBO) approaches support this conclusion and highlight the structure directing role of the cations. Whereas one can infer that the 2 Columbic attraction is the driver for assembly, the contribution of the non-covalent interaction is to direct the molecular-level arrangement (or disposition) of the tectons.« less

Authors:
 [1]; ORCiD logo [2];  [3];  [3]; ORCiD logo [4];  [3]; ORCiD logo [1]
  1. Department of Chemistry, The George Washington University, 800 22nd Street NW, Washington, D.C. 20052, United States
  2. Department of Fundamental Chemistry, Institute of Chemistry, University of São Paulo, Av. Prof. Lineu Prestes 748, São Paulo 05508-000, Brazil
  3. Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States
  4. Department of Chemistry, University at Buffalo, State University of New York, 312 Natural Sciences Complex, Buffalo, New York 14260, United States
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1378034
Report Number(s):
PNNL-SA-127519
Journal ID: ISSN 0002-7863; 45304036L
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society; Journal Volume: 139; Journal Issue: 31
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Surbella, Robert G., Ducati, Lucas C., Pellegrini, Kristi L., McNamara, Bruce K., Autschbach, Jochen, Schwantes, Jon M., and Cahill, Christopher L. Transuranic Hybrid Materials: Crystallographic and Computational Metrics of Supramolecular Assembly. United States: N. p., 2017. Web. doi:10.1021/jacs.7b05689.
Surbella, Robert G., Ducati, Lucas C., Pellegrini, Kristi L., McNamara, Bruce K., Autschbach, Jochen, Schwantes, Jon M., & Cahill, Christopher L. Transuranic Hybrid Materials: Crystallographic and Computational Metrics of Supramolecular Assembly. United States. doi:10.1021/jacs.7b05689.
Surbella, Robert G., Ducati, Lucas C., Pellegrini, Kristi L., McNamara, Bruce K., Autschbach, Jochen, Schwantes, Jon M., and Cahill, Christopher L. Wed . "Transuranic Hybrid Materials: Crystallographic and Computational Metrics of Supramolecular Assembly". United States. doi:10.1021/jacs.7b05689.
@article{osti_1378034,
title = {Transuranic Hybrid Materials: Crystallographic and Computational Metrics of Supramolecular Assembly},
author = {Surbella, Robert G. and Ducati, Lucas C. and Pellegrini, Kristi L. and McNamara, Bruce K. and Autschbach, Jochen and Schwantes, Jon M. and Cahill, Christopher L.},
abstractNote = {A family of twelve supramolecular [AnO2Cl4]2- (An = U, Np, Pu) containing compounds assembled via hydrogen and halogen bonds donated by substituted 4-X-pyridinium cations (X = H, Cl, Br, I) is reported. These materials were prepared from a room-temperature synthesis wherein crystallization of unhydrolyzed and valence pure [An(VI)O2Cl4]2- (An = U, Np, Pu) tectons are the norm. We present a hierarchy of assembly criteria based on crystallographic observations, and subsequently quantify the strengths of the non-covalent interactions using Kohn-Sham density functional calculations. We provide, for the first time, a detailed description of the electrostatic potentials (ESPs) of the actinyl tetrahalide dianions and reconcile crystallographically observed structural motifs and non-covalent interaction (NCI) acceptor-donor pairings. Our findings indicate that the average electrostatic potential across the halogen ligands (the acceptors) changes by only ~2 kJ mol-1 across the AnO22+ series, indicating the magnitude of the potential is independent of the metal center. The role of the cation is therefore critical in directing structural motifs and dictating the resulting hydrogen and halogen bond strengths, the former being stronger due to the positive charge centralized on the pyridyl nitrogen N-H+. Subsequent analyses using the Quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) approaches support this conclusion and highlight the structure directing role of the cations. Whereas one can infer that the 2 Columbic attraction is the driver for assembly, the contribution of the non-covalent interaction is to direct the molecular-level arrangement (or disposition) of the tectons.},
doi = {10.1021/jacs.7b05689},
journal = {Journal of the American Chemical Society},
number = 31,
volume = 139,
place = {United States},
year = {Wed Jul 26 00:00:00 EDT 2017},
month = {Wed Jul 26 00:00:00 EDT 2017}
}