Synthesis, characterization, and density functional theory investigation of (CH 6 N 3 ) 2 [NpO 2 Cl 3 ] and Rb[NpO 2 Cl 2 (H 2 O)] chain structures

Harindu Rajapaksha; Grant C Benthin; Emma L Markun; Sara E Mason; Tori Z Forbes

doi:10.1039/d3dt03630h

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Synthesis, characterization, and density functional theory investigation of (CH 6 N 3 ) 2 [NpO 2 Cl 3 ] and Rb[NpO 2 Cl 2 (H 2 O)] chain structures

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Synthesis, characterization, and density functional theory investigation of (CH 6 N 3 ) 2 [NpO 2 Cl 3 ] and Rb[NpO 2 Cl 2 (H 2 O)] chain structures

Harindu Rajapaksha, Grant C Benthin, Emma L Markun, Sara E Mason and Tori Z Forbes

Dalton transactions : an international journal of inorganic chemistry, Vol.53(7), pp.3397-3406

2024

DOI: 10.1039/d3dt03630h

PMID: 38265201

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Abstract

The actinyl tetrachloro complex [An(V/VI)O2Cl4]2−/3− tends to form discrete molecular units in both solution and solid state materials, but related aquachloro complexes have been observed as both discrete coordination compounds and 1-D chain topologies. Subtle differences in the inner sphere coordination significantly influence the formation of structural topologies in the actinyl chloride system, but the exact reasoning for these variations has not been delineated. In the current study, we present the synthesis, structural characterization, and vibrational analysis of two 1-D neptunyl(V) chain compounds: (CH6N3)2[NpO2Cl3] (Np-Gua) and Rb[NpO2Cl2(H2O)] (Np-Rb). Bonding and non-covalent interactions (NCIs) in the systems were evaluated using periodic Density Functional Theory (DFT) to link these properties to related phases. We observed ∼6.5% and ∼3.9% weakening of Np[double bond, length as m-dash]O bonds in Np-Gua and Np-Rb compared to the reference Cs3[NpO2Cl4]. NCI analysis distinguished specific assembly modes, where Np-Gua was connected via hydrogen bonding (N–H⋯Cleq and N–H⋯Oyl) and Np-Rb contained both cation interactions (Rb+⋯Oyl and Rb+⋯Cleq) and hydrogen bonding (Oeq–H⋯Oyl) networks. Thermodynamically viable formation pathways for both compounds were explored using DFT methodology. The [NpO2Cl4](aq)3− and [NpO2Cl3(H2O)](aq)2− substructures were identified as precursors to Np-Gua and [NpO2Cl3(H2O)](aq)2− and [NpO2Cl2(H2O)2](aq)− were isolated as the primary building units of Np-Rb. Finally, we utilized DFT to analyze the vibrational modes for Np-Gua and Np-Rb, where we found evidence of the Np[double bond, length as m-dash]O bond weakening within the Np(V) chain structures compared to [NpO2Cl4]3−.

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Title: Subtitle: Synthesis, characterization, and density functional theory investigation of (CH 6 N 3 ) 2 [NpO 2 Cl 3 ] and Rb[NpO 2 Cl 2 (H 2 O)] chain structures
Creators: Harindu Rajapaksha - University of Iowa
Grant C Benthin - University of Iowa
Emma L Markun - University of Iowa
Sara E Mason - University of Iowa
Tori Z Forbes - University of Iowa
Resource Type: Journal article
Publication Details: Dalton transactions : an international journal of inorganic chemistry, Vol.53(7), pp.3397-3406
DOI: 10.1039/d3dt03630h
PMID: 38265201
NLM abbreviation: Dalton Trans
ISSN: 1477-9226
eISSN: 1477-9234
Publisher: Royal Society of Chemistry
Grant note: DOI: 10.13039/100006151, name: Basic Energy Sciences, award: DE-SC0021420
Language: English
Electronic publication date: 01/24/2024
Date published: 2024
Academic Unit: Civil and Environmental Engineering; Core Research Facilities; Chemistry
Record Identifier: 9984548853702771

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