Unexpected structural complexity of thorium coordination polymers and polyoxo cluster built from simple formate ligands

Zi Jian Li; Shangyao Guo; Huangjie Lu; Yongjia Xu; Zenghui Yue; Linhong Weng; Xiaofeng Guo; Jian Lin; Jian Qiang Wang

doi:10.1039/c9qi01263j

Unexpected structural complexity of thorium coordination polymers and polyoxo cluster built from simple formate ligands

Zi Jian Li
, Shangyao Guo
, Huangjie Lu
, Yongjia Xu
, Zenghui Yue
, Linhong Weng
, Xiaofeng Guo
, Jian Lin
, Jian Qiang Wang

Chinese Academy of Sciences
Fudan University
Washington State University Pullman

Research output: Contribution to journal › Article › peer-review

32 Scopus citations

Abstract

A simple binary synthetic approach with variable [HCOOH]/[Th(iv)] ratios and the addition of water resulted in the self-Assembly of six novel thorium formate complexes with well-controlled structures ranging from 0D clusters and 2D layered networks to 3D frameworks. Specifically, small [HCOOH]/[Th(iv)] promoted the formation of the hexanuclear Th₆O₄(OH)₄(HCOO)₁₂ core, a secondary building unit for the construction of 3D [Th₆Na(μ₃-O)₄(μ₃-OH)₄(HCOO)₁₄]·[NH₂(CH₃)₂]·(DMF)₃(H₂O)₅ (Th-SINAP-1), 2D [Th₆(μ₃-O)₄(μ₃-OH)₄(HCOO)₁₂(DMF)₂]·(H₂O)₁₀ (Th-SINAP-2), and 0D [Th₆(μ₃-O)₄(μ₃-OH)₄(HCOO)₁₂(H₂O)₆]·G (Th-SINAP-3). The large [HCOOH]/[Th(iv)] inhibited the olation/oxolation reaction, affording 3D frameworks of [Th₂(HCOO)₉]·[NH₂(CH₃)₂]·(DMF)(H₂O)₂ (Th-SINAP-4), [Th₂(HCOO)₉]·[NH₂(CH₃)₂]·(DMF)(H₂O)₄ (Th-SINAP-5), and [Th₂(HCOO)₈(H₂O)(DMF)]·(H₂O)₃ (Th-SINAP-6) with monomeric Th(iv) cations as the metal nodes. The addition of water not only affected the hydrolysis of Th(iv) to form nucleophilic hydroxo/oxo-Aquo Th species, but also influenced the overall solid-state packing via the competition between H₂O, HCOO^-, OH^-/O^2-, and DMF for coordination with Th⁴⁺ cations. This unexpected structural complexity of thorium formates opens a new avenue for the targeted design and synthesis of atypical coordination polymers, e.g. open-framework materials of actinides, for applications in diverse fields such as radionuclide adsorption.

Original language	English
Pages (from-to)	260-269
Number of pages	10
Journal	Inorganic Chemistry Frontiers
Volume	7
Issue number	1
DOIs	https://doi.org/10.1039/c9qi01263j
State	Published - 7 Jan 2019
Externally published	Yes

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@article{f36de6ead6c94a62a320f7a9f760666b,

title = "Unexpected structural complexity of thorium coordination polymers and polyoxo cluster built from simple formate ligands",

abstract = "A simple binary synthetic approach with variable [HCOOH]/[Th(iv)] ratios and the addition of water resulted in the self-Assembly of six novel thorium formate complexes with well-controlled structures ranging from 0D clusters and 2D layered networks to 3D frameworks. Specifically, small [HCOOH]/[Th(iv)] promoted the formation of the hexanuclear Th6O4(OH)4(HCOO)12 core, a secondary building unit for the construction of 3D [Th6Na(μ3-O)4(μ3-OH)4(HCOO)14]·[NH2(CH3)2]·(DMF)3(H2O)5 (Th-SINAP-1), 2D [Th6(μ3-O)4(μ3-OH)4(HCOO)12(DMF)2]·(H2O)10 (Th-SINAP-2), and 0D [Th6(μ3-O)4(μ3-OH)4(HCOO)12(H2O)6]·G (Th-SINAP-3). The large [HCOOH]/[Th(iv)] inhibited the olation/oxolation reaction, affording 3D frameworks of [Th2(HCOO)9]·[NH2(CH3)2]·(DMF)(H2O)2 (Th-SINAP-4), [Th2(HCOO)9]·[NH2(CH3)2]·(DMF)(H2O)4 (Th-SINAP-5), and [Th2(HCOO)8(H2O)(DMF)]·(H2O)3 (Th-SINAP-6) with monomeric Th(iv) cations as the metal nodes. The addition of water not only affected the hydrolysis of Th(iv) to form nucleophilic hydroxo/oxo-Aquo Th species, but also influenced the overall solid-state packing via the competition between H2O, HCOO-, OH-/O2-, and DMF for coordination with Th4+ cations. This unexpected structural complexity of thorium formates opens a new avenue for the targeted design and synthesis of atypical coordination polymers, e.g. open-framework materials of actinides, for applications in diverse fields such as radionuclide adsorption.",

author = "Li, \{Zi Jian\} and Shangyao Guo and Huangjie Lu and Yongjia Xu and Zenghui Yue and Linhong Weng and Xiaofeng Guo and Jian Lin and Wang, \{Jian Qiang\}",

note = "Publisher Copyright: This journal is {\textcopyright} the Partner Organisations.",

year = "2019",

month = jan,

day = "7",

doi = "10.1039/c9qi01263j",

language = "英语",

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journal = "Inorganic Chemistry Frontiers",

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T1 - Unexpected structural complexity of thorium coordination polymers and polyoxo cluster built from simple formate ligands

AU - Li, Zi Jian

AU - Guo, Shangyao

AU - Lu, Huangjie

AU - Xu, Yongjia

AU - Yue, Zenghui

AU - Weng, Linhong

AU - Guo, Xiaofeng

AU - Lin, Jian

AU - Wang, Jian Qiang

PY - 2019/1/7

Y1 - 2019/1/7

N2 - A simple binary synthetic approach with variable [HCOOH]/[Th(iv)] ratios and the addition of water resulted in the self-Assembly of six novel thorium formate complexes with well-controlled structures ranging from 0D clusters and 2D layered networks to 3D frameworks. Specifically, small [HCOOH]/[Th(iv)] promoted the formation of the hexanuclear Th6O4(OH)4(HCOO)12 core, a secondary building unit for the construction of 3D [Th6Na(μ3-O)4(μ3-OH)4(HCOO)14]·[NH2(CH3)2]·(DMF)3(H2O)5 (Th-SINAP-1), 2D [Th6(μ3-O)4(μ3-OH)4(HCOO)12(DMF)2]·(H2O)10 (Th-SINAP-2), and 0D [Th6(μ3-O)4(μ3-OH)4(HCOO)12(H2O)6]·G (Th-SINAP-3). The large [HCOOH]/[Th(iv)] inhibited the olation/oxolation reaction, affording 3D frameworks of [Th2(HCOO)9]·[NH2(CH3)2]·(DMF)(H2O)2 (Th-SINAP-4), [Th2(HCOO)9]·[NH2(CH3)2]·(DMF)(H2O)4 (Th-SINAP-5), and [Th2(HCOO)8(H2O)(DMF)]·(H2O)3 (Th-SINAP-6) with monomeric Th(iv) cations as the metal nodes. The addition of water not only affected the hydrolysis of Th(iv) to form nucleophilic hydroxo/oxo-Aquo Th species, but also influenced the overall solid-state packing via the competition between H2O, HCOO-, OH-/O2-, and DMF for coordination with Th4+ cations. This unexpected structural complexity of thorium formates opens a new avenue for the targeted design and synthesis of atypical coordination polymers, e.g. open-framework materials of actinides, for applications in diverse fields such as radionuclide adsorption.

AB - A simple binary synthetic approach with variable [HCOOH]/[Th(iv)] ratios and the addition of water resulted in the self-Assembly of six novel thorium formate complexes with well-controlled structures ranging from 0D clusters and 2D layered networks to 3D frameworks. Specifically, small [HCOOH]/[Th(iv)] promoted the formation of the hexanuclear Th6O4(OH)4(HCOO)12 core, a secondary building unit for the construction of 3D [Th6Na(μ3-O)4(μ3-OH)4(HCOO)14]·[NH2(CH3)2]·(DMF)3(H2O)5 (Th-SINAP-1), 2D [Th6(μ3-O)4(μ3-OH)4(HCOO)12(DMF)2]·(H2O)10 (Th-SINAP-2), and 0D [Th6(μ3-O)4(μ3-OH)4(HCOO)12(H2O)6]·G (Th-SINAP-3). The large [HCOOH]/[Th(iv)] inhibited the olation/oxolation reaction, affording 3D frameworks of [Th2(HCOO)9]·[NH2(CH3)2]·(DMF)(H2O)2 (Th-SINAP-4), [Th2(HCOO)9]·[NH2(CH3)2]·(DMF)(H2O)4 (Th-SINAP-5), and [Th2(HCOO)8(H2O)(DMF)]·(H2O)3 (Th-SINAP-6) with monomeric Th(iv) cations as the metal nodes. The addition of water not only affected the hydrolysis of Th(iv) to form nucleophilic hydroxo/oxo-Aquo Th species, but also influenced the overall solid-state packing via the competition between H2O, HCOO-, OH-/O2-, and DMF for coordination with Th4+ cations. This unexpected structural complexity of thorium formates opens a new avenue for the targeted design and synthesis of atypical coordination polymers, e.g. open-framework materials of actinides, for applications in diverse fields such as radionuclide adsorption.

UR - https://www.scopus.com/pages/publications/85077024659

U2 - 10.1039/c9qi01263j

DO - 10.1039/c9qi01263j

M3 - 文章

AN - SCOPUS:85077024659

SN - 2052-1553

VL - 7

SP - 260

EP - 269

JO - Inorganic Chemistry Frontiers

JF - Inorganic Chemistry Frontiers

IS - 1

ER -

Unexpected structural complexity of thorium coordination polymers and polyoxo cluster built from simple formate ligands

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