A Water-Stable 3D Luminescent Metal−Organic Framework Based on Heterometallic [EuIII6ZnII] Clusters Showing Highly Sensitive, Selective, and Reversible Detection of Ronidazole

Zhang, Qingfu; Lei, Mingyuan; Yan, Hui; Wang, Jin-Yun; Shi, Yang

doi:10.1021/acs.inorgchem.7b01156

“…Such synthetic approaches are essential for optimizing materials function, including catalysis, 13 magnetism, [14][15][16][17][18] and luminescence. [19][20] Building-block synthetic approaches have been hypothesized in metal-oxo systems including; 1) assembly of Pd84 and Pd72 Pd-oxo toroids from a Pd6 fragment; [21][22][23] 2) Mn84 and Mn70 built from a Mn12 oxo-acetate; [24][25] 3) growth of giant molybdate POMs from smaller clusters; 26-27 4) assembly of successively larger Lnx species (x = 12-140) from a Ln4 oxocluster building unit; 18,[28][29][30][31] , 5) isolation of various sized LnxNiyoxoclusters (up to 164 metal polyhedra) from smaller oxocluster building blocks, 15,[32][33] and 6) capping and linking of POMs into rigid chains and frameworks, and flexible polymers. [34][35][36] The d-block and f-block tetravalent metal cations (M IV =Zr/Hf/Ce/U/Np/Pu IV ) are amongst the most studied metal-oxo cluster families.…”

Section: Introductionmentioning

confidence: 99%

Snapshots of Ce₇₀ Toroid Assembly from Solids and Solution

Colliard

¹

,

Brown

²

,

Fast

³

et al. 2021

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Crystallization at the solid-liquid interface is difficult to spectroscopically observe and therefore challenging to understand and ultimately control at the molecular level. The Ce70-torroid formulated [Ce IV 70(OH)36(O)64(SO4)60(H2O)10] 4-, part of a larger emerging family of M IV 70materials (M=Zr, U, Ce), presents such an opportunity. We have elucidated assembly mechanisms by X-ray scattering (small-angle scattering and total scattering) of solutions and solids, as well as crystallizing and identifying fragments of Ce70 by single-crystal X-ray diffraction. Fragments show evidence for templated growth (Ce5, [Ce5(O)3(SO4)12] 10-) and modular assembly from hexamer (Ce6) building units (Ce13, [Ce13(OH)6(O)12(SO4)14(Η2Ο)14] 6and Ce62, [Ce62(OH)30(O)58(SO4)58] 14-). Ce62, an almost complete ring, precipitates instantaneously in the presence of ammonium cations as two torqued arcs that interlock by hydrogen boding through NH4 + , which can also be replaced by other cations, demonstrated with Ce III . Room temperature rapid assembly of both Ce70 and Ce62, respectively, by addition of Li + and NH4 + , along with ionexchange and redox behavior, invite exploitation of this emerging material family in environmental and energy applications. Ce70, [Ce IV 70(OH)36(O)64(SO4)60] 4-, was described prior, and is also isostructural with Zr70 and U70. [49][50][51][52] Briefly, the Ce70 cluster can be viewed as ten Ce6-hexamers that alternate with ten Ce1-monomers. Four sulfates bridge each Ce6 and Ce1 along the outer rim, and four additional sulfates bridge only Ce6 units along the inner rim. Each fragment discussed later can be viewed in the same context. The Ce62, [Ce62(OH)30(O)58(SO4)58] 14-, consisting of ~90% of the ring, contains nine Ce6 and eight Ce1. Ce13, [Ce13(OH)6(O)12(SO4)14(Η2Ο)14] 6-, consists of two Ce6 and Ce1, and is approximately 20% of the ring. Ce5 [Ce5(O)3(SO4)12] 10-, resembles half of the Ce6 plus two flanking monomers. These clusters and their intrinsic relation to the Ce70, summarized in figure 1, serve as crystallographic snapshots of mechanistic pathways for ring formation.

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“…Third, UV–vis absorption spectra of compound 1 were observed to appear as a new absorption band at 290 nm after adding pyrimidine analytes (uracil, cytosine, and thymine), which indicates that they form a ground-state complex between compound 1 and pyrimidine analytes (Figure S12). 39,40 However, when the concentration of thymine increases, no new emission peaks appear, further indicating that the ground-state complex does not emit luminescence (Figure S13). Compound 1 and thymine formed a ground-state complex, reducing the concentration of compound 1 , resulting in a decrease in the fluorescence intensity of the system.…”

Section: Resultsmentioning

confidence: 99%

Two Highly Stable Luminescent Lead Phosphonates Based on Mixed Ligands: Highly Selective and Sensitive Sensing for Thymine Molecule and VO₃^– Anion

Cai

¹

,

Sun

²

,

Shao

³

et al. 2018

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Two luminescent lead phosphonates with two-dimensional (2D) layer and three-dimensional (3D) framework structure, namely, Pb 3 [(L 1 ) 2 (Hssc)(H 2 O) 2 ] ( 1 ) and [Pb 2 (L 2 ) 0.5 (bts)(H 2 O) 2 ]·H 2 O ( 2 ) (H 2 L 1 = O(CH 2 CH 2 ) 2 NCH 2 PO 3 H 2 , H 4 L 2 = H 2 PO 3 CH 2 NH(C 2 H 4 ) 2 NHCH 2 PO 3 H 2 , H 3 ssc = 5-sulfosalicylic acid, NaH 2 bts = 5-sulfoisophthalic acid sodium) have been prepared via hydrothermal techniques. The two compounds not only show excellent thermal stability but also remain intact in aqueous solution within an extensive pH range. Moreover, the atomic absorption spectroscopy analysis experiment indicates that there does not exist the leaching of Pb 2+ ions from the lead phosphonates, which show they are nontoxic in aqueous solution. In compound 1 , the Pb(1)O 4 , Pb(2)O 7 , Pb(3)O 4 , and CPO 3 polyhedra are interlinked into a one-dimensional chain, which is further connected to adjacent chain by sharing the Hssc 2– to form a 2D layer. Interestingly, compound 1 as a highly selective and sensitive luminescent material can be used to detect the thymine molecule with a very low detection limit of 8.26 × 10 –7 M. In compound 2 , the Pb(1)O 6 and Pb(2)O 5 polyhedra are interlinked into a dimer via edge sharing, which is further connected to adjacent dimer to form a tetramer via corner sharing, and such a tetramer is then interlinked into a 2D layer through bts 3– ligands; the adjacent 2D layers are finally constructed to a 3D structure by sharing the L 2 4– ligand. Compound 2 can be applied as an excellent luminescent sensor for sensing of VO 3 – anion. Furthermore, the probable fluorescent quenching mechanisms of the two compounds have also been studied.

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“…Such synthetic approaches are essential for optimizing materials function, including catalysis, 13 magnetism, [14][15][16][17][18] and luminescence. [19][20] Building-block synthetic approaches have been hypothesized in metal-oxo systems including; 1) assembly of Pd84 and Pd72 Pd-oxo toroids from a Pd6 fragment; [21][22][23] 2) Mn84 and Mn70 built from a Mn12 oxo-acetate; [24][25] 3) growth of giant molybdate POMs from smaller clusters; 26-27 4) assembly of successively larger Lnx species (x = 12-140) from a Ln4 oxocluster building unit; 18,[28][29][30][31] , 5) isolation of various sized LnxNiyoxoclusters (up to 164 metal polyhedra) from smaller oxocluster building blocks, 15,[32][33] and 6) capping and linking of POMs into rigid chains and frameworks, and flexible polymers. [34][35][36] The d-block and f-block tetravalent metal cations (M IV =Zr/Hf/Ce/U/Np/Pu IV ) are amongst the most studied metal-oxo cluster families.…”

Section: Introductionmentioning

confidence: 99%

Snapshots of Ce70 Toroid Assembly from Solids and Solution

Colliard¹,

Brown²,

Fast³

et al. 2021

Preprint

0

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Crystallization at the solid-liquid interface is difficult to spectroscopically observe and therefore challenging to understand and ultimately control at the molecular level. The Ce70-torroid formulated [CeIV70(OH)36(O)64(SO4)60(H2O)10] 4- , part of a larger emerging family of MIV70- materials (M=Zr, U, Ce), presents such an opportunity. We have elucidated assembly mechanisms by X-ray scattering (small-angle scattering and total scattering) of solutions and solids, as well as crystallizing and identifying fragments of Ce70 by single-crystal X-ray diffraction. Fragments show evidence for templated growth (Ce5, [Ce5(O)3(SO4)12] 10- ) and modular assembly from hexamer (Ce6) building units (Ce13, [Ce13(OH)6(O)12(SO4)14(Η2Ο)14] 6- and Ce62, [Ce62(OH)30(O)58(SO4)58] 14- ). Ce62, an almost complete ring, precipitates instantaneously in the presence of ammonium cations as two torqued arcs that interlock by hydrogen boding through NH4 +, which can also be replaced by other cations, demonstrated with CeIII. Room temperature rapid assembly of both Ce70 and Ce62, respectively, by addition of Li+ and NH4 +, along with ion?exchange and redox behavior, invite exploitation of this emerging material family in environmental and energy applications.

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A Water-Stable 3D Luminescent Metal−Organic Framework Based on Heterometallic [Eu^III₆Zn^II] Clusters Showing Highly Sensitive, Selective, and Reversible Detection of Ronidazole

Cited by 130 publications

References 41 publications

Snapshots of Ce₇₀ Toroid Assembly from Solids and Solution

Snapshots of Ce₇₀ Toroid Assembly from Solids and Solution

Two Highly Stable Luminescent Lead Phosphonates Based on Mixed Ligands: Highly Selective and Sensitive Sensing for Thymine Molecule and VO₃^– Anion

Snapshots of Ce70 Toroid Assembly from Solids and Solution

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A Water-Stable 3D Luminescent Metal−Organic Framework Based on Heterometallic [EuIII6ZnII] Clusters Showing Highly Sensitive, Selective, and Reversible Detection of Ronidazole

Cited by 130 publications

References 41 publications

Snapshots of Ce70 Toroid Assembly from Solids and Solution

Snapshots of Ce70 Toroid Assembly from Solids and Solution

Two Highly Stable Luminescent Lead Phosphonates Based on Mixed Ligands: Highly Selective and Sensitive Sensing for Thymine Molecule and VO3– Anion

Snapshots of Ce70 Toroid Assembly from Solids and Solution

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A Water-Stable 3D Luminescent Metal−Organic Framework Based on Heterometallic [Eu^III₆Zn^II] Clusters Showing Highly Sensitive, Selective, and Reversible Detection of Ronidazole

Snapshots of Ce₇₀ Toroid Assembly from Solids and Solution

Snapshots of Ce₇₀ Toroid Assembly from Solids and Solution

Two Highly Stable Luminescent Lead Phosphonates Based on Mixed Ligands: Highly Selective and Sensitive Sensing for Thymine Molecule and VO₃^– Anion