Rare metal-ion metathesis of a tetrahedral Zn(<scp>ii</scp>) core of a noncentrosymmetric (3,4)-connected 3D MOF

Lee, Li Wei; Kao, Ya Chuan; Chung, Mei Ying; Chang, Ben; Lee, Gene Hsiang; Peng, Shie Ming; Wang, Chih Min; Liu, Yen Hsiang; Lee, Sheng Long; Lu, Kuang Lieh

doi:10.1039/c8dt04472d

Cited by 7 publications

(2 citation statements)

References 74 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…With this in mind, we turned our attention to the ligand ( L , Figure ), whose capabilities for spin crossover properties − and anion−π interactions have been well known. Besides, this bent ligand has been exploited for the construction and design of novel metal–organic frameworks (MOF S ) − and documented independently by the group Du et al as cocrystals with a series of organic carboxylic acids.…”

Section: Introductionmentioning

confidence: 99%

Inorganic Anion-Mediated Supramolecular Entities of 4-Amino-3,5-Bis(4-Pyridyl)-1,2,4-Triazole Salts Assisted by the Interplay of Noncovalent Interactions

Mahajan

Marttinen

Forsblom

et al. 2023

Crystal Growth & Design

View full text Add to dashboard Cite

The development of new families of synthetic molecular systems projecting neutral, bi-, or multi-H-bonding donor units is significant to acquire the desired selectivity within the fascinating area of anion recognition. Here, we illustrate the reaction between a neutral 4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole ligand (L) with acidic solutions containing either chloride, bromide, nitrate, phosphate, iodide, sulfate, hexafluorosilicate, fluoride, tetrafluoroborate or perchlorate anions, yielding 16 new anion-mediated supramolecular entities, H2LCl2 (1), H2LBr2 (2), H2L(NO3)2 (3), HL(H2PO4) (4), H2L(H2PO4)2 (5), [H2L]2I4 (6), H2L(NO3)2 (7), H2L(SO4)·H2O (8), H2LSiF6 (9), H2LSiF6·2H2O (10), H2L(HF2)2 (11), H3LI3 (12), H3L(BF4)3 (13), H3L(ClO4)3 (14), H3L(ClO4)3·2H2O (15), and H3LH3O(SiF6)2·2H2O (16), thoroughly examined by elemental analyses, Fourier transform-attenuated total reflectance-infrared (FT-ATR-IR), thermal analysis, powder diffraction, and single-crystal X-ray diffraction. We identified the propensity of H2PO4 – into a cyclic hexameric cluster (H2PO4 –)6 stabilized by a bent ligand L via a combination of functionalities such as an amino group, pyridyl terminals, and a triazolyl core. Additionally, we also found the anion–water clusters ranging from a cyclic tetramer [(SO4)2–(H2O)2]4– and an octameric cluster [(SiF6)4–(H2O)4]∞ 8– to an acyclic tetramer [(ClO4 –)2(H2O)2]. As shown by the study, subtle modulation in the crystallization environment offers the possibility to yield entirely distinctive forms of molecular salts comprising both anhydrous and a few hydrates with different protonated numbers (mono-, di- or triprotonated). A systematic study indicates that the molecular salts obtained from different anions construct diverse supramolecular extended architectures (e.g., bricklayer, columns, zig-zag, stair-steps, wave-like, helical, double chain, and criss-cross orientation) self-assembled by a combination of noncovalent interactions, constituting distinct H-bonded geometry patterns, essentially depending on the molecular conformation of the bent ligand and the type of the anion utilized (linear, spherical, triangular, tetrahedral, and octahedral) in the preparation of salts.

show abstract

Section: Introductionmentioning

confidence: 99%

Inorganic Anion-Mediated Supramolecular Entities of 4-Amino-3,5-Bis(4-Pyridyl)-1,2,4-Triazole Salts Assisted by the Interplay of Noncovalent Interactions

Mahajan

Marttinen

Forsblom

et al. 2023

Crystal Growth & Design

View full text Add to dashboard Cite

show abstract

“…Investigation resulted in 16 distinct crystal structures, demonstrating the ligand’s ability to exhibit a versatile spectrum of molecular conformations ranging from planar to nearly perpendicularly tilted pyridyl end groups. To date, the bpt ligand has already been utilized in the MOF syntheses; − however, pairing it with the tdc ligand has not yet been reported. Second, considering aspects of a secondary building unit (SBU) with metal centers supported by carboxylates, tdc ligand may provide alternative binding modes, potentially endowing frameworks with unique coordination environments.…”

Section: Introductionmentioning

confidence: 99%

3D Zinc–Organic Frameworks Based on Mixed Thiophene Dicarboxylate and 4-Amino-3,5-bis(4-pyridyl)-1,2,4-triazole Linkers: Syntheses, Structural Diversity, and Single-Crystal-to-Single-Crystal Transformations

Mahajan,

Lahtinen

2023

Crystal Growth & Design

View full text Add to dashboard Cite

In this study, for the first time two new interpenetrated 3D pillared-layer metal−organic frameworks (MOFs), namely, {[Zn(bpt)(tdc)]•dmf} n (MOF-1-Zn) and {[Zn 2 (bpt)-(tdc) 2 ]•2(dmf)} n (MOF-2-Zn), as well as a homochiral 3D framework {[Zn(bpt)(tdc)(H 2 O)]•dmf} n (MOF-3-Zn), were prepared under different synthesis conditions (bpt = 4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole, H 2 tdc = 2,5-thiophenedicarboxylic acid, and dmf = N,N′-dimethylformamide). Synthesis products were thoroughly characterized by single-crystal and powder X-ray diffraction and thermoanalytical methods. Remarkably, in the case of MOF-2-Zn, dmf molecules in the voids can be exchanged for different solvents, e.g., chloroform, methanol, ethanol, isopropyl alcohol, acetonitrile, acetone, tetrahydrofuran, 1,4-dioxane, and cyclohexane in a single-crystal-to-single-crystal (SCSC) manner. With different solvent types, the bpt ligands adapted slightly different conformations by adjusting the orientation of the NH 2 -triazole core unit and the tilting of the pyridyl groups. In comparison, most changes for planar tdc ligands were observed on the dihedral angles of the adjacent thiophene rings (e.g., 69.5 vs 78.5°for MOF-2-Zn and 2-CHCl 3 , respectively). Desolvation of the MOF illustrated systematic structural adaptability of {Zn 2 }-"paddlewheel" in SCSC fashion, and the MOF's crystallinity and 3D networked structure were preserved even after vacuum and heat-assisted desolvation. Finally, preliminary CO 2 adsorption tests for MOFs were conducted utilizing a custom-built fixed-bed adsorption/desorption device, resulting in about 0.1 mmol COd 2 /g sorbent at 400−4000 ppmv CO 2 and about 1 mmol COd 2 /g sorbent at 15 vol % CO 2 .

show abstract

Self-powered ethanol gas sensor based on the piezoelectric Ag/ZnO nanowire arrays at room temperature

Zhang

Wang

Zhang

et al. 2021

J Mater Sci: Mater Electron

View full text Add to dashboard Cite

Rare metal-ion metathesis of a tetrahedral Zn(ii) core of a noncentrosymmetric (3,4)-connected 3D MOF

Abstract: An SHG-active framework of 1-Zn can undergo metal metathesis, in which the tetrahedrally coordinated Zn(ii) ions are completely exchanged with Cu(ii) ions while retaining the integrity of the network.

Cited by 7 publications

References 74 publications

Inorganic Anion-Mediated Supramolecular Entities of 4-Amino-3,5-Bis(4-Pyridyl)-1,2,4-Triazole Salts Assisted by the Interplay of Noncovalent Interactions

Inorganic Anion-Mediated Supramolecular Entities of 4-Amino-3,5-Bis(4-Pyridyl)-1,2,4-Triazole Salts Assisted by the Interplay of Noncovalent Interactions

3D Zinc–Organic Frameworks Based on Mixed Thiophene Dicarboxylate and 4-Amino-3,5-bis(4-pyridyl)-1,2,4-triazole Linkers: Syntheses, Structural Diversity, and Single-Crystal-to-Single-Crystal Transformations

Self-powered ethanol gas sensor based on the piezoelectric Ag/ZnO nanowire arrays at room temperature

Contact Info

Product

Resources

About