Metal phosphonates incorporating metalloligands: assembly, structures and properties

Bao, Song‐Song; Qin, Ming-Feng; Zheng, Li‐Min

doi:10.1039/d0cc03850d

Cited by 41 publications

(36 citation statements)

References 119 publications

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“…Metal phosphonates have the potential to offer ultra‐stable structures owing to more charge‐assisted bonding. This has led to marked interest with no fewer than ten reviews in this subfield since 2018 [36,38–46] . The coordinative pliancy of the phosphonate functional group can enable multiple coordination scenarios with relatively small energy differences that can allow ligand packings to optimize and compromise porosity.…”

Section: Discussionmentioning

confidence: 99%

“…This has led to marked interest with no fewer than ten reviews in this subfield since 2018. [36,[38][39][40][41][42][43][44][45][46] The coordinative pliancy of the phosphonate functional group can enable multiple coordination scenarios with relatively small energy differences that can allow ligand packings to optimize and compromise porosity. Because of this, the geometry and packing of the carbon spacer within the linker plays a more impactful role in promoting porosity.…”

Section: Discussionmentioning

confidence: 99%

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Orthogonalization of Polyaryl Linkers as a Route to More Porous Phosphonate Metal‐Organic Frameworks

Glavinović

Perras

Gelfand

et al. 2022

Chemistry A European J

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The coordinative pliancy of the phosphonate functional group means that metal-phosphonate materials often self-assemble as well-packed structures with minimal porosity, as efficient inter-ligand packing is enabled. Here, we report a multistep synthesis of a novel aryl-phosphonate linker with an orthogonalized ligand core, 1,3,5-tris(4'-phosphonophenyl)-2,4,6-trimethylbenzene (H 6 L2) designed to form more open structures. A series of crystalline metal-phosphonate frameworks (CALF-35 to -39) have been assembled by coordinating to divalent metals (Ba, Sr, Ca, Mg, Zn). H 6 L2 is unable to pack efficiently and, as a consequence, yields several distinct microporous structures. The resulting structures are discussed in detail, with a focus on the solid-state packing of the sterically rigidified linker. Combined with larger cations (Sr, and Ba), H 6 L2 packs in a parallel-offset manner, yielding isomorphous and microporous metal-organic frameworks , and (Ba)). When coordinated to smaller metals (Ca, Mg, Zn), H 6 L2 forms four new structures. Two Ca MOFs of different stoichiometry, (CALF-36 and 37) and a Mg MOF CALF-38 show narrow pores and have high selectivities for CO 2 over N 2 and CH 4 . Finally, in CALF-39 (Zn), H 6 L2 linkers pack in a herringbone fashion, resulting in a material with 10.9 × 10.1 Å 2 square channels. The stability of all structures was tested, and the most porous structure, CALF-39 (Zn), was found to retain its structure and gas adsorption after immersion in water over pH 3-11.

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Orthogonalization of Polyaryl Linkers as a Route to More Porous Phosphonate Metal‐Organic Frameworks

Glavinović

Perras

Gelfand

et al. 2022

Chemistry A European J

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“…[ 19‐23 ] To extend this field, our group has been interested in employing a different strategy, incorporating a luminescent organometallic salt as ligands, to develop a new system with magneto‐optical bifunctions. [ 24‐25 ] The phosphorescent iridium(III) complexes are selected, due to their well‐known high luminescent efficiency and tunable excitation and emission wavelength over the whole visible region. [ 26‐27 ] By harnessing [Ir(ppy) 2 (bppH)] and [Ir(ppy) 2 (Hdcbpy)] (Hppy = 2‐phenylpyridine, H 2 bpp = 2‐pyridylphosphonic acid, H 2 dcbpy = 2,2’‐bipyridine‐4,4’‐ dicarboxylic acid) as metalloligands, we have isolated a series of Ir‐Ln (Ln = Dy, Er, Yb) complexes, which integrate SMM or field‐induced SMM behavior arising from the lanthanide ions with photoluminescence originating from either Ir moieties or sensitized lanthanide ions.…”

Section: Background and Originality Contentmentioning

confidence: 99%

Engineering Heteronuclear Arrays from Ir^III‐Metalloligand and Co^II Showing Coexistence of Slow Magnetization Relaxation and Photoluminescence

Fan

Bao

et al. 2022

Chin. J. Chem.

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Comprehensive Summary Three heteronuclear IrIII‐CoII arrays, [Co(H2O)6]2[Ir(ppyCOO)(ppyCOOH)(bpy)]2[Ir(ppyCOO)2(bpy)]2(NO3)2⋅10.5H2O (2), [Co(H2O)6]{Co(H2O)4[Ir(ppyCOO)2(bpy)]2}[Ir(ppyCOO)2(bpy)]2⋅15H2O (3) and {Co(H2O)2[Ir(ppyCOO)2(bpy)]2}⋅2CH3OH⋅3H2O (4), have been synthesized by combining paramagnetic CoII ion with luminescent IrIII‐metalloligand, [Ir(ppyCOOH)2(bpy)][Ir(ppyCOO)2(bpy)]⋅5H2O (1), where ppyCOOH = 3‐(pyridin‐2‐yl)benzoic acid and bpy = 2,2'‐bipyridyl. Owing to the variable charged states of compound 1 at different pH, compounds 2 and 3 are discrete ionic complexes containing hydrated Co2+ cations and deprotonated [Ir(ppyCOO)2(bpy)]– anions as well as coexisting neutral [Ir(ppyCOO)(ppyCOOH)(bpy)] (for 2) or Co(H2O)4[Ir(ppyCOO)2(bpy)]2 trinuclear molecule (for 3). Whereas compound 4 consists of self‐assembled two‐dimensional coordination polymer with Co‐metalloligand dative bonds. The hexa‐coordinated CoII cores in all complexes display octahedral geometries with varying degrees of distortion. In a bias dc field, the ac susceptibilities for 2—4 reveal slow magnetic relaxation. Moreover, the solid‐state phosphorescence is observed for compounds 2 and 3 due to weak supramolecular interaction between CoII ion and Ir‐moiety but is severely quenched for 4, where the Co center is strongly connected to the metalloligand. To the best of our knowledge, this is the first report of Ir‐Co systems showing both slow magnetization relaxation and photoluminescence.

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“…[4] Among these, porous organic-inorganic metal phosphonate hybrid materials have drawn a growing level of research interest due to their ability to integrate the advantages of both porous materials and periodic organic-inorganic skeleton structures. [9,10] The rational adjustment of organophosphonic bridging groups and metallic nodes provides an almost infinite potential for the intentional control of composition in the hybrid network and/or on the surface, resulting in tunable modes of functionalization of hybrid materials. [11] On the other hand, the incorporation of well-designed porosity would further endow metal phosphonates with improved performance in related energy storage and catalysis fields.…”

Section: Introductionmentioning

confidence: 99%

Nanoporous Metal Phosphonate Hybrid Materials as a Novel Platform for Emerging Applications: A Critical Review

Weng

Zhu

et al. 2021

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Nanoporous metal phosphonates are propelling the rapid development of emerging energy storage, catalysis, environmental intervention, and biology, the performances of which touch many fundamental aspects of portable electronics, convenient transportation, and sustainable energy conversion systems. Recent years have witnessed tremendous research breakthroughs in these fields in terms of the fascinating pore properties, the structural periodicity, and versatile skeletons of porous metal phosphonates. This review presents recent milestones of porous metal phosphonate research, from the diversified synthesis strategies for controllable pore structures, to several important applications including adsorption and separation, energy conversion and storage, heterogeneous catalysis, membrane engineering, and biomaterials. Highlights of porous structure design for metal phosphonates are described throughout the review and the current challenges and perspectives for future research in this field are discussed at the end. The aim is to provide some guidance for the rational preparation of porous metal phosphonate materials and promote further applications to meet the urgent demands in emerging applications.

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Metal phosphonates incorporating metalloligands: assembly, structures and properties

Abstract: Metal phosphonates are an important class of metal-organic hybrid materials that exhibit versatile structures, intriguing functions and high water and thermal stabilities. Despite a large number of metal phosphonates achieved...

Cited by 41 publications

References 119 publications

Orthogonalization of Polyaryl Linkers as a Route to More Porous Phosphonate Metal‐Organic Frameworks

Orthogonalization of Polyaryl Linkers as a Route to More Porous Phosphonate Metal‐Organic Frameworks

Engineering Heteronuclear Arrays from Ir^III‐Metalloligand and Co^II Showing Coexistence of Slow Magnetization Relaxation and Photoluminescence

Nanoporous Metal Phosphonate Hybrid Materials as a Novel Platform for Emerging Applications: A Critical Review

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Metal phosphonates incorporating metalloligands: assembly, structures and properties

Abstract: Metal phosphonates are an important class of metal-organic hybrid materials that exhibit versatile structures, intriguing functions and high water and thermal stabilities. Despite a large number of metal phosphonates achieved...

Cited by 41 publications

References 119 publications

Orthogonalization of Polyaryl Linkers as a Route to More Porous Phosphonate Metal‐Organic Frameworks

Orthogonalization of Polyaryl Linkers as a Route to More Porous Phosphonate Metal‐Organic Frameworks

Engineering Heteronuclear Arrays from IrIII‐Metalloligand and CoII Showing Coexistence of Slow Magnetization Relaxation and Photoluminescence

Nanoporous Metal Phosphonate Hybrid Materials as a Novel Platform for Emerging Applications: A Critical Review

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Engineering Heteronuclear Arrays from Ir^III‐Metalloligand and Co^II Showing Coexistence of Slow Magnetization Relaxation and Photoluminescence