Acentric and chiral heterometallic inorganic–organic hybrid frameworks mediated by alkali or alkaline earth ions: synthesis and NLO properties

Tian, Chong‐Bin; Zhang, Huabin; Du, Shaowu

doi:10.1039/c3ce42419g

Cited by 30 publications

(14 citation statements)

References 90 publications

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“…For example, the intensity of SNNU-75 is about 3 times that of the KDP marker in the particle size of 0.06–0.04 mm. These SHG effects are comparable to those reported NLO MOFs built from chiral or acentric organic ligands, and SNNU-71 surpasses most of them. − In our opinion, the different size of metal cations and coordination numbers are two main factors for the origin of SHG effects of these MOFs. Importantly, SNNU-71 , -72 , -74 , and - 75 all are constructed from the same cheap and common H 3 BTC centric ligands.…”

supporting

confidence: 81%

The Power of Heterometalation through Lithium for Helix Chain-Based Noncentrosymmetric Metal–Organic Frameworks with Tunable Second-Harmonic Generation Effects

Wang

et al. 2017

Crystal Growth & Design

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We demonstrate herein a general strategy for developing acentric or chiral nonlinear optical MOFs from centrosymmetric ligands by shifting the asymmetrical roles to the metal centers through heterometalation. With 1,3,5-benzenetricarboxylic acid (H 3 BTC), a very common polyfunctional centric ligand, the Li + /Zn 2+ , Li + /Co 2+ , or Li + /Cd 2+ heterometallic combinations successfully led to five new noncentrosymmetric metal−organic frameworks, namely, {[Zn(HBTC)(), and {Li 2 [Zn 3 Li 5 (BTC) 4 (MTAZ)(H 2 O) 4 ]} n (MTAZ = 5-methyl tetrazole, SNNU-75). All these MOFs are acentric or chiral on the base of helical chain building blocks and four colorless members of them show remarkable and tunable SHG effects. Remarkably, more than 1000 metal-BTC frameworks are reported to date and most of them are centrosymmetric due to the C 3 -symmery of BTC ligands. Clearly, our heterometalation approach greatly increases the possibility for induction of spontaneous resolution, which provides a fresh opportunity for the development of noncentrosymmetric functional MOF materials.

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supporting

confidence: 81%

The Power of Heterometalation through Lithium for Helix Chain-Based Noncentrosymmetric Metal–Organic Frameworks with Tunable Second-Harmonic Generation Effects

Wang

et al. 2017

Crystal Growth & Design

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“…These drawbacks can often be trounced by developing hybrids with inorganic compounds. The resulting semi-organic nonlinear optical (NLO) materials possess the advantages of high optical nonlinearity and chemical flexibility of organic materials as well as the physical ruggedness of inorganic counterparts [9][10][11][12].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, growth, structure and nonlinear optical properties of a semiorganic 2-carboxy pyridinium dihydrogen phosphate single crystal

Nagapandiselvi

Baby

2015

Optical Materials

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“…In contrast, s-block metal ions feature flexible coordination geometries, but they are not common elements, which serve as building units in coordination chemistry due to the relative liability of coordinative bonds, and thus usually cannot be used to build stable homometallic open frameworks alone . Alternatively, they can serve as cations to compensate the framework charge or as building units together with transition metals to construct bimetallic MOFs . Owning to the small radius and generally tetrahedral geometry of Li(I) ions, the introduction of Li(I) into bimetallic systems is proven to be an effective way to induce new topological structures .…”

Section: Introductionmentioning

confidence: 99%

“…21 Alternatively, they can serve as cations to compensate the framework charge or as building units together with transition metals to construct bimetallic MOFs. 22 Owning to the small radius and generally tetrahedral geometry of Li(I) ions, the introduction of Li(I) into bimetallic systems is proven to be an effective way to induce new topological structures. 23 We speculate that it may have some effect on the formation of tetrahedral coordination metal centers.…”

Section: Introductionmentioning

confidence: 99%

Modulation of High-Spin Co(II) in Li/Co-MOFs as Efficient Fenton-like Catalysts

Ren

Yang

et al. 2021

Inorg. Chem.

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Developing high-performance catalysts toward the Fenton reaction is important for environmental protection and sustainable development, yet it is still challenging. The high-spin states of first-row transition metal atoms with tetrahedral coordination provide a flexible electronic environment to activate the catalyst and elevate its catalytic activity. As a type of material with adjustable structures, metal−organic frameworks (MOFs) are excellent candidate catalysts as they can accurately regulate the coordination configurations of metal ions. In this paper, we investigate and summarize the direct formation of bimetallic carboxylate Li/Co-MOFs with tetrahedral coordination metal centers in a mixed H 2 O/polar organic solvent system. The induction of Li(I) ions is manifested in the generation of hydroxides during the dissociation of the Co(II) solvation structure to trigger the tetrahedral coordination behavior of Co(II). These Li/Co-MOFs containing high-spin Co(II) centers can serve as highly efficient Fenton-like catalysts for organics. This study provides a promising strategy for rational design of MOF-based catalysts with high-spin metal centers for application in environment governance.

show abstract

Acentric and chiral heterometallic inorganic–organic hybrid frameworks mediated by alkali or alkaline earth ions: synthesis and NLO properties

Cited by 30 publications

References 90 publications

The Power of Heterometalation through Lithium for Helix Chain-Based Noncentrosymmetric Metal–Organic Frameworks with Tunable Second-Harmonic Generation Effects

The Power of Heterometalation through Lithium for Helix Chain-Based Noncentrosymmetric Metal–Organic Frameworks with Tunable Second-Harmonic Generation Effects

Synthesis, growth, structure and nonlinear optical properties of a semiorganic 2-carboxy pyridinium dihydrogen phosphate single crystal

Modulation of High-Spin Co(II) in Li/Co-MOFs as Efficient Fenton-like Catalysts

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