Self-Recognition of 3D Porous Frameworks: Fourfold Diamondoid or Threefold Cuboidal Interpenetrating Nets Formed by Varying Pillar Motifs

Hsu, Liang-Ping; Wu, Jing‐Yun; Lu, Kuang‐Lieh

doi:10.1007/s10904-006-9055-6

Cited by 18 publications

(3 citation statements)

References 28 publications

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“…Many factors, including temperature, solvent system, time duration, and steric aspects of the ligands, have been utilized to regulate the degree of interpenetration (DOI). ,, Furthermore, it is not apparent how the DOI can be changed in the MOF crystals as there are no bonds between the interpenetrated structures. Nonetheless, structural transformations between different orders of interpenetration have been accomplished and in many cases in a single-crystal-to-single-crystal manner (SCSC). − …”

Section: Introductionmentioning

confidence: 99%

“…Among the various interesting properties exhibited by MOFs, photophysical properties such as fluorescence, multi-photon photoluminescence, and second and third harmonic generations have been studied extensively. − They have widespread applications in the emerging field of photonics for optical signal transmission, processing, and sensing. MOFs crystallized in the noncentrosymmetric space groups are excellent materials to display nonlinear optical (NLO) properties. − Although a number of solid-state structural transformations arising from the change in the DOI in MOFs have been reported, − only a few have been amenable to changes in their properties, especially sorption due to the change in the surface area and pore volume. Due to the practical difficulty, not all the MOFs could be designed to have noncentrosymmetric packing before and after the structural conversion .…”

Section: Introductionmentioning

confidence: 99%

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Impact of the Structural Modification of Diamondoid Cd(II) MOFs on the Nonlinear Optical Properties

Gupta

Zhu

Kottilil

et al. 2021

ACS Appl. Mater. Interfaces

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A change in the degree of interpenetration (DOI) in metal–organic frameworks (MOFs) prompted by heat, pressure, or exchange of solvents is a fascinating phenomenon that can potentially impact the functional properties of MOFs. Structural transformation involving two noncentrosymmetric MOFs with different DOIs provides a rare opportunity to manipulate their optical properties. Herein, we report an unusual single-crystal-to-single-crystal (SCSC) transformation of a noncentrosymmetric 7-fold interpenetrated diamondoid (dia) Cd(II) MOF into another noncentrosymmetric but 8-fold interpenetrated dia MOF upon the removal of guest solvents. A hydrogen-bond network formed between the lattice solvents and linker trans-2-(4-pyridyl)-4-vinylbenzoate (pvb) in a 7-fold interpenetrated noncentrosymmetric MOF results in a significant increase in the two-photon absorption cross-section (11 times) as compared to that in the desolvated 8-fold interpenetrated MOF. Also, an increase in the DOI in the noncentrosymmetric crystals strengthened the π···π interaction between the individual diamondoid networks and enhanced the second-order nonlinear optical (NLO) coefficient (deff) by 4.5 times. These results provide a way to manipulate the optical properties of MOFs using a combined strategy of the formation of hydrogen bonds and interpenetration for access to tunable single-crystal NLO devices in an SCSC manner. By changing the experimental conditions, another dia Cd(II) MOF with 4-fold interpenetration can be isolated. In this centrosymmetric MOF, the olefin groups in the backbone of the ligand (pvb) undergo a [2 + 2] cycloaddition reaction quantitatively under UV light but in a non-SCSC fashion.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Impact of the Structural Modification of Diamondoid Cd(II) MOFs on the Nonlinear Optical Properties

Gupta

Zhu

Kottilil

et al. 2021

ACS Appl. Mater. Interfaces

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“…Research on porous metal–organic frameworks (MOFs) has attracted considerable interest in the past decade , because of their intriguing network topologies , and tunable host–guest interactions, making them potential candidates for specific gas adsorption and separation, molecular recognition and sensing, catalysis, drug delivery, and related processes . The generation of porous MOFs can be achieved by applying an approach involving a two-ligand assembly system, since an isoreticular 3D porous framework can be considered to have a pillared-layer structure − in which the 2D metal–carboxylate layered motifs are pillared by (rigid) linear bis-pyridyl linkers (Scheme ). This provides a simple route to preparing desired porous frameworks with adjustable pore sizes and tunable structural properties by simply adjusting the length of the linear ligands or by changing the multicarboxylate moieties. ,, As the length of the bridging ligands is increased, MOFs usually possess network interpenetration characteristics that tends to diminish the porosity.…”

Section: Introductionmentioning

confidence: 99%

Correlation of Mesh Size of Metal–Carboxylate Layer with Degree of Interpenetration in Pillared-Layer Frameworks

Lee

et al. 2014

Crystal Growth & Design

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Two porous cobal−organic frameworks showing threefold interpenetration of pillared-layer structures, constructed from two-dimensional (2D) neutral metal−carboxylate layers and neutral bis-pyridyl-bis-amide pillars, were hydro(solvo)thermally synthesized and structurally characterized by single-crystal X-ray diffraction. Compound {[Co 2 (thdc) 2 (bpda) 2 (DMF)]•2DMF} n (1, thdc = 2,5-thiophenedicarboxylate; bpda = N,N′-bis(4-pyridinyl)-1,4-benzenedicarboxamide) adopts a uninodal 6-connected threedimensional (3D) framework with a {4 12 •6 3 }-pcu topology in which 2D rhomboid-like 4 4 -sql Co−thdc layers are pillared by bpda ligands. While compound {[Co 3 (btc) 2 (bpda) 3 ]•2DMF• 9H 2 O} n (2, btc = 1,3,5-benzenetricarboxylate) is composed of a binodal (3,4)-connected 3D framework with a (6 3 ) 2 (6 4 •8•10) 3 topology that can be described in terms of two building subunitsa 2D porous honeycomb-like 6 3 -hcb Co−btc layer and a bpda pillar. An in-depth analysis showed that the mesh size of the metal−carboxylate layer, in addition to the pillar length, is highly correlated with the degree of interpenetration in the pillared-layer framework. The structural characteristics of frameworks 1 and 2 fully support this relationship.

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Multifunctional Fourfold Interpenetrating Diamondoid Network: Gas Separation and Fabrication of Palladium Nanoparticles

Cheon

Suh

2008

Chemistry A European J

180

116

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A fourfold interpenetrating diamondoid network, [{[Ni(cyclam)]2-(mtb)}(n)].8n H2O.4n DMF (1) (MTB=methanetetrabenzoate, DMF=dimethylformamide), has been assembled from [Ni(cyclam)][ClO4]2 (cyclam=1,4,8,11-tetraazacyclotetradecane) and methanetetrabenzoic acid (H4MTB) in DMF/H2O (7:3, v/v) in the presence of triethylamine (TEA). Despite the high-fold interpenetration, 1 generates 1D channels that are occupied by water and DMF guest molecules. Solid 1, after removal of guest molecules, exhibits selective gas adsorption behavior for H2, CO2, and O2 rather than N2 and CH4, suggesting possible applications in gas separation technologies. In addition, solid 1 can be applied in the fabrication of small Pd (2.0+/-0.6 nm) nanoparticles without any extra reducing or capping agent because a Ni II macrocyclic species incorporated in 1 reduces Pd II ions to Pd 0 on immersion of 1 in the solution of Pd(NO3)2.2H2O in MeCN at room temperature.

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Self-Recognition of 3D Porous Frameworks: Fourfold Diamondoid or Threefold Cuboidal Interpenetrating Nets Formed by Varying Pillar Motifs

Cited by 18 publications

References 28 publications

Impact of the Structural Modification of Diamondoid Cd(II) MOFs on the Nonlinear Optical Properties

Impact of the Structural Modification of Diamondoid Cd(II) MOFs on the Nonlinear Optical Properties

Correlation of Mesh Size of Metal–Carboxylate Layer with Degree of Interpenetration in Pillared-Layer Frameworks

Multifunctional Fourfold Interpenetrating Diamondoid Network: Gas Separation and Fabrication of Palladium Nanoparticles

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