Solid‐State Structural Transformations from 2D Interdigitated Layers to 3D Interpenetrated Structures

Medishetty, Raghavender; Koh, Lip Lin; Kole, Goutam Kumar; Vittal, Jagadese J.

doi:10.1002/anie.201104106

Cited by 114 publications

(53 citation statements)

References 41 publications

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“…55 The paddle-wheel SBU, {Zn 2 (O 2 C-C) 4 } has been found in two isotypical interdigitated photoreactive CPs, [Zn 2 (cca) 2 (4-spy) 2 ] (40) and [Zn 2 (ndc) 2 (4-spy) 2 ] (41). The linear dicarboxylate ligands 4-carboxycinnamate (cca) or 2,6-naphthalenedicarboxylate (ndc) are connecting the paddle-wheel nodes to form the 2D layer structure with (4,4) connectivity.…”

Section: Photoreactivity Of 2d Interdigitated Cp Leading To 3d Mofmentioning

confidence: 99%

“…Such localized heat release was designed to trigger molecular desorption or release by integrating the GNRs inside the MOFs in mesoscale so that the heat transfer will be effective. GNRs coated with Alumina was allowed to react in a microwave reactor with an organic ligand 1,4-naphthalenedicarboxylic acid H 2 (1,4-ndc) as a linker to obtain a porous CP, GNR@[Al(OH)(1,4-ndc)] n (55). Metal@MOF composites were designed with controlled particle size for molecular release studies for the first time.…”

Section: Light-induced Release Of Molecules From Mofsmentioning

confidence: 99%

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Metal‐Organic Frameworks: Photoreactive Frameworks

Chanthapally

Vittal

2014

Encyclopedia of Inorganic and Bioinorganic Chemistry

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This chapter deals with various photoreactive coordination polymers (CPs) and metal‐organic frameworks (MOFs) that undergo [2+2] cycloaddition reactions in the solid state, solid‐state structural transformations, post‐synthetic modification of surfaces creating reactive sites, radicals that are not possible by conventional synthetic routes, polymerization on the surfaces, cis‐trans isomerization of the guest molecules in the cavities as well as the dynamic behavior of the CP and MOF structures. Further the formation of these compounds by photochemical methods is also discussed. The three‐dimensional (3D) structural characterization of the products of a number of photochemical and photo‐polymerization reactions were hampered by the lack of a suitable structural tool other than single crystal X‐ray crystallography. On the other hand, most of the examples discussed in this chapter do maintain single crystals at the end of the reactions such that 3D structural elucidation is possible by single crystal X‐ray crystallography to understand the reactivity completely. A few examples have been illustrated where [2+2] cycloaddition reaction has been used to monitor the formation of ladder structures in the solid state in the absence of crystal structures.

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Section: Photoreactivity Of 2d Interdigitated Cp Leading To 3d Mofmentioning

confidence: 99%

Section: Light-induced Release Of Molecules From Mofsmentioning

confidence: 99%

Metal‐Organic Frameworks: Photoreactive Frameworks

Chanthapally

Vittal

2014

Encyclopedia of Inorganic and Bioinorganic Chemistry

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“…In this example, the use of 4spy in linking the 2D layers to form interpenetrated 3D structures by [2þ2] cycloaddition reaction is described [51]. Two isotypical interdigitated photo-reactive CPs, [Zn 2 (cca) 2 (4spy) 2 ] (40) Kitagawa and coworkers have demonstrated how to control the reactivity and pore surface of MOFs by photo-irradiation [52].…”

Section: Transformation Of 2d Interdigitated Cp To 3d Mofmentioning

confidence: 99%

Metal-Organic Frameworks for Photochemical Reactions

Medishetty

Vittal

2013

Metal-Organic Frameworks for Photonics Applications

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In this chapter, various photochemical reactions involving coordination polymers and metal-organic frameworks have been described. These include structural transformations, post-synthetic modification of surfaces to create reactive sites, radicals which are not possible by convention synthetic routes, polymerization on the surfaces, and cis-trans isomerization of the guest molecules in the cavities using the dynamic behavior of the structures. Further, a few examples have been provided where [2þ2] cycloaddition reaction has been used as a tool to monitor the changes in the solid-state structures in the absence of crystal structures. The structures of the resultant products of a number of polymerization reactions such as alkenoates were hampered due to the lack of suitable structural tool other than single crystal X-ray crystallography. On the other hand, most of the examples discussed in this chapter do maintain the single crystals at the end of the reactions making them amenable for structural elucidation to understand the reactivity completely.

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“…It is amazing that such a chemical reaction which normally involves bond breaking and forming could take place in the solid state and not destroy the long range ordering, in other words the structural transformation is completed from the crystalline state to the crystalline state. [1][2][3][4][5][6] A three interpenetrated independent 3D network in [Fe(pmd)(H 2 O){M(CN 2 ) 2 }]Á4H 2 O (pmd = pyrimidine) was reported to undergo a transformation to a single 3D network due to the coordination substitution of a water molecule by a pmd ligand during dehydration and such a process is reversible; the accompanying magnetic properties changed as well. 1 The first example of such a topochemical conversion of a H-bonded network to a covalently bonded framework was in a square pyramidal Zn complex, 7 where the apical water molecule was substituted by the carboxylate ion in the network; however such a conversion is irreversible even though the symmetry and space group do not change.…”

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“…Here we report a ligand substitution on an octahedrally bonded iron(II) complex, [Fe(m-atrz)(atrz) 2 …”

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confidence: 99%