Solid-state reactivity and structural transformations involving coordination polymers

Kole, Goutam Kumar; Vittal, Jagadese J.

doi:10.1039/c2cs35234f

Cited by 490 publications

(276 citation statements)

References 92 publications

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“…The power of TG-DTA lies in its ability to identify energy changes that occur in the sample with no loss of mass, which TG analysis alone cannot identify. 31,32 For example, we have used TG-DTA to identify molecular rearrangements in porous MOFs that are not accompanied by mass loss or a change of phase.…”

Section: Thermal Studies Of 1-2 4-6 Andmentioning

confidence: 99%

The synthesis and characterisation of coordination and hydrogen-bonded networks based on 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoic acid

et al. 2015

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. (2015). The synthesis and characterisation of coordination and hydrogen-bonded networks based on 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoic acid. Dalton Transactions: an international journal of inorganic chemistry, 44 (19), 9269-9280.The synthesis and characterisation of coordination and hydrogen-bonded networks based on 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoic acid AbstractThe synthesis, structural and thermal characterisation of a number of coordination complexes featuring the N,O-heteroditopic ligand 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoate, HL are reported. The reaction of H2L with cobalt(II) and nickel(II) nitrates at room temperature in basic DMF/H2O solution gave discrete mononuclear coordination complexes with the general formula {[M(HL)2(H2O)4]·2DMF} (M = Co (1), Ni (2)), whereas the reaction with zinc(II) nitrate gave [Zn(HL)2]∞, 3, a coordination polymer with distorted diamondoid topology and fourfold interpenetration. Coordination about the tetrahedral Zn(II) nodes in 3 are furnished by two pyrazolyl nitrogen atoms and two carboxylate oxygen atoms to give a mixed N2O2 donor set. The desolvation of 8 was followed by powder X-ray diffraction and single crystal X-ray diffraction which show desolvation induces the transition to a more closely packed structure while the coordination geometry about the copper ions and the network topology is retained. Powder X-ray diffraction and microanalysis were used to characterise the bulk purity of the coordination materials 1-6 and 8. The thermal characteristics of 1-2, 4-6 and 8 were studied by TG-DTA. This led to the curious observation of small exothermic events in networks 4, 6, and 8 that appear to be linked to their decomposition. In addition, the solid state structures of H2L and that of its protonated salt, H2L·HNO3, were also determined and revealed that H2L forms a 2-D hydrogen bonded polymer incorporating helical chains formed through N-HO and O-HN interactions, and that [H3L]NO3 forms a 1-D hydrogen-bonded polymer. The synthesis and characterisation of coordination and hydrogen-bonded networks based on 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoic acid donor sets with trans-square planar geometry and is fourfold interpenetrated. The desolvation of 8 was followed by powder X-ray diffraction and single crystal X-ray diffraction which show desolvation induces the transition to a more closely packed structure while the coordination geometry about the copper ions and the network topology is retained. Powder X-ray diffraction and microanalysis were used to characterise the bulk purity of the coordination materials 1-6 and 8. The thermal characteristics of 1-2, 4-6 and 8 were studied by TG-DTA. This led to the curious observation of small exothermic events in networks 4, 6, and 8 that appear to be linked to their decomposition. In addition, the solid state structures of H 2 L and that of its protonated salt, H 2 L•HNO 3 , were also determined and revealed that H

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Section: Thermal Studies Of 1-2 4-6 Andmentioning

confidence: 99%

The synthesis and characterisation of coordination and hydrogen-bonded networks based on 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoic acid

et al. 2015

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“…The classical work of G. Schmidt and coworkers in 1960s paved away the field of solidstate organic photochemistry as well as crystal engineering [12][13][14]. Due to this historical importance, this double bonds containing spacer and terminal ligands have been incorporated into coordination polymers (CPs) and porous CPs (PCPs) which is also popularly called as metal-organic frameworks (MOFs) to design photo-reactive solids [15][16][17]. The metal-coordination bond offers very important role in directing the organic linkers and/or guest molecules to satisfy the geometry criteria required for the photoreactions.…”

Section: Introductionmentioning

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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“…[12][13][14] In the past decades, a number of photoreactive coordination polymers (CPs) and metal-organic frameworks (MOFs) have also been made by bringing the olefin bonds present in the spacer and terminal ligands closer in parallel to undergo photo-dimerization reactions. [15][16][17] The strength and directionality of the metal-coordination bond and the bridging nature of certain anions play prominent roles to direct the C=C bonds in the organic linkers, terminal ligands and/or guest molecules to satisfy the geometric criteria required for the cycloaddition reactions. Since the crystallization process is often controlled by the kinetic factors, it has been a challenge to obtain the desired photoreactive solids experimentally.…”

Section: Introductionmentioning

confidence: 99%

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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Solid-state reactivity and structural transformations involving coordination polymers

Cited by 490 publications

References 92 publications

The synthesis and characterisation of coordination and hydrogen-bonded networks based on 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoic acid

The synthesis and characterisation of coordination and hydrogen-bonded networks based on 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoic acid

Metal-Organic Frameworks for Photochemical Reactions

Metal‐Organic Frameworks: Photoreactive Frameworks

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