Single‐Crystal‐to‐Single‐Crystal Transformations of Two Three‐Dimensional Coordination Polymers through Regioselective [2+2] Photodimerization Reactions

Liu, Dong; Ren, Zhi‐Gang; Li, Hong‐Xi; Lang, Jian‐Ping; Li, Ni-Ya; Abrahams, Brendan F.

doi:10.1002/anie.201001551

Cited by 339 publications

(84 citation statements)

References 43 publications

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“…These ligands present many interesting possibilities for studying photoreactivity. 59 In the case of Zn(II) MOF, a 2D layer [Zn 4 (μ 3 -OH) 2 (5-sipa) 2 ] with (6,3) connectivity related CdI 2 is formed by linking six equivalent 5-sipa with three equivalent {Zn 4 (μ 3 -OH) 2 }. Further the axial positions of these {Zn 4 (μ 3 -OH) 2 } sheets are pillared by two pairs of bpeb ligands to form the double-pillared 3D network structure.…”

Section: Photoreactive Double-pillared Mofs With Conjugated C=c Bond mentioning

confidence: 99%

“…As a result, UV irradiation of this compound showed quantitative photoreaction between the 'out of phase' C=C pairs only and resulted in the formation of another 3D structure in an SCSC manner ( Figure 29). 59 In the case of Cd(II) MOF, 49 the (4,4) sheets formed by the {Cd 2 (1,3-pda) 4 } are further pillared by the bpeb pairs to yield another double-pillared 3D structure. In the 'face-to-face' arrangement of the bpeb ligand-pairs, the C=C bonds are separated by 3.886 and 4.023 Å.…”

Section: Photoreactive Double-pillared Mofs With Conjugated C=c Bond mentioning

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: Photoreactive Double-pillared Mofs With Conjugated C=c Bond mentioning

confidence: 99%

Section: Photoreactive Double-pillared Mofs With Conjugated C=c Bond mentioning

confidence: 99%

Metal‐Organic Frameworks: Photoreactive Frameworks

Chanthapally

Vittal

2014

Encyclopedia of Inorganic and Bioinorganic Chemistry

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“…[36][37] Further, the CPs containing ligands with olefins are of great importance in order to synthesize photoreactive coordination polymers. [38][39][40][41][42][43][44][45][46][47] Bis-(4-pyridyl)-ethylene is well utilized ligand for building up photoreactive CPs. [48][49][50][51][52][53] Recently, it was shown by us and others that the photoreactive coordination polymers of bis-olefin containing ligands have an ability to produce CPs of organic polymers via post synthetic irradiation.…”

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confidence: 99%

Diversity in the Coordination Polymers of 2-(2-(Pyridin-4/3-yl)vinyl)-1H-benzimidazole and Dicarboxylates/Disulfonates: Photochemical Reactivity and Luminescence Studies

Garai

Somnath

Biradha

2016

Crystal Growth & Design

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Solvothermal reactions of Cd(II) or Zn(II) with two unsymmetrical olefinic ligands containing benzimidazole and 3-pyridyl/4-pyridyl moieties and ancillary anionic linkers such as dicarboxylates or disulfonates resulted in the coordination polymers containing diversified geometries. The crystal structure analyses of about eight such CPs reveal that the coordination networks found here include one-dimensional (1D) chains of metal and dicarboxylates/disulfonates with ligands as pendents, two-dimensional corrugated layers containing rectangular grids, and a three-dimensional (3D) coordination network. In two of the complexes, Cd2O2 acts as a secondary building unit (SBU) to form a two-dimensional (2D) layer of metal and dicarboxylates. The interdigitation of the pendent ligands of 1D-chains resulted in the required alignment of double bonds of L 1 or L 2 for photochemical [2 + 2] reaction, in two of the CPs. These CPs upon irradiation were found to undergo solid state [2 + 2] cycloaddition reactions with 100% conversion. All the complexes including irradiated ones were found to exhibit intense emission in solid state luminescence studies.

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“…In order to obtain these materials, the common approach is to use multitopic organic ligands containing pyridyl, pyrazolyl and imidazolyl groups to bind various metals [4][5][6][7][8][9][10][11][12]. In such an assembly process, some external factors such as solvents [13], pH values [14] and so on [15][16][17] are all known to play crucial roles in determining the structures of coordination complexes.…”

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confidence: 99%