Loading of Two Related Metal-Organic Frameworks (MOFs), [Cu2(bdc)2(dabco)] and [Cu2(ndc)2(dabco)], with Ferrocene

Abstract

Abstract:We have studied the loading of two related, similar porous metal-organic frameworks (MOFs) [Cu 2 (bdc) 2 (dabco)] (1), and [Cu 2 (ndc) 2 (dabco)] (2) with ferrocene by exposing bulk powder samples to the corresponding vapor. On the basis of powder X-ray diffraction data and molecular dynamics (MD) calculations we propose that each pore can store one ferrocene molecule. Despite the rather pronounced similarity of the two MOFs a quite different behavior is observed, for 1 loading with ferrocene leads to an anisotropic 1% contraction, whereas for 2 no deformation is observed. Mössbauer spectroscopy studies reveal that the Fe oxidation level remains unchanged during the process. Time dependent studies reveal that the diffusion constant governing the loading from the gas-phase for 1 is approximately three times larger than the value for 2. OPEN ACCESSPolymers 2011, 3 1566

Electrochemical Applications of Ferrocene‐Based Coordination Polymers

“…In fact, CPs can be easily functionalized via the postsynthetic introduction of various functional groups (e. g., Fc units) to achieve specific properties not directly accessible by conventional methods of CP synthesis. [65,75,76] For instance, Fc-containing organic ligands can be used to construct porous Fc-based MOFs. [77,78] On the other hand, many studies relied on the postsynthetic linking of Fc derivatives to the MOF backbone to prepare redox-active MOFs.…”

“…This result is important for the electronic applications of insulator MOFs. [75] In 2011, Heck et al reported the incorporation of Fc into [Cu 2 (ndc) 2 (dabco)] and [Cu 2 (bdc) 2 (dabco)] upon exposure to Fc vapor and showed that the slower diffusion of Fc into [Cu 2 (ndc) 2 (dabco)] pores is due to the grandeur of the ndc ligand. The loaded Fc molecules did not undergo any chemical redox reaction immediately upon impregnation and could therefore act as redox-active sites.…”

“…The loaded Fc molecules did not undergo any chemical redox reaction immediately upon impregnation and could therefore act as redox-active sites. [75] Among the various types of postsynthetic methods used to prepare Fc-CPs, encapsulation is particularly effective for targeted drug delivery and other electrochemical applications. The capsule has a core-shell structure and a skin that can be made of polymeric materials.…”

“…As mentioned above, CPs can be covalently modified using postsynthetic methods, [74] which are generally well suited for the creation of functionalized CPs and for the formation of high‐sensitivity MOF cavities that can be used in a specific field. In fact, CPs can be easily functionalized via the postsynthetic introduction of various functional groups (e. g., Fc units) to achieve specific properties not directly accessible by conventional methods of CP synthesis [65,75,76] . For instance, Fc‐containing organic ligands can be used to construct porous Fc‐based MOFs [77,78] .…”

Polypyrrole decorated metal–organic frameworks for supercapacitor devices

“…11 This strategy was utilized to synthesize analogues of MOF-74, Mn 2 (DSBDC)(DMF) 2 , where thiolated ligand H 4 DSBDC forms an innite 1D metal-sulfur chain (-M-S-in contrast to typical -M-Ochains in MOF-74) that act as the charge transport pathways. 12 Method (2) of addressing MOF's conductivity is by loading redox active compounds (ferrocene, iodine, and tetracyanoquinodimethane) [13][14][15] introduced either during the synthesis or infused in various post-synthetic treatments. As a result, redox active sites are created inside the MOF's structure which help facilitate charge transfer.…”