Cryochemical synthesis of Mg-containing poly(p-xylylene)

A Computational Study of Tetrafluoro-[2.2]Cyclophanes

“…Cyclophanes have found applications in several different areas. Their use in the preparation of conducting polymers consisting of units that alternate a metal and the cyclophane is of particular interest . Polymers prepared from cyclophanes by chemical deposition in the vapor phase (CVD) can form biomimetic layers containing incorporated functional groups (proteins, antigens, cell receptors), which allow the control of interactions between biomaterials and organisms .…”

“…Their use in the preparation of conducting polymers consisting of units that alternate a metal and the cyclophane is of particular interest. 2 Polymers prepared from cyclophanes by chemical deposition in the vapor phase (CVD) 3 can form biomimetic layers containing incorporated functional groups (proteins, antigens, cell receptors), which allow the control of interactions between biomaterials and organisms. 4 These compounds can also act as synthetic selective receptors of anions such as carboxylates and phosphates, which exhibit biological functions.…”

Metal‐Containing Polymers: Cryochemical Synthesis, Structure, and Physicochemical Properties

“…This was confirmed by quantum chemical calculations [36]. Polymerization under UV radiation at 77 K is accompanied by the shift of band from 340 to 310 nm (Figure 2.3), which means the transformation of initial complexes into organomagnesium units of PPX backbone chains [-CH 2 -C 6 H 4 -CH 2 -Mg n -] with Mg-C bonds [35,36] close to s bonds of organomagnesium compounds. The fact that the absorbance maximum of Mg-C bonds in Mg-PPX is at 310 nm and not in the range 270-300 nm indicates some deformation of these bonds as compared to those of usual stable organomagnesium compounds.…”

“…Cryochemical synthesis is based on low-temperature solid-state polymerization in conditions of frozen molecular mobility in the reacting system. Earlier it was shown that a number of monomers, such as acrylonitrile [18], formaldehyde [19][20][21], or p-xylylene (PX) and its derivatives [22][23][24], polymerize in solid state under g or UV radiation at 77 K and even close to the liquid helium temperature [18,20]. It is suggested that such polymerization is caused by specific supramolecular organization of solid-monomer-containing molecular aggregates, which are precursors of polymer chains [25].…”

“…The structure and polymerization of the vapor-deposited PX-Mg monomer system were described in references 23 and 34-37. Taking into consideration IR and UV-Vis spectral data, it was concluded that the co-condensation of Mg with PX at 77 does not lead to the PX polymerization but results in formation of charge transfer complexes where PX is in the benzenoid form [35,36] (Scheme 2.4).…”