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A number of 3D-coordination polymers, constructed via [ d M(CN) 6 ] building blocks and (Me 3 E) connecting units, have been prepared and characterized by X-ray powder diffraction and different spectroscopic methods. 1-Methyl-4-(4′- R -styryl) or (2′- R -styryl) pyridinium cations (stp) have been successfully encapsulated within the expandable wide channels of the 3D-coordination polymers by tribochemical or ion exchange reactions producing novel molecular composites. Apart from 6 , [(4′-OCH 3 -stp)(Me 3 Sn) 3 Fe II (CN) 6 –MeOH] ∞ which exhibits thermochromic behaviour, the molecular composites [(stp) x (Me 3 E) 3 Fe III 1– x Fe II x (CN) 6 ] ∞ , 1 – 12 are mixed valence materials exhibiting localized interaction between the mixed valence iron. The results indicated an ion charge transfer interaction between the guest stp-cations and the host matrix. The molecular composites [(stp)(Me 3 E) 3 M II (CN) 6 ] ∞ , 13 – 18 are due to the facile readiness of the coordination polymers [(Me 3 E) 4 M(CN) 6 ] ∞ and [(Et 4 N)(Me 3 Sn) 3 Fe(CN 6 )] ∞ to ion exchange. |
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