College
College of Arts & Sciences
Mentor Information
Randy Larsen
Description
Metal organic frameworks (MOFs) are a class of porous materials capable of encapsulating photoactive guests for applications in light harvesting, gas storage, and photocatalysis. Here we investigate the attempted co-encapsulation of Ru(II)tris(2,2′-bipyridine)(RuBpy3) and Co(II)tris(2,2′-bipyridine) (CoBpy3) or Os(II)tris(2,2′-bipyridine) (OsBpy3) in an RWLC-3 Zn(II) based MOF, for the development of a solid-state directional photoinduced electron transfer (PET) system. The synthesis of the co-encapsulated RuBpy3 and CoBpy3 MOF (RWLC-3 (RuBpy3:CoBpy3)) was conducted using CoBpy3 in place of RuBpy3 under RWLC-3 synthesis conditions, giving a crystalline suspension with a distinctive powder x-ray diffraction (PXRD). Single crystal x-ray diffraction (SCD) revealed a 2D chain with Co(II) ions connected through terephthalic acid ligands with capping Bpy. Thus, under high temperature synthesis conditions two Bpy ligands thermally dissociate from the CoBpy3, leaving open coordination sites to form the 2D chain. While attempts to co-encapsulate RuBpy3 and CoBpy3 complexes within RWLC-3 framework did not result in the desired material, a new synthesis pathway for Co(II) crystalline frameworks was identified. Attempts to synthesize RWCL-3 (RuBpy3:OsBpy3) using varying mass ratios of RuBpy3 to OsBpy3 resulted in a crystalline suspension with a similar PXRD pattern to that of RLWC-3. SCD revealed a previously reported MOF and no RuBpy3 or OsBpy3 within the channels. Although SCD shows the absence of OsBpy3 and RuBpy3inside the channels of the MOF, subsequent photophysical analyses reveal the presence of RuBpy3 and OsBpy3 and implies they are most likely electrostatically surface bound to the crystals.
Development of a Zn(II) Based MOF for Directional Photo-Induced Electron Transfer
Metal organic frameworks (MOFs) are a class of porous materials capable of encapsulating photoactive guests for applications in light harvesting, gas storage, and photocatalysis. Here we investigate the attempted co-encapsulation of Ru(II)tris(2,2′-bipyridine)(RuBpy3) and Co(II)tris(2,2′-bipyridine) (CoBpy3) or Os(II)tris(2,2′-bipyridine) (OsBpy3) in an RWLC-3 Zn(II) based MOF, for the development of a solid-state directional photoinduced electron transfer (PET) system. The synthesis of the co-encapsulated RuBpy3 and CoBpy3 MOF (RWLC-3 (RuBpy3:CoBpy3)) was conducted using CoBpy3 in place of RuBpy3 under RWLC-3 synthesis conditions, giving a crystalline suspension with a distinctive powder x-ray diffraction (PXRD). Single crystal x-ray diffraction (SCD) revealed a 2D chain with Co(II) ions connected through terephthalic acid ligands with capping Bpy. Thus, under high temperature synthesis conditions two Bpy ligands thermally dissociate from the CoBpy3, leaving open coordination sites to form the 2D chain. While attempts to co-encapsulate RuBpy3 and CoBpy3 complexes within RWLC-3 framework did not result in the desired material, a new synthesis pathway for Co(II) crystalline frameworks was identified. Attempts to synthesize RWCL-3 (RuBpy3:OsBpy3) using varying mass ratios of RuBpy3 to OsBpy3 resulted in a crystalline suspension with a similar PXRD pattern to that of RLWC-3. SCD revealed a previously reported MOF and no RuBpy3 or OsBpy3 within the channels. Although SCD shows the absence of OsBpy3 and RuBpy3inside the channels of the MOF, subsequent photophysical analyses reveal the presence of RuBpy3 and OsBpy3 and implies they are most likely electrostatically surface bound to the crystals.
