Uranyl Coordination Polymers Incorporating eta(5)-Cyclopentadienyliron-Functionalized eta(6)-Phthalate Metalloligands: Syntheses, Structures and Photophysical Properties

作者：Kerr Andrew T; Kumalah Sayon A; Holman K T; Butcher Ray J; Cahill Christopher L^*

来源：Journal of Inorganic and Organometallic Polymers and Materials, 2014, 24(1): 128-136.

DOI：10.1007/s10904-013-9980-0

• Uranyl
• Metalloligand
• Luminescence
• Hydrolysis
• Hydrothermal

The reaction of two eta(5)-cyclopentadienyliron(II)-functionalized terephthalate and phthalate metalloligands, namely [(eta(5)-C5H5)Fe-II(eta(6)-1,4-HO2CC6H4CO2H)][(eta(5)-C5H5)Fe-II(eta(6)-1,4-HO2CC6H4CO2)][PF6] and [(eta(5)-C5H5)Fe-II(eta(6)-1,2-HO2CC6H4CO2H)][(eta(5)-C5H5)Fe-II(eta(6)-1,2-HO2CC6H4CO2)][PF6]-hereafter [H-2 CpFeTP][HCpFeTP][PF6] and [H-2 CpFeP][HCpFeP][PF6], respectively-with [UO2(NO3)(2)]center dot 6H(2)O under hydrothermal conditions yielded four new coordination polymers; (1) [(UO2)F(HCpFeTP)(PO4H2)]center dot 2H(2)O, (2) [(UO2)(2)(CpFeTP)(4)]center dot 5H(2)O, (3) [(UO2)(2)F-3(H2O)(CpFeP)], and (4) [H-2 CpFeP][UO2F3]. The use of metalloligands has proven to be a viable route towards the incorporation of a secondary metal center into uranyl bearing materials. Depending upon the protonation state, the iron sandwich metalloligands may vary from zwitterionic neutral or monoanionic coordinating species as observed in compounds 1-3, or a positively charged species that hydrogen bonds with anionic [UO2F3](-) chains as observed in 4. Further, the hydrolysis of the charge balancing PF6 (-) anion increases the diversity of UO2 (2+) coordinating species by contributing both F- and PO4 (3-) anions (1, 3, 4). The luminescent properties of 1-4 were also studied and revealed the absence of uranyl emission, suggestive of a possible energy transfer from the uranyl cation to the iron(II) metal center.

• 出版日期2014-1