Martí Angel A, Rivera Noritza, Soto Karla, Maldonado Lorena, Colón Jorge L
Department of Chemistry, P.O. Box 23346, University of Puerto Rico, Río Piedras, Puerto Rico.
Dalton Trans. 2007 May 7(17):1713-8. doi: 10.1039/b618802h. Epub 2007 Mar 9.
The intercalation of fac-tricarbonylchloro-1,10-phenanthrolinerhenium(i) (Re(phen)(CO)(3)Cl) within zirconium phosphate (ZrP) has been achieved using a hydrated ZrP phase that possesses six water molecules per formula unit. This intercalation occurs only at high solution molar ratios (Re : ZrP, 3 : 1) and is characterized by the emergence of a new phase in the X-ray powder diffraction (XRPD) pattern with an interlayer distance of 15.6 A. The XRPD patterns show a decrease in the crystallinity upon intercalation of the inorganic complex. The MLCT absorption bands of Re(phen)(CO)(3)Cl-containing ZrP materials are red shifted in comparison with the complex in acetonitrile whilst the luminescence spectra at different loading levels are blue shifted up to 30 nm in comparison with the complex in acetonitrile. This blue shift is consistent with the rigidochromic effect. The luminescence lifetime of Re(phen)(CO)(3)Cl within ZrP was increased in comparison with its lifetime in acetonitrile solution but is shorter than that of Re(phen)(CO)(3)Cl in frozen glass and polyesther resins. To our knowledge, this is the first example of a water insoluble metal complex intercalated within the layers of ZrP, which opens up new possibilities in the intercalation chemistry of this lamellar material and in the study of host-guest interactions.
利用每个化学式单元含有六个水分子的水合磷酸锆（ZrP）相，已实现了 fac-三羰基氯-1,10-菲咯啉铼（i）（Re(phen)(CO)₃Cl）在磷酸锆（ZrP）中的插层。这种插层仅在高溶液摩尔比（Re : ZrP，3 : 1）下发生，其特征是在X射线粉末衍射（XRPD）图谱中出现一个新相，层间距为15.6 Å。XRPD图谱显示，无机配合物插层后结晶度降低。含Re(phen)(CO)₃Cl的ZrP材料的MLCT吸收带与乙腈中的配合物相比发生红移，而不同负载水平下的发光光谱与乙腈中的配合物相比蓝移高达30 nm。这种蓝移与刚性变色效应一致。ZrP中Re(phen)(CO)₃Cl的发光寿命与其在乙腈溶液中的寿命相比有所增加，但比其在冷冻玻璃和聚酯树脂中的寿命短。据我们所知，这是水不溶性金属配合物插层到ZrP层内的首个实例，这为这种层状材料的插层化学以及主客体相互作用的研究开辟了新的可能性。
