Intercalation of Re(phen)(CO)3Cl into zirconium phosphate:: a water insoluble inorganic complex immobilized in a highly polar rigid matrix
Intercalation of Re(phen)(CO)3Cl into zirconium phosphate:: a water insoluble inorganic complex immobilized in a highly polar rigid matrix
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DOI：
10.1039/b618802h
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发表时间：
2007-01-01
影响因子：
4
通讯作者：
Colon, Jorge L.
中科院分区：
文献类型：
--
作者：
Marti, Angel A.;Rivera, Noritza;Colon, Jorge L.
采用六个水分子的水合磷酸锆（ZrP）相，实现了α-三羰基氯-1，10-菲咯啉铼（I）（Re（phen）（CO）（3）Cl）在ZrP中的插层。这种插层仅在高溶液摩尔比（Re：ZrP，3：1）下发生，并且其特征在于在X射线粉末衍射（XRPD）图案中出现层间距为15.6埃的新相。XRPD图谱显示无机复合物插层后结晶度降低。含Re（phen）（CO）（3）Cl的ZrP材料的MLCT吸收带与乙腈中的配合物相比发生了红移，而不同负载量下的发光光谱与乙腈中的配合物相比发生了蓝移，最大蓝移达30 nm。这种蓝移与刚色效应一致。Re（phen）（CO）（3）Cl在ZrP中的发光寿命比在乙腈溶液中的发光寿命长，但比Re（phen）（CO）（3）Cl在玻璃和聚酯树脂中的发光寿命短。据我们所知，这是水不溶性金属配合物插入ZrP层内的第一个例子，这为这种片状材料的插层化学和主客体相互作用的研究开辟了新的可能性。
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 angstrom. 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.