Intercalation of Re(phen)(CO)₃Cl into zirconium phosphate: a water insoluble inorganic complex immobilized in a highly polar rigid matrix

Abstract

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.

Photophysical Characterization of the Interactions among Tris(2,2′-bipyridyl)ruthenium(II) Complexes Ion-Exchanged within Zirconium Phosphate

“…The similarity of the λ max values is indicative of the polar microenvironment experienced by the Ru(bpy) 3 2+ probes in the interlayer region, which is consistent with the highly hydrated state of the ZrP and with the ionic nature of the lattice 24. The observed blue shift is in-keeping with the rigidochromic effect, due to the more rigid environment in the interlayer region of the exchanged material 35,36.…”

“…The bandpass of the emission monochromator was 6.25 nm. Time-resolved luminescence experiments were performed using an Oriel lifetime spectrometer as described elsewhere 24. The models used to fit the transients were single exponential and double exponential decays models, using Sigma Plot 8.0 software.…”

Metal Complexes Supported on Solid Matrices for Visible‐Light‐Driven Molecular Transformations

“…a-ZrP allows for intercalation of large guest molecules within the restricted interlayer space via an ion-exchange or phase-boundary mechanism, taking the advantage of the strong electrostatic interaction between the exchangeable proton and the guest molecules with positive charge. [77] Although property changes induced by the macroheterogeneous surroundings of a-ZrP have been reported on intercalation of various luminescent complexes, such as [Ru(bpy) 3 ] 2 + , [78] [Pt(tpy)Cl] + , [79] and [Re(phen)(CO) 3 Cl], [80] their prominent photocatalytic activities have scarcely been investigated to date. [81] Much effort has been dedicated to the efficient photocatalytic conversion of CO 2 into energetically beneficial molecules, such as carbon monoxide, methane, formic acid, or methanol.…”

Three‐Dimensional Solvent‐Vapor Map Generated by Supramolecular Metal‐Complex Entrapment

“…The supercages of the NaY zeolite have a diameter of approximately 13 (large enough to accommodate the complex with a diameter of ca. 9 ) [19] and pore entrances of approximately 7.4 . Therefore, the rhenium complex can fit into the supercage, but once it has been entrapped inside, it is too large to diffuse out of the cage through the pore entrance.…”