| The intercalation of platinum(II) complexes, such as chloro(2,6-bis(N-methylbenzimidazol-2-yl)pyridine)platinum(II) ([Pt(Me2bzimpy)Cl]+), chloro(2,2':6',2"-terpyridine)platinum(II) ([Pt(tpy)Cl]+), 2,4,6-trimethyl-phenyl(2,2':6',2"-terpyridine)platinum(II) ([Pt(tpy)mes]+), di-(mu-pyrazolate)-bis(4,4'-dimethyl-2,2'-bipyridine)platinum(II) ([{Pt(4,4-dmbpy)(mu-pz)}2]2+), and 1,4,7-trithiacyclononane(2,2'-bipyridine)platinum(II) ([Pt(bpy)ttcn]2+) into zirconium phosphate layers have been investigated for future use as chemosensors.;[Pt(Me2bzimpy)Cl]+, [Pt(tpy)Cl]+ and [Pt(tpy)mes] + are readily ion-exchanged into 10.3 A-ZrP to give novel luminescent materials. Spectroscopic measurements show that the physical and chemical structures of the complexes and the layers are maintained. The results are consistent with an expansion of the interlayer spacing to ∼18 A in order to accommodate aggregates of closely interacting platinum complexes. [Pt(Me2bzimpy)Cl]+-exchanged ZrP exhibits distinct absorption and emission spectroscopic signatures that are independent of loading levels and characteristic of low-lying MMLCT states resulting from short Pt···Pt spacings. By contrast, the spectroscopic properties of [Pt(tpy)Cl] +-exchanged ZrP are dependent on loading levels, suggesting the existence of more than one type of intercalated platinum aggregate.;In order to ensure the presence of Pt···Pt interactions and tune the photophysical properties, we also accomplished the direct ion-exchange of [{Pt(4,4-dmbpy)(mu-pz)}2]2+ into 10.3 A-ZrP layers. The zirconium phosphate layers promote the formation of a mixed-valence platinum system incorporated in a rigid-framework matrix and interesting photophysical differences between powders and colloidal suspensions. The spectroscopic properties of this new system are consistent with little-to-no metal-metal interactions. The "platinum blues" are not known to be emissive and the [{Pt(4,4'-dmbpy)(mu-pz)} 2]2+-exchanged ZrP materials are brightly emissive in colloidal suspensions and powders at room temperature. We have achieved blue-green, blue, and near-UV emission from suspensions of the intercalated material in different solvents suggesting that they play key roles that facilitate structural changing processes within the ZrP microenvironment.;To better access the influence of axial interactions on the electronic structures and tune the photophysical properties, we also accomplished the direct ion-exchange of [Pt(bpy)ttcn]2+ into 10.3 A-ZrP layers. The zirconium phosphate layers promote a fluxional behavior of the apical Pt-S distances, which accounts for interesting photophysical differences between powders and colloidal suspensions.;Powders and thin films of the platinum(II) complexes-exchanged ZrP materials exhibit distinctive colors and show intense emission at room temperature, depending on their stacking properties within the layers. These intercalated materials exhibit reversible vapochromic and vapoluminescent behavior upon exposure to polar and non-polar VOCs, such as methylene chloride, methanol, acetonitrile, tetrahydrofurane, benzene, and hexane. |
