The diffusion of carbon monoxide into thin, transparent, porous film media is studied by doping the film with an iron porphyrin and spectroscopically monitoring the chemical interaction between the reduced iron porphyrin and the diffusing solute. The films are spin-cast from metal alkoxide carboxylates. Both optical absorption and resonance Raman spectroscopies have been used to study the porphyrin-doped film and the diffusion process.

The studies yield information on the effective pore size and homogeneity of the materials, and show that redox chemistry can be performed on incorporated metallo-porphyrins. This investigation also demonstrates the usefulness of porphyrin-doped films as chemical sensors, showing a sensitivity below 70 ppb to aqueous carbon monoxide.

Porous stable metal-organic films can be processed under mild conditions by the hydrolysis of carboxylic acid and titanium isopropoxide mixtures. It is of importance to establish the structure of such materials. Raman spectroscopy is a useful technique in determining structural changes in titanium isopropoxide carboxylate solutions, but weak scattering does not allow for study of thin films unless surface enhancement is used. In an attempt to elucidate the relationship between coating solutions and the final structure of a cast film, we discuss Raman spectra of precursor solutions in a variety of conditions.

Titanium alkoxides modified by carboxylic acids have been widely studied as the molecular precursors to ceramic materials. These alkoxide complexes have also been very useful in the formation of stable, porous, optically clear films having many novel applications such as chemical sensors, catalytic supports, and ion-exchange media. To improve the processing of these materials, it is essential to better understand the kinetics of the chemical transformations which occur.

The kinetics of the hydrolysis reaction are studied for selected carboxylic acids using Raman spectroscopy to probe the chemistry of the process. The study has a special emphasis on the titanium isopropoxide-valeric acid system due to the superior quality of these films over other carboxylates. Greater knowledge of the hydrolysis kinetics allows increased control over the quality of the film materials and should be of general interest to those working with modified metal alkoxides.

Sol-gel derived molecular composites exhibiting intense luminescence, induced from efficient energy transduction processes, have been prepared. The composites are comprised of an Eu3+⊂ 2.2.1 cryptate complex or native Eu3+ ion embedded in sol-gel derived titania glass films. The titania glasses contain interconnected porous networks that permit the diffusion of exogenous substrates, such as the salts of benzoic and 4-tert-butylbenzoic acids, through the film. Interaction of the substrate with the embedded lanthanide complex is indicated by enhanced luminescence from the lanthanide ion. The carboxylic acid salts whose electronic excited states are produced upon capture of incident photons, undergo facile transfer of their electronic energy to the lanthanide ion. By monitoring europium ion luminescence, the diffusion constants of the benzoate and 4-tert-butylbenzoate salts have been measured. Although the diffusion of the 4-tert-butylbenzoate is slower than that of benzoate, the overall higher sensitivity of the former is consistent with hydrophobic guest-host interactions. These new molecular composites relying on the immobilization of an absorption-energytransfer- emission molecular assembly in porous, optically transparent ceramic glasses may be useful in the design of practical sensing devices.

Metal-organic films were produced at ambient temperatures and pressures by the controlled hydrolysis of carboxylic acid and titanium isopropoxide mixtures. Pre-resonance Raman spectroscopy was used to study the effect of the organic acid chain length upon the nature of the resulting film. Propionic, butyric, valeric, hexanoic, and octanoic acids were studied, resulting in a proposed correlation between film quality and certain spectroscopic features of the alkoxide carboxylates. The choice of the carboxylic acid and the presence of an appropriate amount of water were shown to be critical in the development of a good film.

Standard sol-gel procedures have been modified to permit sol-gel synthesis to be performed at varying hydrogen ion concentrations and in a variety of organic solvents. These modifications greatly expand the variety of guest molecules that can be incorporated into nondense glassy environments. Processing conditions can be controlled such that the guest compounds generally retain their solution properties thereby allowing new molecular composites to be formed. Reported herein is the incorporation of both porphyrins and metalloporphyrins into silica matrices. Electronic absorption, vibrational, and excited state luminescence properties of the resulting composites clearly demonstrate that the molecular and electronic structure of the porphyrins and metalloporphyrins are preserved during sol-gel processing and in the ceramic matrices. This retention of properties has been shown for guest molecules doped into monoliths as well as films.

Metallo-organic materials are often used as precursors for highly refractory oxides and hightemperature composites. The feasibility of producing hafnium metallo-organic films and gels by sol-gel techniques is demonstrated in the present study. Since hafnium alkoxides are not commercially available, their preparation is an obstacle in the development of their sol-gel processing applications. A common synthesis technique was used to produce hafnium isopropoxide, which was subsequently hydrolyzed under acid catalyzed conditions to produce films and gels. The films were prepared by spin casting and remained optically transparent. Initially, the gels were also optically transparent, but became translucent upon drying. Raman, IR, and light scattering spectroscopies were used to characterize this sol-gel process, and it is compared with the analogous processing of titanium and zirconium alkoxides.

Luminescent oxide gels were prepared by hydrolysis of silicon alkoxides in solutions containing the luminescent hexanuclear molybdenum cluster Mo6Cl12. The resulting gel exhibited emission and lifetime behavior characteristic of Mo6Cl12 thereby indicating that the excited-state properties of the metal cluster species are not significantly perturbed by the gel environment.

The use of Raman spectroscopy can be greatly hindered by the presence of fluorescing impurities. Even at low concentrations, fluorescence can completely obscure the Raman signal. In the current study, Raman spectra were recorded for various titanium alkoxides (ethoxide, isopropoxide, isobutoxide) as a function of concentration and laser excitation wavelength. It has been shown that fluorescence can be avoided by using uv-excitation (363.8 nm). In addition, titanium alkoxides exhibit a preresonance Raman enhancement as the excitation wavelength appreaches the UV. This result is confirmed by a uv-visible absorption spectrum of the isopropoxide.