Search

Research has been conducted on the hetero- and homometallic aquare complexes. The preparation and photochemistry of the self-assembly transition-metal-based macrocyclic compounds bridged by the photoisomerizable 4,4'-azopyridine or 1,2-bis(4-pyridyl)ethylene ligand are described.

Research has been conducted on the polypyridyl d (super)6-W(0) and Re(I) carbonyl complexes. The results of the photophysical and photochemical analysis of some of these complexes which incorporate ferrocene end-capped pyridine ligands are reported.

Research demonstrates synthesis of four octanuclear organometallic squares by self-assembly between ligand complexes. Structural and elemental analyses reveal that the squares incorporate terpyridyl metal complexes as bridging ligands. All four heterometallic complexes exhibit strong visible absorption characteristic of iron, rubidium, or osmium metals.

A photochemical study of the (eta-5-C5H5)Fe(Co)2 was presented to determine the optimum photochemical conditions for the complexes. The heterocyclic cleavage of iodide which was needed to form (eta-5-C5H5)Fe(Co)2(eta-1-N-pyrrolyl) was investigated due to irradiation at various wavelengths. Results revealed that most effective photoconversion took place with excitation at long wavelengths into weak low-lying absorption bands and long-wavelength irradiation was a means of effecting heterolytic Fe-I dissociation which facilitates synthetic pathway to azaferrocene.

Photoreactivity measurements were conducted on the intermolecular C-H bond activation process of (HBPz'3)Rh(CO)2 in different hydrocarbon solutions at room temperature. Absolute quantum efficiencies for C-H activation were obtained and were observed to be dependent on the excitation wavelength and the nature of the substrate. A short-lived monocarbonyl (HBPz'3)Rh(CO) intermediate was implicated in the C-H bond activation pathway, and this reaction was facilitated most effectively upon ultraviolet photolysis.

The thermal chemistry and photochemistry of the intermolecular C-H bond activating complex (HBPz'3)Rh(CO)2, where Pz = 3,5-dimethylpyrazolyl, have been investigated. Excitations were performed at 313-458 nm into the lowest energy absorption band and were monitored by in-situ UV-vis and FTIR spectroscopies. The results showed that the photochemistry is exceptionally clean, with complete conversion of the complex to the (HBPz'3)Rh(CO)(R)H photoproducts. The photochemical reactions were shown to originate from two low-lying LF state with different activities.

A kinetic procedure for measuring the photochemical quantum efficiencies of reactions in which several components have overlapping absorbances is fully described. This method has been found to be particularly suitable for photochemical determinations where inner filter effects are substantial, such as those typically observed in the ligand substitution and intermolecular C-H/Si-H bond activation mechanisms of metal complexes. The quantitative measurement of the Si-H bond activation photochemistry of ([[Eta].sup.5]-[C.sub.5][H.sub.5])Rh[(CO).sub.2] in triethylsilane solution is demonstrated in detail, although the procedure has widespread application in photochemistry.

A method for monitoring the extent of photoinitiated acrylate and epoxy polymerixations is presented. The complex fac-CIRe(CO)3(4,7-Ph2phen) (4,7-Ph2phen = 4,7-diphenyl-1,10-phananthroline) is an effective spectroscopic probe which can monitor the progress of photochemical curing reactions. Its useful key properties include solubility and thermal stability in nonpolar thin film materials, intense visible absorptions and their low-lying MLCT excited states which yield detectable emissions in the red region of the spectrum.

The photophysical properties of the complexes CpRe(CO)2(3-benzoylpyridine) and CpRe(CO)3(4-benzoylpyridine) are determined by examining their electronic absorption, emission and excitation spectra ans emission lifetimes. The results show that CpRe(CO)2(3-benzoylpyridine) exhibits multiple emission from triplet-centered n,pi* intraligands and metal-to-ligand charge-transfer (MLCT) levels while CpRe(CO)2(4-benzoylpyridine) exhibits only one emission spectra which is assigned to the lowest energy MLCT state. The difference were attributed to the electronic and geometric differences in the excited states.

A study was done on the pathways for photosubstitution and C-H/Si-H bond activation reactions in (n super 5-C5R5)Rh(CO)2(R=H,Me) complexes. It was shown that photoreactions involving the solutions involve clean and complete conversion to the corresponding CpRh(CO)PR3 and Cp*Rh(CO)PR3 products. The reactions occur from ligand field excited states and ligand photosubstitution proceed through an associative mechanism.

The quantitative photochemistry of Cp'Pt(CH3)(sub 3) (Cp' = eta(super 5)-C5H4CH3) in solution has been investigated. The photoefficiencies indicate that the qualitative photochemistry is 2 orders of magnitude higher than previously recognized.

Wavelength-dependent photochemistry of W(CO)4(ethylenediamine) was analyzed through a substitution reaction designed to replace the CO group with a ligand. Results of the substitution reaction analysis indicate that the quantum yield of the substituted tungsten ethylenediamine is determined by the excitation wavelength. This indicate that photosubstitution in the ligand field is achieved through a different photophysical pathway and that this reduces the efficiency of the photoreaction.

Solution photochemistry of C-H bond activation reactivity of (HBPz*3)Rh(CO)2 (Pz* = 3,5-dimethylpyrazolyl) complex in hydrocarbon solution reveals that wavelength of light excitation influences the C-H bond activation process. Different reactivities are observed in the two electronically excited states of the complex. An eta 3 to eta 2 ligand dichelation mechanism accounts for the photoinertness of the lower energy level. C-H bond activation is high in the upper energy excited state, indicating CO dissociation as the first step in the oxidative addition mechanism.

A new experiment in mechanistic organometallic photochemistry that involves measuring the photochemical efficiency for arene displacement from a mixed compound of iron is described. The experiment teaches students a wide range of laboratory skills and instrumentation and students learn how to prepare and handle solutions of light-sensitive compounds for photochemical studies.

Research has been conducted on luminescent anion receptors. The authors report the development of these receptors containing ruthenium(I) tricarbonyl signaling units and amide-type anion binding site.

It is stated the photo chemistry of the [CpFe(Eta(super 6)-arene)] x system were investigated in several different solvents at 293K as a function of excitation wavelength at 355,458,488,514,633 and 683nm, The results illustrated that the photoreaction was extremely efficient in the uv and visible regions, particularly if polar solvents were employed.

A series of molecular squares with the general molecular formula [fac-Br (Co) 3Re(u- (pyterpy)(sub 2) M)](sub 4)(PF6)(sub 8), where pyterpy is 4'-(4''' - pyridyl)-2,2': 6E, 2EE -terpyridine and M=Fe, Ru, or Os are prepared. The spectroscopic properties and a preliminary anion binding study of these novel octanuclear molecular squares are studied.

A study concerning the preparation of the luminescent rhenium(I)-based molecular triangle and square complexes is presented. The associated photophysical data are described.

Self assembly triangular and square rhenium(I) tricarbonyl compounds were prepared.