The reaction of [Ti(mu-ONep)(ONep)3]2 (ONep = OCH2C(CH3)3) with a series of heterocyclic methanol derivatives [tetrahydrofurfuryl alcohol (H-OTHF), thiophene methanol (H-OTPM), or 2-pyridylcarbinol (H-OPy)-collectively termed H-OR*], led to the isolation of a novel family of OR*-substituted titanium alkoxide precursors. Independent of the initial stoichiometry for the H-OTHF reaction, a monosubstituted, dinuclear species was isolated as [(ONep)3Ti(muc-OTHF)]2 (1). For 1, each Ti was octahedrally (Oh) bound by three terminal ONep ligands, one bidentate bridging OTHF ligand (muc-OTHF), and an oxygen from the other muc-OTHF ligand. For the OTPM derivatives, the product was identified as [(ONep)3Ti(mu-OTPM)]2 (2). For this ligand, the soft S atom does not bind to the Ti but the O atom does act as a bridge between the two trigonal bipyramidal bound Ti metal centers. The OPy system yielded (OPy)2Ti(OR)2 independent of the OR and the stoichiometry used [OR = ONep (3), OCHMe2 (4), OCMe3 (5)]. For 3-5, the two OPy ligands chelate to the Oh-bound Ti metal center with two terminal OR ligands. Compounds 1-5 were fully characterized using a variety of analytical techniques. An initial investigation of the proposed chemical stability of the '(OPy)2Ti' moiety of 3-5 to alcoholysis exchange pathways involving (i) alkyl alcohols, (ii) aryl alcohols, (iii) substituted phenols, (iv) H-OR* derivatives, and (v) silanols proved successful through the isolation of a novel family of structurally characterized (OPy)2Ti(OR')2 (7-24) compounds.

The stepwise modifications of stoichiometric mixtures of titanium chloride (TiCl 4) and titanium iso-propoxide (Ti(OPr (i)) 4) by 2-pyridine methanol (H-OPy) led to the isolation of a systematically varied, novel family of compounds. The 3:1 reaction mixture of Ti(OPr (i)) 4:TiCl 4 yielded [Cl(OPr (i)) 2Ti(mu-OPr (i))] 2 ( 1). Modification of 1 with 1 and 2 equiv of H-OPy produced [Cl(OPr (i)) 2Ti(mu c-OPy)] 2 ( 2, where mu c = chelating bridge) and "(OPy) 2TiCl(OPr (i))" ( 3, not crystallographically characterized), respectively. Altering the Ti(OPr (i)) 4 to TiCl 4 stoichiometry to 1:1 led to isolation and identification of another dimeric species [Cl 2(OPr (i))Ti(mu-OPr (i))] 2 ( 4). Upon modification with 1 equiv of H-OPy, [Cl 2(OPr (i))Ti(mu c-OPy)] 2 ( 5) was isolated from toluene and (OPy)TiCl 2(OPr (i))(py) ( 6) from py. An additional equivalent of H-OPy led to the monomeric species (OPy) 2TiCl 2 ( 7). Because of the low solubility and similarity in constructs of these compounds, additional analytical data, such as the beryllium dome or BeD-XRD powder analyses, were used to verify the bulk samples, which were found to be in agreement with the single crystal structures.

The response of a mononuclear, heteroleptic titanium alkoxide [(OPy)2Ti(4MP)2, where OPy = pyridinecarbinol; NC5H4(CH2O) and 4MP = 4-mercaptophenol; OC6H4(SH)] to ultraviolet (UV) irradiation in dilute solution and in solid-state samples has been measured. Vibrational spectroscopy [Fourier transform infrared (FTIR) absorption and Raman scattering] was used to monitor changes in molecular structure upon exposure to 337.1- and 365-nm light. Assignment of spectral features to vibrational modes of the molecule was aided by a normal-mode analysis of the energy-minimized molecular structure within a density-functional theory framework. Photoinduced decreases in peak areas were observed in both FTIR spectra of the precursor solutions and Raman data collected from solution-cast films of the precursor material. These changes were associated with vibrational modes localized at the 4MP ligands. Conversely, no significant modification of vibrational structure associated with the OPy moiety was observed under the excitation conditions examined. In a related study, thin films of the precursor were cast, sampled, and irradiated with UV light in scintillation vials under hydrated air (40% relative humidity) and dry Ar to evaluate the influence of local atmospheric composition on the photoresponse. An increase in the magnitude of photoinduced vibrational changes was observed in the moist-air environment, again associated primarily with the 4MP ligand. The results support an interpretation of these structural changes in terms of a preferential enhancement of hydrolysis at the 4MP site under these conditions. These findings are discussed in the context of an optically driven molecular assembly strategy based on the photoinitiation of intermolecular bonding at selected sites about the metal center.

The effects of ultraviolet irradiation on a heteroleptic titanium alkoxide ((OPy)2Ti(4MP)2) have been investigated. The molecule has been studied in solution and in thin film form using FTIR and Raman spectroscopies. Quantum computational modeling was used to associate vibrational modes with structural moieties present in the molecule. In all cases examined, a preferential photoinduced modification in vibrational resonances linked to the 4-mercaptophenol (4MP) ligand was observed. In contrast, little or no change was exhibited in the vibrational structure of the OPy ligands.