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Insertion of aromatic nitriles into Al-N and Ga-N bonds are reported. Sterically less hindered aluminum amide [PhNHAlMe2]2 (1) undergoes C=N insertion with benzonitrile to give an isomeric mixture of tetracyclic triazaalanes {[PhNC(Ph)N]3[PhNC(Ph)NH]Al[AlMe][AlMe2]2} (2 and 3). A similar reaction with analogous gallium amide affords a tetracyclic triazagallane {[PhNC(Ph)N]3[PhNC(Ph)NH]Ga[GaMe][GaMe2]2} (6) along with a novel bowl shaped carbon containing Ga-N cluster {[PhNC(Ph)N][PhN][GaMe]2}3 (5). On the other hand, when sterically bulky gallium amide (Dipp on N, Dipp = 2,6-diisopropylphenyl) is employed, a tetrameric gallium amidinate {[(Dipp)NC(Ph)N]GaMe}4 (8) is obtained. Tetracyclic triazagallazane 6 is also synthesized from the condensation reaction of N-phenylbenzamidine with GaMe3·OEt2. Unlike AlMe3, this reaction produces only one isomer. In case of amidines with bulkier substituents on N such as Dipp, formation of a bicyclic triazagallane {[(Dipp)NC(Ph)NH]2[(Dipp)NC(Ph)N][GaMe]2} (14) is also observed along with tetrameric gallium amidinate 8, whereas N-tert-butylbenzamidine affords exclusively a tetrameric gallium amidinate {[(tert-Bu)NC(Ph)N]GaMe}4 (15) similar to its Al analogue. However, treating N-(Dipp)acetamidine with GaMe3·OEt2 gives only a bicyclic triazagallane {[(Dipp)NC(Me)NH]2[(Dipp)NC(Me)N][GaMe]2} (16). An intermediate [(tert-Bu)N(H) C(Ph)NGaMe2]2 (17), which is involved in the formation of tetrameric gallium amidinate 15, is also characterized. A comparison of the structural parameters of Ga-N-C and Al-N-C frameworks synthesized in this study is reported. [ABSTRACT FROM AUTHOR]

Although the (GaN)1-x(ZnO)x solid solution is one of the most effective systems for driving overall solar water splitting with visible light, its quantum yield for overall water splitting using visible light photons has not yet reached ten percent. Understanding and controlling the nanoscale morphology of this system may allow its overall conversion efficiency to be raised to technologically relevant levels. We describe the use a Ga2O3(ZnO)16 precursor phase in the synthesis of this phase which naturally results in the production of arrays of nanorods with favorable diameters (~100 nm) and band gaps (~2.5 eV). Substantial absorption within the band gap is observed, part of which is found to follow the E-3 scaling characteristic of free carriers scattered by ionized impurity sites. Compositional analysis suggests that a substantial quantity of cation vacancies (~3%) may be present in some samples. The typical nanorod growth direction and dominant {1011} facet for powders in this system have been identified through electron microscopy methods, leading to the conclusion that polarity may play an important role in the high photoactivity of this family of wurtzite semiconductors. [ABSTRACT FROM AUTHOR]