Groups: Garcia
Telephone:
01223 331696
01223 763881 (shared)
E-mail: fg230@cam.ac.uk
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Group 4 mixed-bridge frameworks: In the reaction of RTiCl3 (R= Cp and Cp*) with pyrimidines, compounds containing oxo- and imido-bridges were obained. This kind of heteroleptic compound is very rare in transition metal chemistry and not previously seen in Group 4.1 The combination of nitrogen and oxygen bridges within a polynuclear Group 4 compound provides an exciting area for structural, catalytic and reactivity studies.
The possibility of a rational design of transition metal mixed bridge compounds by using oxo- bridge complexes as building blocks opens an exciting path for a wide range of novel Group 4 frameworks. The dimensionality of the proposed family of compounds would be driven by (i) the extent of substitution on the metal centre, i.e. RCl2M-O- MCl2R would rise up 3D frameworks, whereas R2ClM-O- MClR2 is expected to produce compounds such as polymers or macrocycles (Scheme 1) and (ii) the steric demands around the metal centres, i.e. the bigger the R groups, the smaller the oligomer formed.
Towards 3D inorganic frameworks appended with radicals: The use of molecular magnetic materials provides many opportunities for low-temperature device fabrication and offers an opportunity to tailor the physical properties at a molecular level via general organic synthesis. However, probably the most appealing aspect of molecule-based magnets is that they present several attributes unavailable in conventional metal and metal-oxide magnets, such as low density, solubility in a wide variety of common solvents and/or volatility. These physical properties provide a number of potentially important opportunities in low temperature processing techniques such as electro-coating, evaporation and chemical vapour deposition.
In collaboration with Dr. A. Alberola-Catalán (UJI, Spain), we are working towards the rational assembly of large macromolecular systems with multiple spin carriers we have started functionalizing dimeric phospha(III)zane [ClP(μ-Npy)]2 with dithiadiazolyl radicals2 in an attempt to synthesise the units that will form part of these macrocycles. The formation of macrocycles and the possibility of 3D structural arrangements would open this area to radical functionalized nanotubes.