Vreshch V. Step-by-step construction of heterobimetallic coordination polymers employing functionality of a pyridyl substituted b-diketonates

The dissertation deals with step-by-step approach for the synthesis of heterobimetallic coordination polymers. The presented strategy is based on the synthesis of b-diketonate complexes from ampolydentate b-diketones as a first step, and the subsequent use of the synthesized complexes with pendant pyridyl groups as ligands in their own way. Accordingly, series of substituted diketones, including phenyl and biphenyl substituted ones as model ligands, and corresponding diketonates of Be(II), Al(III), Fe(III), Zr(IV) were obtained and structurally investigated (19 crystal structures). It was observed, that comparing to the expected rigid-spacer role of the bis-diketonates, the tris-complexes reveal significant flexibility and deflection from trigonal symmetry in the solid state. These observations were supported by quantum-chemical modelling and allowed to suggest, that the linear joint of trigonal blocks could lead to other possibilities than the "honeycomb" hexagonal network - the possible formation offour and eight membered cycles along with anticipated six-membered ones was stated. The diketonate ligands were used for synthesis of heterobimetallic coordination polymers with Cu(I), Cu(II), Ag(I), Zn(II), Cd(II), Co(II) - in total, 34 crystal structures were investigated and the validity of the approach is demonstrated. Main factors, influencing the structures of the coordination polymers are examined with main accent set on the role of limited flexibility of the diketonate building blocks. One of the most interesting results is the predictable observation of bimetallic squares and octagons along with hexagons as main structure motives in the structures of [AlL3] based polymers. The results presented in the dissertation substantiate the use of metal diketonates for synthesis of metal-organic frameworks towards applications and demonstrate the possibilities of rational design of crystal structure by using partially flexible building blocks.