Cu-based metalorganic systems: an ab initio study of the electronic structure

Abstract

Within a first principles framework, we study the electronic structure of the recently synthesized polymeric coordination compound Cu(II)-2,5-bis(pyrazol-1-yl)-1,4-dihydroxybenzene (CuCCP), which has been suggested to be a good realization of a Heisenberg spin-½ chain with antiferromagnetic coupling. By using a combination of classical with ab initio quantum mechanical methods, we design on the computer reliable modified structures of CuCCP aimed at studying effects of Cu-Cu coupling strength variations on this spin-½ system. For this purpose, we performed two types of modifications on CuCCP. In one case, we replaced H in the linker by (i) an electron donating group (NH₂) and (ii) an electron withdrawing group (CN), while the other modification consisted of adding H₂O and NH₃ molecules in the structure which change the local coordination of the Cu(II) ions. With the Nth order muffin tin orbital (NMTO) downfolding method, we provide a quantitative analysis of the modified electronic structure and the nature of the Cu-Cu interaction paths in these new structures and discuss its implications for the underlying microscopic model.