Executive Summary : | The effect of external electric fields (EEFs) on the structure and reactivity of molecules has been captured very recently. Of late, it has been reported that EEFs can be utilised to exert unprecedented control over chemical reactivity, offering a plethora of new synthetic tools for the organic, organometallic, bioinorganic and materials chemists to explore this approach. The possibilities and applications offered by this “new” technology (EEFs) seem to be endless and offer a non-chemical way to fine-tune various properties/reactions eliminating the need to make hundreds of compounds to achieve the desired target. Despite this advantage, several practical impediments to its widespread adoption in synthetic chemistry remain to be addressed as very little is understood about how EEFs influence the molecular geometry and related properties/functions of interest. Using computational tools such as DFT/CASSCF methods, we recently proposed a way to fine-tune the magnetic anisotropy of Ln(III) SMMs using EEF and suggested that by applying an electric field in a particular direction, convert a non-SMMs to SMM with barrier height for magnetisation reversal exceeding 1500 cm-1. It is well known that magnetic fields are hardly suitable to control electron spins because of their poor spatial locality, whereas electric fields are a convenient alternative because strong electric fields can be applied at high spatial resolution. The electric field modulation of spin in molecule offers various advantages (i) they can be applied to a very small volume via an STM tip, (ii) they can be turned on and off rapidly. In this proposal, we aim to study the effect of EEFs using DFT and ab initio methods (i) to modulate magnetic anisotropy of transition metal SMMs (ii) fine-tune SMM behaviour of Lanthanide magnets, (iii) offer a viable way to switch toroidal states in Ln(III) SMTs (iv) study spin-electric coupling in spin-frustrated magnetic triangular systems (iv) explore the catalytic behaviour of high-valent metal-oxo species towards C-H bond activation. |