@article { ISI:000372756700003, title = {DFT based assay for tailor-made terpyridine ligand-metal complexation properties}, journal = {Molecular Simulations}, volume = {42}, number = {8}, year = {2016}, month = {MAY}, pages = {618-627}, publisher = {TAYLOR \& FRANCIS LTD}, type = {Article}, address = {4 PARK SQUARE, MILTON PARK, ABINGDON OX14 4RN, OXON, ENGLAND}, abstract = {
Electron-rich terpyridine ligand and its metal complexes have a potential to grow as responsive surfaces by adapting their physicochemical properties as a function of environment. The responsiveness is brought about by judicious molecular level designing that is currently hindered due to lack of information and control on terpyridine (TPy)-metal (M) interactions at single molecule level. So far there is no organised understanding on the binding of different metals with TPy ligand and ways to modulate it. Being a large conjugated [GRAPHICS] system, TPy has a large scope to be functionalised with electron exchanging groups to alter its electronic structure and consequently its binding with metal atoms. In first report of such a kind, using density functional theory (DFT), we demonstrate that convenient modulation of TPy-M binding is possible through functionalisation of TPy for [GRAPHICS] , Ru, Fe, Mo and Au. Electron donating groups viz., CH [GRAPHICS] , OCH [GRAPHICS] , C [GRAPHICS] H [GRAPHICS] , NH [GRAPHICS] and electron withdrawing groups viz., CF [GRAPHICS] , COOH, CN and NO [GRAPHICS] are considered for functionalisation of TPy ligand. Significantly, the present work focuses on the functionalisation at 4 and 4 [GRAPHICS] positions of TPy molecule. The role of such a functionalisation in influencing the ligands structure-property correlation is missing in the literature to the best of our knowledge. The present investigation quantifies that by pertinent functionalisation of TPy, TPy-M binding energies can be modified up to [GRAPHICS] 60kcal/mol. Our results reveal that functionalisation leads to a considerable charge redistribution within the TPy-M complex with carbon atoms in pyridine rings functioning as major electron sink/source with a corresponding red/blue shift of [GRAPHICS] stretching frequency. This modifies the red-ox, optical and other chemical properties of TPy-M complexes. In brief, the present report illustrates a way to design ligands such as TPy for diverse applications through tailor-made functionalisation using electronic structure methodology.
}, keywords = {Binding energy, charge redistribution, Density functional theory, functionalisation, Metal organic complexes, metal-ligand interactions, terpyridine}, issn = {0892-7022}, doi = {10.1080/08927022.2015.1067368}, author = {Joshi, Krati and Krishnamurty, Sailaja and Singh, Iksha and Selvaraj, Kaliaperumal} }