Coordination chemistry has been a consistently active branch of chemistry since Werner's seminal theory of coordination compounds inaugurated in 1893, with the central focus on transition metal complexes. However, control and measurement of metal-ligand interactions at the single-molecule level remain a daunting challenge. Here we demonstrate an interdisciplinary and systematic approach that enables measurement and modulation of the coordinative bonding forces in a transition metal complex. Terpyridine is derived with a thiol linker, facilitating covalent attachment of this ligand on both gold substrate surfaces and gold-coated atomic force microscopy tips. The coordination and bond breaking between terpyridine and osmium are followed in situ by electrochemically controlled atomic force microscopy at the single-molecule level. The redox state of the central metal atom is found to have a significant impact on the metal-ligand interactions. The present approach represents a major advancement in unravelling the nature of metal-ligand interactions and could have broad implications in coordination chemistry.
|Publication status||Published - 2013|
Bibliographical noteFunding Information:
We are grateful for the financial support from the Lundbeck Foundation (Grant No. R49-A5331 to Q.C.) and the Danske Universiteter for a postdoc fellowship to X.H. in Denmark. H.W. thanks the support from MOST (Grant No. 2011CB933600), NSFC (Grant No. 21073181) and the ‘100 Talent Program’ of CAS in China. K.M.-P. acknowledges the funding from the Chalmers Materials and Energy Areas of Advance in Sweden. J.U. acknowledges the financial support from the Villum Kann Rasmussen Foundation. K.S.T. acknowledges the support from the Danish Council for Independent Research’s Sapere Aude Program (Grant No. 11-1051390). J.Z., H.W., X.H. and Q.C. thank Professor Erkang Wang for the career development with this paper dedicated to the occasion of his 80th birthday.