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Multimetallic complexes and functionalized gold nanoparticles based on a combination of d- and f-Elements

Stasiuk, Graeme J.; Bell, Jimmy D.; Holmes, Holly; Sung, Simon; Toscani, Anita; Wainwright, Luke; White, Andrew J. P.; Wilton-Ely, James D. E. T.


Graeme J. Stasiuk

Jimmy D. Bell

Holly Holmes

Simon Sung

Anita Toscani

Luke Wainwright

Andrew J. P. White

James D. E. T. Wilton-Ely


The new DO3A-derived dithiocarbamate ligand, DO3A-ᵗBu-CS₂K, is formed by treatment of the ammonium salt [DO3A-ᵗBu]HBr with K₂CO₃ and carbon disulfide. DO3A-ᵗBu-CS₂K reacts with the ruthenium complexes cis-[RuCl₂(dppm)₂] and [Ru(CH═CHC₆H₄Me-4)Cl(CO)(BTD)(PPh₃)₂] (BTD = 2,1,3-benzothiadiazole) to yield [Ru(S₂C-DO3A-ᵗBu)(dppm)₂]+ and [Ru(CH═CHC₆H₄Me-4)(S₂C-DO3A-ᵗBu)(CO)(PPh₃)₂], respectively. Similarly, the group 10 metal complexes [Pd(C,N-C6H4CH₂NMe₂)Cl]₂ and [PtCl2(PPh₃)₂] form the dithiocarbamate compounds, [Pd(C,N-C₆H₄CH₂NMe₂)(S₂C-DO3A-ᵗBu)] and [Pt(S₂C-DO3A-ᵗBu)(PPh₃)₂]+, under the same conditions. The linear gold complexes [Au(S₂C-DO3A-ᵗBu)(PR₃)] are formed by reaction of [AuCl(PR₃)] (R = Ph, Cy) with DO3A-ᵗBu-CS₂K. However, on reaction with [AuCl(tht)] (tht = tetrahydrothiophene), the homoleptic digold complex [Au(S2C-DO3A-ᵗBu)]₂ is formed. Further homoleptic examples, [M(S₂C-DO3A-ᵗBu)₂] (M = Ni, Cu) and [Co(S₂C-DO3A-ᵗBu)₃], are formed from treatment of NiCl₂·6H₂O, Cu(OAc)₂, or Co(OAc)₂, respectively, with DO3A-ᵗBu-CS₂K. The molecular structure of [Ni(S₂C-DO3A-ᵗBu)₂] was determined crystallographically. The tert-butyl ester protecting groups of [M(S₂C-DO3A-ᵗBu)₂] (M = Ni, Cu) and [Co(S₂C-DO3A-ᵗBu)₃] are cleaved by trifluoroacetic acid to afford the carboxylic acid products, [M(S₂C-DO3A)₂] (M = Ni, Cu) and [Co(S₂C-DO3A)₃]. Complexation with Gd(III) salts yields trimetallic [M(S₂C-DO3A-Gd)₂] (M = Ni, Cu) and tetrametallic [Co(S₂C-DO3A-Gd)₃], with r¹ values of 11.5 (Co) and 11.0 (Cu) mM⁻¹ s⁻¹ per Gd center. DO3A-ᵗBu-CS₂K can also be used to prepare gold nanoparticles, Au@S₂C-DO3A-ᵗBu, by displacement of the surface units from citrate-stabilized nanoparticles. This material can be transformed into the carboxylic acid derivative Au@S2C-DO3A by treatment with trifluoroacetic acid. Complexation with Gd(OTf)3 or GdCl3 affords Au@S₂C-DO3A-Gd with an r¹ value of 4.7 mM⁻¹ s⁻¹ per chelate and 1500 mM⁻¹ s⁻¹ per object.


Stasiuk, G. J., Bell, J. D., Holmes, H., Sung, S., Toscani, A., Wainwright, L., …Wilton-Ely, J. D. E. T. (2014). Multimetallic complexes and functionalized gold nanoparticles based on a combination of d- and f-Elements. Inorganic chemistry, 53(4), 1989-2005.

Acceptance Date Jul 26, 2013
Online Publication Date Feb 4, 2014
Publication Date Feb 17, 2014
Deposit Date Feb 19, 2016
Publicly Available Date Feb 19, 2016
Journal Inorganic chemistry
Print ISSN 0020-1669
Electronic ISSN 1520-510X
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 53
Issue 4
Pages 1989-2005
Keywords Multimetallic; Dithiocarbamates; Nanoparticles; Images
Public URL
Publisher URL
Additional Information “This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see


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