pubs.acs.org/cm Published on Web 08/25/2009 r 2009 American Chemical Society Chem. Mater. 2009, 21, 4233–4240 4233 DOI:10.1021/cm901200h Nanoparticles and Thin Films of Silver from Complexes of Derivatives of N-(Diisopropylthiophosphoryl)thioureas Damir A. Safin,* ,† Phumlane S. Mdluli, ‡ Neerish Revaprasadu, ‡ Kibriya Ahmad, § Mohammad Afzaal, § Madeleine Helliwell, § Paul O’Brien,* ,§ Elmira R. Shakirova, # Maria G. Babashkina, † and Axel Klein † † Institut f :: ur Anorganische Chemie, Universit :: at zu K :: oln, Greinstrasse 6, D-50939 K :: oln, Germany, ‡ Department of Chemistry, University of Zululand, Private bag X1001, KwaDlangezwa 3886, South Africa, § The School of Chemistry and Manchester Materials Science Centre, University of Manchester, Oxford Road, Manchester M13 9PL, United Kingdom, and # A.M. Butlerov Chemistry Institute, Kazan State University, 420008, Kremlevskaya Street 18, Kazan, Russian Federation Received April 30, 2009. Revised Manuscript Received July 24, 2009 The derivatives of N-(diisopropylthiophosphoryl)thiourea RC(S)NHP(S)(O i Pr) 2 (R=C 5 H 11 N, C 5 H 6 N 2 or C 10 H 7 NH 2 ) followed by their complexation with silver are reported. All complexes are decomposed in hot hexadecylamine (HDA) to give HDA-capped silver nanoparticles. The absorp- tion spectra of the HDA-capped silver nanoparticles exhibit surface plasmon resonance (SPR) absorption in the 400-420 nm region. Transmission electron microscopy (TEM) images of all particles are close to spherical in shape; with sizes ranging from 17 to 20 nm. The X-ray diffraction (XRD) patterns of the silver nanoparticles obtained from all three complexes could be indexed to face centered cubic silver. Scanning electron microscopy (SEM) image confirmed the spherical shape of the particles. The silver complex of 1-naphthylamine was also used to deposit thin films of silver by the aerosol-assisted chemical vapor deposition (AACVD). Introduction The use of single molecular precursors is becoming a common route for preparing nanostructured materials. 1-8 Various approaches have been taken to the preparation of thin films and finely divided particles of metals such as silver or gold; but there have been relatively few reports on the use of specific precursor chemistry for metal nanopar- ticles. The most commonly reported routes to such species are from solutions of readily available metal salts which are reduced at room temperature, in the presence of stabilizing agents to give surface derivatized metal particles. The dimethyl formamide (DMF) reduction method is, for example, well-established for silver nanoparticles of diverse morphology. 9-12 Alternative methods for the formation of silver nanorods using solid-liquid phase arc-discharge or ultraviolet irradiation-photoreduction have been reported by Zhou and co-workers. 13 A microwave polyol reduction method, in which the molecular weight of PVP is varied, in the presence of nucleation agents such as H 2 PtCl 6 6H 2 O, also produces nanowires. 14 Murphy and co-workers have also synthesized silver nanorods and nanowires by using a rodlike micelle template of cetyltrimethylammonium bro- mide (CTAB). 15 Green and co-workers reported the syn- thesis of trialkyl phosphine oxide/amine stabilized silver nanocrystals. 16 Nath et al. have synthesized hexadecyl- amine (HDA)-capped silver organosols which were stable for over a year. 17 Chen et al., 18 developed an important method using tri-n-octylphosphine (TOP) as the reducing agent, solvent, and surfactant. Thin films of silver have been deposited by vari- ous methods including sputtering, 19 thermal evaporation, *Corresponding author. (1) Pickett, N. L.; O’Brien, P. Chem. Rec. 2001, 1, 467. (2) Malik, M. A.; O’Brien, P.; Revaprasadu, N. Phosphorus, Sulfur Silicon 2005, 180, 689. (3) Malik, M. A.; Revaprasadu, N.; O’Brien, P. Chem. Mater. 2001, 13, 913. (4) Trindade, T.; O’Brien, P.; Pickett, N. L. Chem. Mater. 2001, 13, 3843. (5) Burda, C.; Chen, X.; Narayanan, R.; El-Syed, M. A. Chem. Rev. 2005, 105, 1025. (6) Li, Y.; Li, X.; Yang, C.; Li, Y. J. Mater. Chem. 2003, 13, 2641. (7) Revaprasadu, N.; Mlondo, S. N. Pure Appl. Chem. 2006, 78, 1691. (8) Bruce, J. C.; Revaprasadu, N.; Koch, K. R. New J. Chem. 2007, 31, 1647. (9) Pastoriza-Santos, I.; Liz-Marzan, L. M. Pure Appl. Chem. 2000, 72, 83. (10) Deivaraj, T. C.; Lala, N. L.; Lee, J. Y. J. Colloid Interface Sci. 2005, 289, 402. (11) Suber, L.; Sondi, I.; Matijevi c, E.; Goia, D. V. J. Colloid Interface Sci. 2005, 288, 489. (12) Mdluli, P. S.; Revaprasadu, N. J. Alloys Compd. 2009, 469, 519. (13) Zhou, Y.; Yu, S. H.; Cui, X. P.; Wang, C. Y.; Chen, Z. Y. Chem. Mater. 1999, 11, 545. (14) Tsuji, M.; Nishizawa, Y.; Matsumoto, K.; Kubokawa, M.; Miyamae, N.; Tsuji, T. Mater. Lett. 2006, 60, 834. (15) Murphy, C. J.; Sau, T. K.; Gole, A. M.; Orendorff, C. J.; Gao, J.; Gou, L.; Hunyadi, S. E.; Li, T. J. Phys. Chem. B 2005, 109, 13857. (16) Green, M.; Allsop, N.; Wakefield, G.; Dobson, P. J.; Hutchison, J. L. J. Mater. Chem. 2002, 12, 2671. (17) Nath, S.; Praharaj, S.; Panigrahi, S.; Kundu, S.; Ghosh, S. K.; Basu, S.; Pal, T. Colloids Surf., A 2006, 274, 145. (18) Chen, Z.; Gao, L. Mater. Res. Bull. 2007, 42, 1657. (19) Hauder, M.; Gst :: ottner, J.; Hansch, W.; Schmitt-Landsiedel, D. Appl. Phys. Lett. 2001, 78, 838. (20) Carter, A. C.; Chang, W.; Qadri, S. B.; Horwitz, J. S.; Leuchtner, R.; Chrisey, D. B. J. Mater. Res. 1998, 13, 1418. Downloaded by MUENSTER LIBRARIES on September 16, 2009 | http://pubs.acs.org Publication Date (Web): August 25, 2009 | doi: 10.1021/cm901200h