Disilver(I) Coordination Complexes: Synthesis, Reaction Chemistry, and Their Potential Use in CVD and Spin-Coating Processes for Silver Deposition

• Published in: European Journal of Inorganic Chemistry 2010-07, Vol.2010 (19), p.2975-2986
• Main Authors: Jakob, Alexander, Rüffer, Tobias, Schmidt, Heike, Djiele, Patrice, Körbitz, Kathrin, Ecorchard, Petra, Haase, Thomas, Kohse-Höinghaus, Katharina, Frühauf, Swantje, Wächtler, Thomas, Schulz, Stefan, Gessner, Thomas, Lang, Heinrich
• Format: Article
• Language: English
• Subjects: Chemical vapor deposition; Dicarb­oxylate ligands; Phosphanes; Silver; Thin films
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.201000159

The synthesis of complexes [Ag2X] [X = O2CCO2 (3a), C4O4 (3b), O2CCH2CO2 (3c), O2C(CH2)2CO2 (3d), cis‐O2CCH=CHCO2 (3e), trans‐O2CCH=CHCO2 (3f), para‐O2CC6H4CO2 (3g)] and [(R3P)mAgXAg(PR3)m] [R = Ph, X = C4O4, m = 2 (10a), m = 3 (10b); R = nBu, X = O2CCH2CO2, m = 2 (10c), m = 3 (10d); X = O2C(CH2)2CO2, m = 1 (10e), m = 2 (10f), m = 3 (10g); X = cis‐O2CCH=CHCO2, m = 1 (10h), m = 2 (10i), m = 3 (10j); X = trans‐O2CCH=CHCO2, m = 1 (10k), m = 2 (10l), m = 3 (10m); X = para‐O2CC6H4CO2, m = 2 (10n)] is reported. Compoundds 3a–3g are accessible by the reaction of [AgNO3] (1) with H2X (2a–2g), while 10a–10n can be prepared by treatment of 3a–3g with PR3 (9a, R = Ph; 9b, R = nBu) in the ratios of 1:2, 1:4, or 1:6. When [{Ag(bipym)(NO3)·H2O}n] (6) (bipym = bipyrimidine) reacts with (HNEt3)2(O2CCO2) (7), [{Ag(bipym)Ag(O2CCO2)·4H2O}n] (5) and [{(bipym)(Ag(O2CCO2H))2}n] (8) are formed. The molecular structures for 5, 6, and 8 in the solid state are reported. For 5, the formation of a 3D network is characteristic, in which 1D chains of {Ag(bipym)Ag(O2CCO2)}n interact with each other through π–π interactions between the bipym ligands to extend in one direction, while H2O molecules act as connectivities thorugh the intermolecular H‐bridge formation to extend in the other direction. Polymeric 6 consists of 2D layers formed by individual 1D chains of {Ag(bipym)Ag(bipym)}n with π–π interactions between the bipym ligands. In 8, {(HO2CCO2)Ag(bipym)Ag(O2CCO2H)} units undergo intermolecular H‐bridge formation to create 2D layers, π–π interactions between individual bipym ligands produce a 3D network. The use of 10d as a CVD precursor in the deposition of Ag on glass by using a direct liquid injection system is discussed. The Ag films show a rough appearance and contain C impurities. The use of 10e and 10f as spin‐coating precursors for the deposition of Ag on TiN‐coated oxidized Si wafers is reported. Straightforward synthesis methodologies for the preparation of several phosphane disilver dicarboxylate and squarate complexes are presented. The application of selected disilver compounds in CVD and spin‐coating processes for the deposition of silver films is discussed.