Synthesis of [{AgOCCHOMe(PPh)} ] and theoretical study of its use in focused electron beam induced deposition.

The synthesis, chemical and physical properties of [{AgOCCHOMe} ] () and [{AgOCCHOMe(PPh)} ] () are reported. Consecutive reaction of AgNO with HOCCHOMe gave , which upon treatment with PPh produced . Coordination compound forms a 1D coordination polymer in the solid state as evidenced by single crystal X-ray structure analysis. The coordination geometry at Ag is of the [3 + 1] type, whereby the carboxylate anions act as bridging ligands. The formation of PPh-Ag(I) coordinative bonds results in distorted T-shaped AgPO units, which are stabilized further by an additional O-Ag dative bond. TG and TG-MS measurements show that and decompose at 190-250 °C () and 260-300 °C () via decarboxylation, involving Ag-P (), C-C and C-O bond cleavages to give elemental silver as confirmed by PXRD studies. In order to verify if polymeric is suitable as a FEBID precursor for silver deposition, its vapor pressure was determined ( = 5.318 mbar, = 126.1 kJ mol), evincing little volatility. Also EI and ESI mass spectrometric studies were carried out. The dissociation of the silver(I) compound under typical electron-driven FEBID conditions was studied by DFT (B3LYP) calculations on monomeric [AgOCCHOMe(PPh)]. At an energy of the secondary electrons up to 0.8 eV elimination of PPh occurs, giving Ag and OCCHOMe. Likewise, by release of PPh from [AgOCCHOMe(PPh)] the fragment [AgOCCHOMe] is formed from which Ag and OCCHOMe is generated, further following the first fragmentation route. However, at 1.3 eV the initial step is decarboxylation giving [AgCHOMe(PPh)], followed by Ag-P and Ag-C bond cleavages.