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Determination of the X\u2010ray crystal structures of several compounds bearing different carbon backbones between the phosphorus atoms reveals the influence of the nature of the phosphane spacer on the establishment of intra and\/or intermolecular gold\u2013gold interactions. The absorption and emission properties of the complexes were analysed by taking into account the presence or absence of intermetallic interactions. Although UV\/Vis spectra show differences for compounds with intramolecular Au\u2013Au contacts, a conclusive trend was not observed in the emission behaviour. (\u00a9 Wiley\u2010VCH Verlag GmbH &amp; Co. 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