RATIONALE: Carbon-phosphides are new and promising strategic materials with applications e.g. in optoelectronics. However, their chemistry and methods of synthesis are not completely understood, and only a limited number of C-P clusters have been detected up to now. Laser ablation synthesis (LAS) or laser desorption ionisation (LDI) has great potential to generate Cm Pn clusters in the gas phase and to act as the basis for the development of new technology. METHODS: The LAS of carbon phosphides using mixtures of nano-carbon sources (graphene, nanodiamonds) with phosphorus allotropes (red, black, and phosphorene) was examined. Since phosphorene is not commercially available, it was synthesised. A reflectron time-of-flight mass spectrometer was used to produce and identify the C-P clusters. A transmission electron microscope was used to characterise the prepared composites. RESULTS: LDI of various carbon-phosphorus composites generated a range of carbon-phosphides. From graphene-red phosphorus, Cm P+ (m = 3-47), Cm P2+ (m = 2-44), Cm P3+ (m = 1-42), Cm P4+ (m = 1-39), Cm P5+ (m = 1-37), Cm P6+ (m = 1-34), Cm P7+ (m = 1-31), Cm P8+ (m = 1-29), Cm P9+ (m = 1-26), Cm P10+ (m = 1-24), Cm P11+ (m = 1-21), and Cm P12+ (m = 1-19) clusters were detected, while nanodiamond composites with red/black phosphorus and with phosphorene yielded C24 P5 + 2n+ (n = 0-28), C24 P5 + 2n+ (n = 0-16), and C24 P5 + 2n+ (n = 0-14) clusters, respectively. In total, over 300 new carbon-phosphide clusters were generated. CONCLUSIONS: The novel series of carbon-phosphide clusters generated from graphene or nanodiamond composites with red/black phosphorus or with phosphorene demonstrated rich carbon-phosphide chemistry that might inspire the development of novel nano-materials with specific properties.

Department of Chemistry Faculty of Science Masaryk University A14 326 Kamenice 753 5 625 00 Brno Czech Republic

Department of Chemistry Faculty of Science Masaryk University A14 326 Kamenice 753 5 625 00 Brno Czech Republic International Clinical Research Center St Anne's University Hospital Pekařská 53 656 91 Brno Czech Republic

Department of Histology and Embryology Faculty of Science Masaryk University Kamenice 3 625 00 Brno Czech Republic International Clinical Research Center St Anne's University Hospital Pekařská 53 656 91 Brno Czech Republic

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