Laser Desorption Mass Spectrometry of End Group-Protected Linear Polyynes: Evidence of Laser-Induced Cross-Linking

End group-protected linear polyynes of composition Tr*–(CC)_<i>n</i>–Tr* (with Tr* representing the super trityl group and <i>n</i> = 2, 4, 6, 8, 10) and <i>t</i>Bu–(CC)₆–<i>t</i>Bu (with <i>t</i>Bu being the tertiary butyl group) have been studied by laser desorption ionization (LDI) time-of-flight (ToF) mass spectrometry. <i>t</i>Bu-terminated polyyne molecules show considerably higher stability during laser activation than Tr*-end-capped polyyne molecules. A key feature is the abundant formation of oligomeric species upon laser activation. Tandem mass spectrometry reveals strong bonding within the oligomers which indicates cross-linking of the former polyynes within the oligomers. The process is more abundantly occurring and less energy demanding than the laser-induced coalescence of C₆₀. Cross-linking is more efficient with the smaller end group (<i>t</i>Bu), and larger oligomers are formed when the chain length of the polyyne increases, both a result of enhanced interaction of the triple bonds in neighboring chains. The presence of the matrix molecules in matrix-assisted (MA)­LDI hinders the polyyne interaction, and oligomer formation is markedly reduced