Conformation driven in situ interlock: from discrete metallocycles to infinite polycatenanesElectronic supplementary information (ESI) available: Additional details of the experimental procedure, additional figures and ESI-MS spectra of compounds 1-3. CCDC 1054664-1054666 and 1058370. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5cc04854k

A novel conformation driven self-assembly system, where four metallocycles with different conformations have been in situ self-assembled, has been reported. Interestingly, only square metallocycles can further interlock into polycatenanes. However, rectangular and rhombus metallocycles fail to overcome such an entropically unfavourable process, which constitutes an obstacle to the formation of polycatenanes. Are these three metallocycles, [Hg 2 L 2 Cl 4 ], [Ag 2 L 2 (CF 3 SO 3 ) 2 ] and [Zn 2 L 2 Cl 4 ], have the desired conformations as we expected? Which metallocycle inclines to interlock each other to form catenane?