A new class of D-3-symmetric tris(spiroborate) cyclophanes has been designed and prepared for the construction of supramolecular chain structures by iterative host-guest interaction with ditopic guest molecules. The treatment of these compounds with [Ir(tpy)(2)](PF6)(3) complex in solution led to the formation of the chain structure, which was confirmed by H-1 NMR and CSI-MS studies. The chain structure exhibited rapid temperature-responsive gelation behavior in their HMPA solution.