Tripodal [2]rotaxane, 3, and the structurally related axle, 2, incorporating a viologen moiety, a crown ether, and three thiol anchoring groups have been synthesized. Analogous monopodal derivatives, 1, have also been prepared. Self-assembled monolayers of the above tripodal and monopodal systems on gold have been studied by cyclic voltammetry. It has been shown that a thiol anchoring group is required to attach the monopodal viologen 1 to the surface of gold and that the maximum surface coverage of I corresponds to 2.7 x 10(-10) mol center dot cm(-2). The adsorbed monopodal viologen I does not thread bis-p-phenylene-34-crown- 10 ether, 6. However, the tripodal axle 2 adsorbed on the surface of gold threads the crown ether 6 to form a hetero, [2]rotaxane. In the case of the tripodal axle 2, the surface coverage is 7 X 10(-11) mol center dot cm(-2), while for the tripodal [2]rotaxane 3 the surface coverage reaches 1.1 X 10(-10) mol center dot cm(-2.)