A series of diarylacetylene (tolane) derivatives functionalised at the 4-and 4 0 -positions by thiolate, thioether, or amine groups capable of serving as anchor groups to secure the molecules within a molecular junction have been prepared and characterised. The series of compounds have a general form X-B-X, Y-B-Y, and X-B-Y where X and Y represent anchor groups and B the molecular bridge. The single-molecule conductance values determined by the scanning tunnelling microscope break-junction method are found to be in excellent agreement with the predictions made on the basis of a recently proposed 'molecular circuit law', which states 'the conductance G XBY of an asymmetric molecule X-B-Y is the geometric mean ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi G XBX G YBY p of the conductance of the two symmetric molecules derived from it, G XBX and G YBY .' The experimental verification of the circuit law, which holds for systems in which the constituent moieties X, B, and Y are weakly coupled and whose conductance takes place via off-resonance tunnelling, gives further confidence in the use of this relationship in the design of future compounds for use in molecular electronics research.