A series of diarylacetylene (tolane) derivatives functionalised at the 4- and 4′-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 CH21136_IE1.gif of an asymmetric molecule X-B-Y is the geometric mean CH21136_IE2.gif of the conductance of the two symmetric molecules derived from it, CH21136_IE3.gif and CH21136_IE4.gif.' 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. © 2021 Journal Compilation CH21136_TOC.jpg