A series of new multitopic ligands with rigid linear geometry are formed by joining tris(pyrazolyl)methane and tris(pyrazolyl)borate units with arenyl and alkynyl linkers using Sonogashira and related alkynyl coupling reactions. These ligands are new examples of “third generation” poly(pyrazolyl)borate and poly(pyrazolyl)methane ligands, ligands functionalized at the non-coordinating “back” positions of either the boron or central carbon atoms. The reaction of Na[OCH₂C(pz)₃] with propargyl bromide yields HC₂CH₂OCH₂C(pz)₃ (2) and homocoupling of this alkyne yields [-C₂CH₂OCH₂C(pz)₃]₂. The reaction of Na[OCH₂C(pz)₃] with 3,5-(BrCH₂)₂C₆H₃I yields 3,5-[(pz)₃CCH₂OCH₂]₂C₆H₃I (4), which can be converted to 3,5-[(pz)₃CCH₂OCH₂]₂C₆H₃(C₂H) (6) by reaction with HC₂SiMe₃ followed by removal of the SiMe₃ group. Compounds 4 and 6 can be combined to form {3,3′,5,5′-[(pz)₃CCH₂OCH₂]₄(1,1′-C₆H₃C₂C₆H₃) (7) and 6 homocoupled to form {3,5-[(pz)₃CCH₂OCH₂]₂C₆H₃C₂-}₂. Compound 6 reacts with p-I₂C₆H₄ to produce 3,3′,5,5′-[(pz)₃CCH₂OCH₂]₄[p-(1,1′-C₆H₃C₂)₂C₆H₄], which can also be formed by the reaction of 4 with bis(ethynyl)benzene. The reaction of 2 with Fe[(p-IC₆H₄)B(pz)₃]₂ yields the bitopic, metalloligand Fe[(pz)₃CCH₂OCH₂-C₂-C₆H₄B(κ³-N,N′,N″-pz)₃]₂ (10) and a similar reaction with 6 yields the tetratopic metalloligand Fe[{3,5-[(pz)₃CCH₂OCH₂]₂C₆H₃C₂}C₆H₄B(κ³-N,N′,N″-pz)₃]₂. The molecular structures of 2, 4, 7, and 10·4CH₂Cl₂ are reported and their supramolecular structures, organized by a series of CH⋯I and CH–π interactions, are detailed.