Potential Impact of Substituents on the Crystal Structures and Properties of Tl(I) Ferrocenyl/Picolyl‐Functionalized Dithiocarbamates; Tl⋯H‐CAnagostic Interactions

New ferrocenyl/pyridyl functionalized dithiocarbamate complexes, [Tl(dtc)] ∞ (dtc=(N‐ferrocenyl‐N‐2‐methylpyridyl) dithiocarbamate (L1) 1 , (N‐ferrocenyl‐N‐methyl) dithiocarbamate (L2) 2 , (N‐methylthiophene‐N‐3‐methylpyridyl) dithiocarbamate (L3) 3 , (N‐4‐chlorobenzyl‐N‐3‐methylpyridyl) dithiocarbamate (L4) 4 and (N‐4‐methylbenzyl‐N‐3‐methylpyridyl) dithiocarbamate (L5) 5 ) have been synthesized and characterized by elemental analyses, IR, UV‐Vis., 1 H and 13 C { 1 H} NMR spectroscopy. Their crystal structures revealed polymeric structures based on dimeric [Tl(dtc)] 2 scaffolds which are linked via Tl⋯Tl, Tl‐N(Py) and Tl⋯S bonds and rare C−H⋯Tl anagostic, C–S⋯Tl, Tl⋯N(dtc), Tl⋯C and Tl⋯π(arene) intermolecular bonding interactions which have been assessed by theoretical calculations.The supramolecular structures in these complexes have been sustained by weak C−H⋯S, C−H⋯N, C−H⋯Cl, C−H⋯π, π⋯ π and H⋯H interactions. Except for 1 and 2 having ferrocene groups as quenchers, all the complexes show luminescent characteristics in the solid phase. Complexes 1–5 are weakly conducting (σ rt ,10 −4 ‐10 −7 S cm −1 , Ea=0.89‐1.00 eV) but show semiconducting behavior in the solid state. The TGA decomposition products of 1—5 revealed formation of binary TlS and ternary Fe 2 Tl 4 S 5 and Fe 3 Tl 2 S 4 sulfide materials.