Intermolecular Tl⋯H–C anagostic interactions in luminescent pyridyl functionalized thallium(i) dithiocarbamates

Abstract

Crystal structures of novel pyridyl functionalised [Tl(L)]∞ (L = (N-benzyl-N-methylpyridyl) dithiocarbamate(L1) 1, bis(N-methylpyridyl) dithiocarbamate(L2) 2, (N-methyl(1,4-benzodioxane-6-yl)-N-methylpyridyl)dithiocarbamate(L3) 3, (N-ferrocenyl-N-methylpyridyl) dithiocarbamate(L4) 4) complexes revealed rare intermolecular C-H···Tl anagostic and C-S···Tl interactions forming a six-membered chelate ring about the metal center, which have been assessed by DFT calculations. The strong thallophilic bonding is responsible for the strong luminescent characteristics of the complexes in the solid phase.

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

“…In all five structures the basic unit is a centrosymmetric Tl 2 (dtc) 2 moiety in common with previous thallium structures . In 1 the asymmetric unit contains two independent thallium atoms, Tl(1) and Tl(2), Figure which are bonded to each other at 3.769(1) Å.…”

“…In recent years considerable attention has been paid towards the coordination chemistry and use of metal dithiocarbamates including those of main group metals (Zn, Cd, Sn, and Pb) as molecular precursors for the preparation of thin film metal sulfide nanomaterials . By comparison despite synthetic versatility and practical utility, the corresponding thallium dithiocarbamates have received little attention until recently . The majority of known thallium dithiocarbamates are those containing classical alkyl/aryl dithiocarbamates which form polymeric chain structures containing the dimeric [Tl(dtc)] 2 unit connected via Tl⋯S bonds.…”

“…The majority of known thallium dithiocarbamates are those containing classical alkyl/aryl dithiocarbamates which form polymeric chain structures containing the dimeric [Tl(dtc)] 2 unit connected via Tl⋯S bonds. Recently we demonstrated that the introduction of pyridyl groups on the backbone of dithiocarbamates resulted in the formation of 2D polymeric structures through Tl−N,Tl⋯Tl and Tl⋯H−C and anagostic interactions . Thallium complexes show interesting structural features due to the stereochemical activity of the 6s 2 lone pair of electrons and also exhibit intriguing photophysical properties.…”

“…The thallophilic Tl−Tl contacts within 4.0 Å are generally considered weaker metallophilic interactions between the closed‐shell metal atoms in comparison with strong “aurophilic” bonding in Au(I) complexes . Tl⋯Tl interactions have been found to play key role in the prominent luminescent characteristics of the Tl(I) complexes , , , …”

Sonochemical synthesis of a two‐dimensional supramolecular polymer with nanoporous morphology, linear thallophilic and covalent hydrogen‐bonding interactions

“…A search on reported values in the literature shows that Tl···Tl distances in poly[( μ ‐benzene‐1,4‐dithiolato)dithallium], Tl 2 (SC 6 H 4 S) are equal to 3.49 and 3.58 Å, and in poly[(μ‐benzene‐1,4‐diselenolato)dithallium], Tl 2 (SeC 6 H 4 Se), are equal to 3.54 and 3.63 Å . Also in [Tl(L)] ∞, [L = (N‐benzyl‐N‐methylpyridyl)dithiocarbamate (L1), bis(N‐methylpyridyl)dithiocarbamate (L2), (N‐methylpiperonyl‐N‐methylpyridyl)dithiocarbamate (L3) and (N‐ferrocenyl‐N‐methylpyridyl) dithiocarbamate (L4)], Tl···Tl distances are equal to 3.771 Å and 3.817 Å and 3.763 Å and 3.735 Å, respectively . catena ‐[bis( μ 3 ‐salicylato)dithallium(I)], catena ‐[bis( μ 3 ‐ ortho‐ aminosalicylato)dithallium(I)], catena ‐[(3,5‐dimethoxybenzoato)thallium(I)] have Tl … Tl separations of 4.213 (1) Å, 4.129 Å and 4.1669 (8) Å, respectively .…”