Details

Autor(en) / Beteiligte

• Firdoos, Tahira
• Kumar, Pretam
• Sharma, Nipunn
• Gomila, Rosa M
• Frontera, Antonio
• Sood, Puneet
• Pandey, Sushil K

Titel

Thallium()phosphorodithioates containing intra- and intermolecular π-hole triel bonds

Ist Teil von

• CrystEngComm, 2023-07, Vol.25 (26), p.3777-3789

Ort / Verlag

Cambridge: Royal Society of Chemistry

Erscheinungsjahr

2023

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Thallium compounds, i.e. Tl + [S 2 P{OC 6 H 3 (2,5-(CH 3 ) 2 )} 2 ] − ( 1 ) and Tl + [S 2 P{OC 6 H 3 (3,5-(CH 3 ) 2 )} 2 ] − ( 2 ), stabilized by intra- and intermolecular triel bonds were isolated and characterized by FT-IR, NMR ( 31 P, 1 H and 13 C) spectroscopy, and SC-XRD analysis. The crystal structures of 1 and 2 belong to monoclinic crystal systems with the space group C 2/ c and P 2 1 / n , respectively. Interestingly, the positively charged Tl atom is bonded attractively with the π-holes of the 1,1-dithioate moiety. These compounds exist in ionic form and exhibit Tl S and Tl π contacts (TrBs), which assist the formation of unique supramolecular polymeric architectures owing to the stereochemically active lone pair of electrons and hemi-directed coordination sphere around thallium. A differentiating feature in compound 2 is the formation of a unique Tl π/π π/Tl π self-assembly. The attractive nature of TrB was further confirmed by DFT calculations using the quantum theory of atoms-in-molecules (QTAIM) and non-covalent interaction plot (NCIPlot) index methods. A systematic Hirshfeld surfaces analysis was also carried out to compare the intermolecular interactions. Two new thallium compounds containing intra- and intermolecular triel bonds were isolated and characterized. The triel bonds were studied by HSA and DFT calculations using QTAIM and NCIPlot index methods.