TY - JOUR

T1 - Tuning of the coordination and emission properties of 4-amino-2,1,3-benzothiadiazole by introduction of diphenylphosphine group

AU - Sukhikh, Taisiya S.

AU - Khisamov, Radmir M.

AU - Bashirov, Denis A.

AU - Komarov, Vladislav Yu

AU - Molokeev, Maxim S.

AU - Ryadun, Alexey A.

AU - Benassi, Enrico

AU - Konchenko, Sergey N.

PY - 2020/9/2

Y1 - 2020/9/2

N2 - A novel amino-benzothiadiazole bearing diphenylphosphine groups (L) was designed and synthesized. A number of its coordination compounds of Cu(I) (1·0.75C7H8, 2a,b), Pd(II) (4), and Pt(II) (5) were prepared demonstrating the coordination of L ligand via N and/or P atoms. The reaction with strong Lewis acid Zn(II) resulted in the rearrangement of P - N - P to P-P-N moiety and formation of complex 3. The structures of L, 2-5 were determined by single crystal X-ray (XRD) diffraction, while that of 1·0.75C7H8 was determined by powder XRD analysis. Intermolecular secondary bonding of S···S interactions in the compounds, unusual for benzothiadiazoles, was discussed supported by quantum chemical calculations. Differences in the structures of the compounds cause significant changes of photophysical properties. In particular, the position of the electronic absorption band is featured by the conformation of L, viz., the dihedral angle between the benzothiadiazole unit and the P - N - P moiety, as proved by TD-DFT calculations performed on model molecules. The photophysical properties of the compounds also strongly depend on the coordination mode of L: the presence of a bond between the metal and the N atom of the thiadiazole unit plays an essential role in defining the position of the absorption and emission bands as well as emission lifetime of these compounds. The thermally activated delayed fluorescence and phosphorescence mechanisms in a thermal equilibrium were determined for 1·0.75C7H8. Complex 5 features a broad emission band spanning the entire visible region; moreover, it shows an unusual clear-white luminescence, which remains visible even in the daylight.

AB - A novel amino-benzothiadiazole bearing diphenylphosphine groups (L) was designed and synthesized. A number of its coordination compounds of Cu(I) (1·0.75C7H8, 2a,b), Pd(II) (4), and Pt(II) (5) were prepared demonstrating the coordination of L ligand via N and/or P atoms. The reaction with strong Lewis acid Zn(II) resulted in the rearrangement of P - N - P to P-P-N moiety and formation of complex 3. The structures of L, 2-5 were determined by single crystal X-ray (XRD) diffraction, while that of 1·0.75C7H8 was determined by powder XRD analysis. Intermolecular secondary bonding of S···S interactions in the compounds, unusual for benzothiadiazoles, was discussed supported by quantum chemical calculations. Differences in the structures of the compounds cause significant changes of photophysical properties. In particular, the position of the electronic absorption band is featured by the conformation of L, viz., the dihedral angle between the benzothiadiazole unit and the P - N - P moiety, as proved by TD-DFT calculations performed on model molecules. The photophysical properties of the compounds also strongly depend on the coordination mode of L: the presence of a bond between the metal and the N atom of the thiadiazole unit plays an essential role in defining the position of the absorption and emission bands as well as emission lifetime of these compounds. The thermally activated delayed fluorescence and phosphorescence mechanisms in a thermal equilibrium were determined for 1·0.75C7H8. Complex 5 features a broad emission band spanning the entire visible region; moreover, it shows an unusual clear-white luminescence, which remains visible even in the daylight.

KW - COMPLEXES

KW - BENZOTHIADIAZOLE

KW - CHEMISTRY

KW - SUBSTITUENTS

KW - LIGANDS

KW - PROGRAM

KW - CELLS

KW - SALTS

KW - FORM

UR - http://www.scopus.com/inward/record.url?scp=85085354517&partnerID=8YFLogxK

U2 - 10.1021/acs.cgd.0c00406

DO - 10.1021/acs.cgd.0c00406

M3 - Article

AN - SCOPUS:85085354517

VL - 20

SP - 5796

EP - 5807

JO - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

IS - 9

ER -