TY - JOUR

T1 - Luminescent Zn Halide Complexes with 2-(2-Aminophenyl)benzothiazole Derivatives

AU - Sukhikh, Taisiya S.

AU - Kolybalov, Dmitry S.

AU - Pylova, Ekaterina K.

AU - Konchenko, Sergey N.

N1 - Funding Information: This work is supported by the Russian Science Foundation (project no. 21-73-10096). The powder XRD analysis was carried out with the support of the Ministry of Science and Higher Education of the Russian Federation (No. 121031700313-8 and No. 121031700321-3). Publisher Copyright: © 2022 by the authors.

PY - 2022/9

Y1 - 2022/9

N2 - We report a comparative study of coordination behaviour of 2-(2-aminophenyl)benzothiazole (NH2-pbt) and its phosphorus-containing derivative, α-aminophosphine oxide (PCNH-pbt), towards zinc halides. The corresponding coordination compounds [Zn(L)2Hal2] (L = PCNH-pbt, Hal = Cl, 1 and Hal = Br, 2) and [Zn(L’)Hal2] (L’ = NH2-pbt, Hal = Cl, 3 and Hal = Br, 4) were obtained as single phases. As evidenced by single-crystal X-ray diffraction analysis, L’ ligand coordinates to Zn in a chelate manner via two N atoms. Despite a similar coordination mode in complexes 3 and 4, the spatial geometry of the ligand differs notably, which implies a relatively high flexibility of NH2-pbt. The L ligand exhibits another coordination mode, binding with Zn only via the oxygen of the P=O group. The differences in the structures of NH2-pbt, 3 and 4, and their counterparts, PCNH-pbt, 1 and 2, induce differences in their solid-state photoluminescence properties. The former group of the compounds exhibits conventional single-band emission, while the latter group reveals two bands. The minor band at 450 nm is ascribed to a radiative transition for the regular amine species, while the major band at 520–550 nm can be associated either with the proton-transferred imine species (ESIPT mechanism) or with a charge transfer state (TICT) with a different geometry.

AB - We report a comparative study of coordination behaviour of 2-(2-aminophenyl)benzothiazole (NH2-pbt) and its phosphorus-containing derivative, α-aminophosphine oxide (PCNH-pbt), towards zinc halides. The corresponding coordination compounds [Zn(L)2Hal2] (L = PCNH-pbt, Hal = Cl, 1 and Hal = Br, 2) and [Zn(L’)Hal2] (L’ = NH2-pbt, Hal = Cl, 3 and Hal = Br, 4) were obtained as single phases. As evidenced by single-crystal X-ray diffraction analysis, L’ ligand coordinates to Zn in a chelate manner via two N atoms. Despite a similar coordination mode in complexes 3 and 4, the spatial geometry of the ligand differs notably, which implies a relatively high flexibility of NH2-pbt. The L ligand exhibits another coordination mode, binding with Zn only via the oxygen of the P=O group. The differences in the structures of NH2-pbt, 3 and 4, and their counterparts, PCNH-pbt, 1 and 2, induce differences in their solid-state photoluminescence properties. The former group of the compounds exhibits conventional single-band emission, while the latter group reveals two bands. The minor band at 450 nm is ascribed to a radiative transition for the regular amine species, while the major band at 520–550 nm can be associated either with the proton-transferred imine species (ESIPT mechanism) or with a charge transfer state (TICT) with a different geometry.

KW - coordination compounds

KW - heterocyclic compounds

KW - luminescence

KW - single crystal X-ray diffraction

UR - http://www.scopus.com/inward/record.url?scp=85138722924&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/0bc9a467-c9f1-343e-9a01-a8bce0456996/

U2 - 10.3390/inorganics10090138

DO - 10.3390/inorganics10090138

M3 - Article

AN - SCOPUS:85138722924

VL - 10

JO - Inorganics

JF - Inorganics

SN - 2304-6740

IS - 9

M1 - 138

ER -