TY - JOUR

T1 - White-green photoluminescence of manganese(II) complexes with pyrazolo[1,5-a][1,10]phenanthroline-3-carbonitrile

AU - Vinogradova, Katerina A.

AU - Berezin, Aleksey S.

AU - Taigina, Marina D.

AU - Sannikova, Victoriya A.

AU - Filippov, Igor R.

AU - Pervukhina, Natalia V.

AU - Yu. Naumov, Dmitrii

AU - Kolybalov, Dmitry S.

AU - Vorob'ev, Aleksey Yu

N1 - The work was funded by Russian Science Foundation (grant \u2116 22-73-00255). The authors are grateful to A. A. Shapovalova and A. I. Basov for their help with IR spectra and Dr. Anna P. Zubareva for elemental analysis and to Irina V. Yushina for recording the diffuse reflectance spectra and to M. O. Matveeva for recording X-ray powder diffraction patterns. Also, the authors thanks to Yu. A. Malakhova for synthesis samples of complex [MnL2(H2O)2].L(ClO4)2. The abstract background picture has been created using AI \u201CCraiyon V\u201D https://www.craiyon.com/. The powder XRD analysis (STOE STADI MP powder X-ray diffractometer) was carried out with equipment of the Laboratory of Molecular Design and Ecologically Safe Technologies\u201D at Novosibirsk University.

PY - 2024/9/1

Y1 - 2024/9/1

N2 - Five manganese(II) complexes with a bidentate pyrazolo[1,5-a][1,10]phenanthroline-3-carbonitrile ligand (L) have been prepared and their structures have been determined. The anion effect on the structural diversity of the complexes has been studied using manganese(II) salts with different anions such as Cl¯, ClO4¯, and Ts¯. A reaction between manganese(II) chloride and L in organic solvents leads to complexes [MnL2Cl2]·xCH2Cl2 (1) and [Mn2L2(H2O)Cl4]·L (2), the use of manganese(II) tosylate in the rection yields in [MnL(H2O)3Ts]Ts·L·H2O (3) and [MnL(H2O)3Ts]Ts (4), and finally, in the case of manganese(II) perchlorate [MnL2(H2O)2](ClO4)2·L (5) is formed. According to the single-crystal X-ray analysis the coordination environment of the Mn(II) ions in the complexes is a distorted octahedron with MnN4Cl2 (1), MnN2O4 (3) and MnN4O2 (5) chromophores; the complex 2 is binuclear, in which two manganese atoms have different coordination geometries – distorted octahedron (MnN2Cl3O) and square pyramid (MnN2Cl3). Chloride ions are coordinated anions; perchlorate ions are in the outer coordination sphere. Tosylate ions can play both coordinating and non-coordinating roles in complexes. X-ray analysis shows that in 2 and 5 one molecule of L has no bonds with manganese atoms, and reveals only intermolecular interactions through π-π stacking. This leads to the formation of cocrystals [Mn2L2(H2O)Cl4]·L or [MnL2(H2O)2](ClO4)2·L, that affects the photophysical properties of these compounds. In order to compare the effect of L coordination on the photoluminescence properties of manganese(II) complexes, the complexes [Mn(phen)3](ClO4)2·xSolv with unsubstituted 1,10-phenanthroline have been synthesized. In contrast to [MnL2(H2O)2](ClO4)2·L, the 1,10-phenanthroline-based compound [Mn(phen)3](ClO4)2·H2O has no emission. Complexes 1, 3, 4 and 5 exhibit a white-green emission in the microsecond range with maxima at 530–565 nm in the solid state, and the photoluminescence properties of 5 are studied in solution.

AB - Five manganese(II) complexes with a bidentate pyrazolo[1,5-a][1,10]phenanthroline-3-carbonitrile ligand (L) have been prepared and their structures have been determined. The anion effect on the structural diversity of the complexes has been studied using manganese(II) salts with different anions such as Cl¯, ClO4¯, and Ts¯. A reaction between manganese(II) chloride and L in organic solvents leads to complexes [MnL2Cl2]·xCH2Cl2 (1) and [Mn2L2(H2O)Cl4]·L (2), the use of manganese(II) tosylate in the rection yields in [MnL(H2O)3Ts]Ts·L·H2O (3) and [MnL(H2O)3Ts]Ts (4), and finally, in the case of manganese(II) perchlorate [MnL2(H2O)2](ClO4)2·L (5) is formed. According to the single-crystal X-ray analysis the coordination environment of the Mn(II) ions in the complexes is a distorted octahedron with MnN4Cl2 (1), MnN2O4 (3) and MnN4O2 (5) chromophores; the complex 2 is binuclear, in which two manganese atoms have different coordination geometries – distorted octahedron (MnN2Cl3O) and square pyramid (MnN2Cl3). Chloride ions are coordinated anions; perchlorate ions are in the outer coordination sphere. Tosylate ions can play both coordinating and non-coordinating roles in complexes. X-ray analysis shows that in 2 and 5 one molecule of L has no bonds with manganese atoms, and reveals only intermolecular interactions through π-π stacking. This leads to the formation of cocrystals [Mn2L2(H2O)Cl4]·L or [MnL2(H2O)2](ClO4)2·L, that affects the photophysical properties of these compounds. In order to compare the effect of L coordination on the photoluminescence properties of manganese(II) complexes, the complexes [Mn(phen)3](ClO4)2·xSolv with unsubstituted 1,10-phenanthroline have been synthesized. In contrast to [MnL2(H2O)2](ClO4)2·L, the 1,10-phenanthroline-based compound [Mn(phen)3](ClO4)2·H2O has no emission. Complexes 1, 3, 4 and 5 exhibit a white-green emission in the microsecond range with maxima at 530–565 nm in the solid state, and the photoluminescence properties of 5 are studied in solution.

KW - Crystal structure

KW - Manganese(II) complexes

KW - Synthesis

KW - White-green photoluminescence

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85193539255&origin=inward&txGid=72655422d7920467e6440a5d3914f163

UR - https://www.mendeley.com/catalogue/eb97a0d6-e7cf-3fd2-81ab-cb545a123bf1/

U2 - 10.1016/j.ica.2024.122137

DO - 10.1016/j.ica.2024.122137

M3 - Article

VL - 569

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

SN - 0020-1693

M1 - 122137

ER -