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Photophysical, thermal, and DFT studies on a tetraaryl-azadipyrromethene ligand and its zinc(II) complex.

ABSTRACT: An azadipyrromethene ligand (H1) and homoleptic zinc(II) (H1-Zn) complex were synthesized. The resulting structures were elucidated by NMR, FTIR, and HRMS techniques. The photophysical properties and effects of complexing the zinc(II) atom to azadipyrromethene ligands in solution were studied by means of UV-Vis absorption and fluorescence spectroscopy. Experimental findings were elucidated using density functional theory computations and interfragment charge transfer (IFCT) and electron-hole analyses. The fluorescence features were found to be negligible. The ligand molecule decayed at a rate of 3% while the complex decayed at 2% upon photoirradiation based on photostability experiments. The singlet oxygen quantum yields of the ligand and complex were calculated as 0.127 and 0.233, respectively, signifying low photodynamic activity. The charge transfer transitions were determined between reciprocal ligands responsible for the red shift of the main absorption band by IFCT and electron-hole analysis. Compounds in an inert N₂ atmosphere demonstrated high thermal stability. Although the thermogravimetric analysis (TGA) and derivative thermogravimetry curves of the complexes were similar, zinc(II) coordination and homoleptic complex formation reduced the degradation temperatures. These findings suggest that azadipyrromethene and the Zn(II) class of chromophores have beneficial features for use in the development of novel photo- and thermostable materials that combine charge transfer with low energy in the visible and near infrared regions.

SUBMITTER: Sevinc G

PROVIDER: S-EPMC10965187 | biostudies-literature | 2023

REPOSITORIES: biostudies-literature

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Photophysical, thermal, and DFT studies on a tetraaryl-azadipyrromethene ligand and its zinc(II) complex.

Sevinç Gökhan G

Turkish journal of chemistry 20231010 6

An azadipyrromethene ligand (<b>H1</b>) and homoleptic zinc(II) (<b>H1-Zn</b>) complex were synthesized. The resulting structures were elucidated by NMR, FTIR, and HRMS techniques. The photophysical properties and effects of complexing the zinc(II) atom to azadipyrromethene ligands in solution were studied by means of UV-Vis absorption and fluorescence spectroscopy. Experimental findings were elucidated using density functional theory computations and interfragment charge transfer (IFCT) and ele ...[more]

PMID: 38544707

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Project description:The luminescent, mono-diimine ruthenium complexes [(H)Ru(CO)(PPh3)2(dcbpy)][PF6] (1) (dcbpy = 4,4'-dicarboxy-2,2'-bipyridyl) and [(H)Ru(CO)(dppene)(5-amino-1,10-phen)][PF6] (2) (dppene = bis(diphenylphosphino)ethylene; phen = phenanthroline) were conjugated with 1,2-dihexadecanoyl-sn-glycero-3-phosphoethanolamine (DPPE) and with cholesterol in the case of complex 2. Using standard conjugation techniques, compound 1 gives the bis-lipid derivative [(H)Ru(CO)(PPh3)2(dcbpy-N-DPPE2)][PF6] (3), while 2 provides the monolipid conjugate [(H)Ru(CO)(dppene)(1,10-phen-5-NHC(S)-N-DPPE)][PF6] (4) and the cholesterol derivative [(H)Ru(CO)(dppene)(1,10-phen-5-NHC(O)Ocholesteryl)][PF6] (5). These compounds were characterized by spectroscopic methods, and their photophysical properties were measured in organic solvents. The luminescence of lipid conjugates 3 and 4 is quenched in organic solvents while compound 4 shows a weak, short-lived, blue-shifted emission in aqueous solution. The cholesterol conjugate 5 shows the long-lived, microsecond-time scale emission associated with triplet metal-to-ligand charge-transfer excited states. Incorporation of conjugate 3 in lipid bilayer vesicles restores the luminescence, but with blue shifts (~80 nm) accompanied by nanosecond-time scale lifetimes. In the vesicles conjugate 4 shows a short-lived and blue-shifted emission similar to that observed in solution but with increased intensity. Conjugation of the complex [(H)Ru(CO)(PhP2C2H4C(O)O-N-succinimidyl)2(bpy)][PF6] (6") (bpy = 2,2'-bipyridyl) with DPPE gives the phosphine-conjugated complex [(H)Ru(CO)(PhP2C2H4C(O)-N-DPPE)2(bpy)][PF6] (7). Complex 7 also exhibits a short-lived and blue-shifted emission in solution and in vesicles as observed for complexes 3 and 4. We have also conjugated the complex [Ru(bpy)2(5-amino-1,10-phen)][PF6]2 (8) with both cholesterol (9) and DPPE (10). Neither complex 9 nor the previously reported complex 10 exhibited the blue shifts observed for complexes 3 and 4 when incorporated into large unilamellar vesicles (LUVs). The anisotropies of the emissions of complexes 3, 4, and 7 were also measured in LUVs, and those of complex 5 were measured in both glycerol and LUVs. High fundamental anisotropies were observed for complexes 3, 4, and 7.

Dataset Information

Photophysical, thermal, and DFT studies on a tetraaryl-azadipyrromethene ligand and its zinc(II) complex.

Publications

Photophysical, thermal, and DFT studies on a tetraaryl-azadipyrromethene ligand and its zinc(II) complex.

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