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Substituents make a difference: 6,6″-modified terpyridine complexes with helix configuration and enhanced emission.
- Source :
-
Dalton transactions (Cambridge, England : 2003) [Dalton Trans] 2023 Mar 07; Vol. 52 (10), pp. 3033-3039. Date of Electronic Publication: 2023 Mar 07. - Publication Year :
- 2023
-
Abstract
- A series of complexes L22-M (L2: 6,6″-bis(4-methoxyphenyl)-4'-phenyl-2,2':6',2″-terpyridine, M: Mn <superscript>2+</superscript> , Fe <superscript>2+</superscript> , Co <superscript>2+</superscript> , Ni <superscript>2+</superscript> , Cu <superscript>2+</superscript> , Zn <superscript>2+</superscript> ) were synthesized by coordinating p -methoxyphenyl 6,6″-substituted terpyridine ligand with first-row transition metal ions and characterized by NMR, ESI-MS, and X-ray single crystal diffraction techniques. Single-crystal structures demonstrated that the steric hindrance of p -methoxyphenyl substituents endowed complexes L22-M with obvious longer coordination bond lengths and larger bond angles and dihedral angles compared with unmodified L12-M (L1: 4'-phenyl-2,2':6',2″-terpyridine). The chiral helix geometry was observed for L22-M, in which 2,2':6',2″-terpyridine moiety dramatically twisted to a spiral form in comparison to the nearly coplanar structure of the parent L12-M, resulting in plentiful intramolecular and intermolecular π-π interactions. Also, the appealing racemic (P and M) double helix packed structure for 6,6″-modified bisterpyridine complex L22-Cu was formed in the crystal. The consequent appealing charge transfer (CT) emission for L22-Zn in the solution and solid were investigated via UV-vis and fluorescence spectroscopy techniques and time-dependent density functional theory (TD-DFT) calculations. This work afforded a new method to achieve intriguing chiral geometry and CT optical properties via the subtle design and modification of terpyridine ligands.
Details
- Language :
- English
- ISSN :
- 1477-9234
- Volume :
- 52
- Issue :
- 10
- Database :
- MEDLINE
- Journal :
- Dalton transactions (Cambridge, England : 2003)
- Publication Type :
- Academic Journal
- Accession number :
- 36779408
- Full Text :
- https://doi.org/10.1039/d2dt04006a