Substituents make a difference: 6,6″-modified terpyridine complexes with helix configuration and enhanced emission

Abstract

A series of complexes L2₂-M (L2: 6,6″-bis(4-methoxyphenyl)-4′-phenyl-2,2′:6′,2″-terpyridine, M: Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺) 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.