New Class of Phosphine Oxide Donor-Based Supramolecular Coordination Complexes from an in Situ Phosphine Oxidation Reaction or Phosphine Oxide Ligands

Abstract

A one-pot, multicomponent, coordination-driven self-assembly approach was used to synthesize the first examples of neutral bridging phosphine oxide donor-based supramolecular coordination complexes. The complexes were self-assembled from a fac-Re(CO)3 acceptor, an anionic bridging O donor, and a neutral soft phosphine or hard phosphine oxide donor.

Rhenium‐Carbonyl‐Based Supramolecular Coordination Complexes: Synthesis, Structure and Properties

“…A related study of the effect of donor atoms substitution on the photophysical properties of rhenium metallacycles was demonstrated by Sathiyendiran and coworkers. The multi‐component self‐assembly of metallacycle 17 resulted in a phosphine oxide coordinated dinuclear metallacycle via in‐situ oxidation of the phosphine ligand, thereby generating a neutral oxide donor at the metal‐center with chloranilic acid as the bis‐chelating unit . Compared to the free ligands and related metallacycles possessing N‐donors instead of P=O donors, 17 exhibited strong visible light absorption (ϵ = 14768 M ‐1 ) with nearly 37 fold higher molar absorption coefficient.…”

Dirhenium Coordination Complex Endowed with an Intrinsically Chiral Helical-Shaped Diphosphine Oxide

“…32−35 However, the rhenium-based polynuclear complexes containing O=P ligands are very scarce, based on tetraphenyldichalcogenoimidodiphosphinate anions as ligands, 34,35 and, more recently, flexible alkyl or benzyl diphosphine oxides as neutral ditopic O=P ligands along with a rigid bischelating O donor (e.g., chloranilic acid and 2,5-dihydroxy-1,4-benzoquinone). 32,33 In our continuing studies on the synthesis and characterization of organometallic complexes based on the 7-TH derivatives, we focused on the study of the coordination ability of an uncommon and more rigid helical-based phosphine oxide as a neutral ditopic ligand toward dinuclear rhenium complexes containing chloranilic acid as the anionic donor. Herein, we report the first example of a rhenium(I)-based coordination complex in which 7-TH phosphine oxide (±)- 1 , 9 used as a racemic mixture for this first study, has been selected as a model helical bis(P=O) donor ligand.…”

Utilizing a series of fac-Re(CO)3 core based quinonoid containing complexes for photophysical and cell imaging studies

“…The photophysical properties of fac-Re(CO) 3 core based acyclic complexes, such as visible light absorption, large luminescence lifetimes, NIR region absorption/emission and photostability, have been extensively investigated and applied in a variety of areas, such as electroand chemi-luminescence, light harvesting, photo-dynamic therapy, photo-catalysis, photonics and OLEDs etc [1]. These applications require visible region excitations and hence a strong absorption in the visible range is one of the essential criteria.…”

“…These applications require visible region excitations and hence a strong absorption in the visible range is one of the essential criteria. Recently, a number of fac-[Re(CO) 3 ] complexes have been applied as luminescent live cell imaging agents owing to their favourable biological properties, such as kinetic inertness, lipophilicity, large Stokes shifts, photo-stability, membrane permeability and low cytotoxicity [2]. Particularly, Coogan and coworkers demonstrated the first application of fluorescent Re(I) complexes in cell-imaging by utilizing bipyridine and phenanthroline based lipophilic and hydrophilic mono-nuclear bisimine complexes [2a-d].…”

“…Previously, 2,5-dihydroxy-1,4-benzoquinone derivatives have been used in various fac-Re(CO) 3 core based metallacycles where they play solely a structural role [3]. Recently, with an aim to induce novel properties into the metal complexes, our group and others have started investigating metal complexes containing ligands where the two hydroxyl groups of the 2,5-dihydroxy-1,4-benzoquinone ligand are replaced by the isoelectronic [NR] group to generate two To the best of our knowledge, the synthesis, photophysical properties and biological evaluations of dinuclear Re(I) complexes possessing bis-chelating imino-quinone ligands have never been investigated.…”