Heterobimetallic Cu(I)/Ru(II) Acetylide Bridged Hybrid Complexes Containing Coordination and Organometallic Sites

Abstract

The heterobimetallic complexes [Cu(phen)(NC5H4HC=NC6H4C≡CC6H4C≡CRu(dppe)2Cl)]X (1 a‐4 a) and [Cu(bipy)(NC5H4H C=NC6H4C≡CC6H4C≡CRu(dppe)2Cl)]X (1 b‐4 b) (where X= I, ClO4, BF4, PF6; phen= 1, 10 phenanthroline, bipy= 2, 2′ bipyridine) have been prepared by the reaction of (NC5H4HC=NC6H4C≡CC6H4C≡CRu(dppe)2Cl) with copper salts in presence of phen or bipy as a coligand. Our synthetic attempts and successes are discussed in combination with spectroscopic and electronic characterization of the compounds. Comparison between phen and bipy complexes were studied by thermal and electrochemical analysis where, thermally robust complexes demonstrate quasireversible redox behaviour analogous to CuI/II/RuII/III couple. SEM of representative complexes 2 a and 2 b clarify the average size and morphology of the complexes. Room temperature luminescence influenced by varying coordinating ability of counter anions along with π‐acidic character in green‐yellow region was observed. Solvent dependant emission displays positive solvatochromism at ambient temperature. The second harmonic generation (SHG) efficiency of the complexes was measured by Kurtz‐powder technique indicating that all complexes display the second harmonic generation (SHG) property.

Near-IR/Visible-Emitting Thiophenyl-Based Ru(II) Complexes: Efficient Photodynamic Therapy, Cellular Uptake, and DNA Binding

“…Upon excitation at the 1 MLCT absorption wavelength, a strong solvatochromism was observed for Ru2 from CH 2 Cl 2 (588 nm) to H 2 O (700 nm), suggesting a significantly strong solvent–complex interaction at the excited state. Such a large red shift has rarely been reported in Ru­(II) complexes − and is much more evident than a red shift of only about 25 nm observed for the emission of Ru1 from CH 2 Cl 2 (600 nm) to H 2 O (625 nm) and even a maximum red shift of 40 nm from CH 2 Cl 2 (600 nm) to EtOAc (640 nm). The luminescence quantum yields of Ru1 and Ru2 were measured using [Ru­(bpy) 3 ] 2+ in water as a standard.…”

Organic–Inorganic Hybrid Compound [H2-1,5-Diazabicyclo[3.3.0]octane]ZnBr4 with Reverse Symmetry Breaking Shows a Switchable Dielectric Anomaly and Robust Second Harmonic Generation Effect

“…The switchable nonlinear optical (NLO) materials, especially second harmonic generation (SHG) switches, have characteristics of switching between different states in response to external stimuli (light, heat, electric field), which have attracted extensive attention from scholars in the fields of physics and chemistry. − The switchable SHG foundational molecules have been extensively found in organic–inorganic hybrid compounds, host–guest inclusion compounds, ionic salts, coordinated complexes, and single-component organic crystals. − Based on the crystallographic knowledge, the switchable SHG active materials should crystallize in a non-centrosymmetric (NCS) point group in the low temperature phase (LTP) and conversely in a centrosymmetric (CS) space group in the high temperature phase (HTP). In the past few decades, due to the advantages of molecule designable, structure tunability, lightweight, and environmental friendliness, the organic–inorganic hybrid compounds have won the favor of researchers, not only in the field of phase transformation and dielectrics, but also in nonlinear optics (NLO), ferroelectricity, and ferroelasticity. − …”