Exploring the Optimal Synthetic Pathways towards µ‐Carbido Diruthenium(IV) Bisphthalocyaninates

Abstract

Series of substituted μ-carbido diruthenium(IV) bisphthalocyaninates [Pc*Ru] 2 (μ-C) [where Pc* = tetra-tert-butyl-, octa-n-butoxy-, tetra-15-crown-5-and hexa-n-butoxy-mono-(15-crown-5)-substituted ligands] were synthesized using two alternative approaches -(i) direct metalation of phthalocyanines with Ru 3 (CO) 12 in refluxing o-dichlorobenzene where [Pc*Ru] 2 (μ-C) are formed as by-products together with monomeric complexes [Pc*Ru](CO) and (ii) dimerization of [Pc*Ru]-(CO) by dichlorocarbene generated in situ from chloroform and [a] 1924 Scheme 3. Synthesis of μ-carbido complexes starting from [Pc*Ru](CO) and dichlorocarbene, generated in situ from CHCl 3 and a base (KOH or NMe 4 OH).

Heteroleptic Crown-Substituted Tris(phthalocyaninates) as Dynamic Supramolecular Scaffolds with Switchable Rotational States and Tunable Magnetic Properties

“…Certainly, the influence of the supramolecular factors on the SMM behavior of paramagnetic complexes and magnetization relaxation mechanisms is of undeniable interest; , therefore, these studies are currently in progress on the examples of terbium­(III)-containing [M*,M] complexes. Finally, the described approach to control of the rotational state of the phthalocyanine ligands can be used to tune the properties of the structurally similar family of single-atom-bridged bis­(phthalocyaninates) (μ-X)­[PcM] 2 (X = C, N, O), including siloxane olygomers and catalytically active iron and ruthenium complexes. , …”

“…Finally, the described approach to control of the rotational state of the phthalocyanine ligands can be used to tune the properties of the structurally similar family of single-atom-bridged bis-(phthalocyaninates) (μ-X)[PcM] 2 (X = C, N, O), including siloxane olygomers 51 and catalytically active iron and ruthenium complexes. 52,53 ■ EXPERIMENTAL SECTION were performed on a Bruker Kappa Apex II automatic four-circle diffractometer equipped with an area detector. The unit cell parameters were refined over the whole data set.…”

From mononuclear iron phthalocyanines in catalysis to μ-nitrido diiron complexes and beyond

“…The chemistry of µ-carbido diruthenium porphyrin-like complexes has been less documented [107]. Recently, the synthetic protocols to µ-carbido diruthenium(IV) phthalocyanine complexes have been developed and optimized [108,109]. A series of substituted complexes (Pc*Ru)2(µ-C) with Pc* = tetra-tert-butyl, octa-n-butoxy-, tetra-15-crown-5-and hexa-n-butoxy-mono-(15crown-5)-substituted ligands were prepared by two approaches (Fig.…”

Unusual Cyan-Purple Electrochromism of Sandwich Phthalocyaninates Observed on the Example of µ-Carbido Diruthenium(IV) Complex

“…[42] Previous electrochemical studies of m-X-bridged dimers were mainly referred to unsubstituted compounds which could not be used to form organized thin film materials due to the lack of solubility, however, recently we reported approaches to the synthesis of substituted ruthenium(IV) m-carbido-bisphthalocyaninates. [40,43] Thus, in the present work we report first example of the detailed spectroelectrochemical characterization of the soluble carbido-dimeric complex [tBu 4 PcRu] 2 (μ-С) (Figure 1b) both in solution and in Langmuir-Schaefer films. We show that the behavior of this complex under the application of electrochemical potential is mainly similar to the one of archetypal REE bisphthalocyaninates, however, reversible oxidation/reduction of the film formed by the mentioned complex affords the switching between cyan and purple colors unavailable in the case of REE complexes.…”

“…The complex [tBu 4 PcRu] 2 (μ-С) was synthesized by dimerization of the monomeric complex [tBu 4 PcRu](CO) upon its reaction with chloroform and KOH in isopropanol-toluene mixture as reported previously. [43] UV-Vis spectra and colorimetric data were obtained using fiber optic spectroscopy setup utilizing a combination of Avantes AvaLight-DH-S balanced deuterium halogen light source and two Avantes spectrometers (AvaSpec-ULS2048CL-EVO and AvaSpec-NIR256-1.7), coupled via fiber optic cables through a cell holder with co-axially positioned collimated lenses. This combination allows for detection of UV-Vis-NIR spectra in the wavelength range from 220 to 1760 nm, however, in most cases within the present study, this range was shortened, mainly due to optical filtering of the UV light (to eliminate unnecessary photodamage of the studied dyes) and/or immense absorbance of water (when it was used as electrolyte).…”