Precise Synthesis of Alternate Fe(II)/Os(II)‐Based Bimetallic Metallo‐Supramolecular Polymer

Abstract

We synthesized a novel terpyridine-based bimetallic metallo-supramolecular polymer (polyFeOs) containing alternately complexed Fe(II) and Os(II) ions. For precise synthesis of the polymer, a new three step synthetic pathway is developed to get a high yield (%) of product in each step. The first step is synthesis of dibromo terpyridine-Os(II) complex with a 87% yield, the second step is synthesis of bisterpyridine ligand containing Os(II) (OsL1) with a 74% yield, and the last step is synthesis of polyFeOs with a 90% yield. The polyFeOs exhibits high thermal stability with two degradation This article is protected by copyright. All rights reserved.-2 -temperatures at around 390 and 690 °C, which indicate thermal evaporation of the counter anions (Cland BF 4 -) and degradation of the coordination bonds, respectively. The combination of two different metal ions in polyFeOs results in an enlarged optical window (λ = 315-675 nm) and two highly stable reversible redox states, which can be of huge interest for potential optical, electrooptical and electrochemical applications.

Dual-Redox System of Metallo-Supramolecular Polymers for Visible-to-Near-IR Modulable Electrochromism and Durable Device Fabrication

“…One idea to widen the absorption of the polymer is to introduce multiple metals to the polymer backbone because different metal complexes have different absorption wavelengths. Recently, we reported the polymers having two metal species. ,− So, we will try to widen the absorption feature using multiple metals in this visible-to-NIR EC system in near future for the achievement of the better sun shading performance.…”

Constructing Alternated Heterobimetallic [Fe(II)/Os(II)] Supramolecular Polymers with Diverse Solubility for Facile Fabrication of Voltage-Tunable Multicolor Electrochromic Devices

“…In addition, processability of the EC materials is another important parameter for low-cost and large-area production of solid-state electrochromic devices (ECDs). Considering the industrial requirements, in the past decade, Kurth and Higuchi et al have introduced an organic–inorganic hybrid material known as metallo-supramolecular polymers (MSPs). − The MSPs show attractive electrochromic properties with very high color contrast, low response times, and high coloration efficiencies. Moreover, large-area EC devices can be easily fabricated by making the spray-coating film of MSPs dissolve in low boiling solvent like methanol (MeOH), which is a promising approach that could be integrated with industrially important roll-to-roll (R2R) coating technology. , …”

“…Therefore, very recently we have developed a new three-step synthesis route for precise synthesis of any alternated HBP containing two metal ions that are in the same coordination environment. We have described the preparation of a HBP containing alternated Fe­(II) and Os­(II) ions that are in the same coordination environment made by two 2,2′:6′,2″-terpyridine units . As we know, MSPs are synthesized in such a way that they should be soluble in a low boiling solvent (like MeOH) to enhance the polymer processability for making of a large-area spray-coating EC thin film easily in short time.…”

Synthesis of an Alternated Heterobimetallic Supramolecular Polymer Based on Ru(II) and Fe(II)

“…For example, Stang and co-workers synthesized a Pt(II)-Zn(II)-based heterometallic supramolecular polymer with self-healing properties [13]. Our group reported a heterobimetallic MSP containing Fe(II)-Os(II) with unique electro-optical properties [14,15]. The synthesis of heterobimetallic supramolecular polymers is generally achieved by two strategies.…”

“…One strategy is the introduction of two heterometal ions into the polymer chain in different coordination environments, which is achieved through different binding affinity of the ligand for different metal ions [16]. Another strategy is the introduction of heterometal ions into the MSP chain in identical coordination environments, which is synthetically challenging [14]. In this respect, it should be mentioned that heterobimetallic supramolecular polymers having heterometal ions in identical coordination environments, are of particular interest because the properties of the two heterometallic segments are comparable.…”