Re(I) Complexes as Backbone Substituents and Cross-Linking Agents for Hybrid Luminescent Polysiloxanes and Silicone Rubbers

Abstract

This study focuses on the synthesis of hybrid luminescent polysiloxanes and silicone rubbers grafted by organometallic rhenium(I) complexes using Cu(I)-catalyzed azido-alkyne cycloaddition (CuAAC). The design of the rhenium(I) complexes includes using a diimine ligand to create an MLCT luminescent center and the introduction of a triple C≡C bond on the periphery of the ligand environment to provide click-reaction capability. Poly(3-azidopropylmethylsiloxane-co-dimethylsiloxane) (N3-PDMS) was synthesized for incorporation of azide function in polysiloxane chain. [Re(CO)3(MeCN)(5-(4-ethynylphenyl)-2,2′-bipyridine)]OTf (Re1) luminescent complex was used to prepare a luminescent copolymer with N3-PDMS (Re1-PDMS), while [Re(CO)3Cl(5,5′-diethynyl-2,2′-bipyridine)] (Re2) was used as a luminescent cross-linking agent of N3-PDMS to obtain luminescent silicone rubber (Re2-PDMS). The examination of photophysical properties of the hybrid polymer materials obtained show that emission profile of Re(I) moiety remains unchanged and metallocenter allows to control the creation of polysiloxane-based materials with specified properties.

The Tail Wags the Dog: The Far Periphery of the Coordination Environment Manipulates the Photophysical Properties of Heteroleptic Cu(I) Complexes

“…This is a universal strategy for molecular emitter design, and is widely used for creating ‘hybrid’ complex systems. For example, the approach mentioned above has been favourably applied to systems with covalent conjugations of a polymer and a complex, where it is important to retain the original physicochemical properties of the initial complex [ 9 , 10 , 11 ].…”

Platinum macrocatalyst for heterogeneous Si–O dehydrocoupling

“…According to ref. 15, the ratio of PCC to the units containing azide groups of N 3 -PDMS was 1 : 5. A threefold purification of Pt-PDMS was carried out by dissolving in ethyl acetate and filtration from unreacted PCC.…”

“…The azide-alkyne cycloaddition (CuAAC reaction) between PCC and N 3 -PDMS was chosen to synthesize Pt-containing copolysiloxane (Pt-PDMS) according to our previously reported method. 15 Hydrosilylation between hydride-containing polysiloxanes and PCC was not considered as a synthetic method because there is a high probability of a Si-Si dehydrocoupling reaction between Si-H groups catalyzed by PCC as in ref. 7.…”

“…For the CuAAC reaction, N 3 -PDMS was synthesized via a 3-step procedure 15 including hydrolysis and cyclooligomerization of dichloro(3-chloropropyl)methylsilane and dichlorodimethylsilane, polymerization, and azidation (Scheme S2, ESI †). The number-average molecular weight of N 3 -PDMS was determined by gel permeation chromatography and amounted to M n = 14 600 (dispersity Đ = 1.50) (ESI, section S1.2 †).…”

Silicone Materials for Flexible Optoelectronic Devices

“…This approach provides a uniform distribution of phosphors in the polymer matrix and excludes their washing out by organic solvents. The preparation of silicone luminescent materials based on rhenium-containing polysiloxanes (Figure 9) PMCs by the reaction of azide-alkyne cycloaddition (CuAAC) in the presence of copper (I) catalyzed was described in [99]. However, the rhenium-containing PMCs (Re-PDMS) [Re(CO) Despite the simplicity of the proposed approach, luminescent fillers can be wash out of the silicone material upon prolonged treatment with organic solvents [88].…”