Ligand Exchange Reaction between Ferrocene and Multiwalled Carbon Nanotubes: A Contemporary Approach.

Ligand exchange reaction (LER) between carbon nanoparticles and ferrocene (Cp2Fe) was conducted several times, but there was no convincing evidence of half-sandwich CpFe+ coordination to multiwalled carbon nanotubes (MWCNT). In this study, MWCNT is modified by LER with ferrocene using AlCl3/Al as a catalytic system. The modified MWCNT (Fc-MWCNT) are investigated for better understanding of the processes taking place on the surface of MWCNT using different spectroscopic and electrochemical methods. The formation of the Fe-C covalent bond between CpFe+ and MWCNT is confirmed by changes in the Raman spectrum of Fc-MWCNT compared to pristine MWCNT. The densest structure of Fc-MWCNT is investigated by transmission electronic microscopy. According to density-functional theory calculations of the model interaction between Fe and coronene, the Fe-C bond length is 2.1687-2.1855 Å. X-ray photoelectron spectroscopy also confirms the coordination of the Fe atom to MWCNT by analysis of oxidation states of Fe 2p and deconvolution of C 1s. Utilization of cyclic voltammetry corroborated MWCNT modification via LER. These data are important for both theoretical and practical applications due to increased interest in LER-modified compounds in different areas including thermoelectric devices, sensors, and its potential application in the field of molecular machine construction.

Self-Healing Silicone Materials: Looking Back and Moving Forward.

This review is dedicated to self-healing silicone materials, which can partially or entirely restore their original characteristics after mechanical or electrical damage is caused to them, such as formed (micro)cracks, scratches, and cuts. The concept of self-healing materials originated from biomaterials (living tissues) capable of self-healing and regeneration of their functions (plants, human skin and bones, etc.). Silicones are ones of the most promising polymer matrixes to create self-healing materials. Self-healing silicones allow an increase of the service life and durability of materials and devices based on them. In this review, we provide a critical analysis of the current existing types of self-healing silicone materials and their functional properties, which can be used in biomedicine, optoelectronics, nanotechnology, additive manufacturing, soft robotics, skin-inspired electronics, protection of surfaces, etc.

Platinum macrocatalyst for heterogeneous Si-O dehydrocoupling.

A platinum polymer catalyst (Pt-PDMS) was synthesized by immobilization of a platinum catalytic complex in a polysiloxane chain using an azide-alkyne CuAAC cycloaddition. Insoluble Pt-PDMS can be used as an effective heterogeneous macrocatalyst for Si-O dehydrocoupling. Pt-PDMS is easy to recover, purify, and reuse again for heterogeneous catalysis.

Structural Features of Eu3+ and Tb3+-Bipyridinedicarboxamide Complexes.

Photoluminescent lanthanide complexes of Eu3+ and Tb3+ as central atoms and N6,N6'-diisopropyl-[2,2'-bipyridine]-6,6'-dicarboxamide as ligand were synthesized. The structure of these complexes was established by single-crystal X-ray diffraction, mass spectrometry, 1H and 13C nuclear magnetic resonance, ultraviolet-visible, infrared spectroscopy, and thermogravimetry. Bipyridinic ligands provide formation of coordinatively saturated complexes of lanthanide ions and strong photoluminescence (PL). The Eu3+- and Tb3+-complexes exhibit PL emission in the red and green regions observed at a 340 nm excitation. The quantum yield for the complexes was revealed to be 36.5 and 12.6% for Tb3+- and Eu3+-complexes, respectively. These lanthanide compounds could be employed as photoluminescent solid-state compounds and as emitting fillers in polymer (for example, polyethylene glycol) photoluminescent materials.

Silicone Materials for Flexible Optoelectronic Devices.

Polysiloxanes and materials based on them (silicone materials) are of great interest in optoelectronics due to their high flexibility, good film-forming ability, and optical transparency. According to the literature, polysiloxanes are suggested to be very promising in the field of optoelectronics and could be employed in the composition of liquid crystal devices, computer memory drives organic light emitting diodes (OLED), and organic photovoltaic devices, including dye synthesized solar cells (DSSC). Polysiloxanes are also a promising material for novel optoectronic devices, such as LEDs based on arrays of III-V nanowires (NWs). In this review, we analyze the currently existing types of silicone materials and their main properties, which are used in optoelectronic device development.

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

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.

Deprotonated diaminocarbene platinum complexes for thermoresponsive luminescent silicone materials: both catalysts and luminophores.

C,N-Chelate deprotonated diaminocarbene platinum(II) complexes were synthesized by coupling coordinated isocyanides and azinyl-substituted ureas. The complexes act as catalysts of α,ω-divinylpolydimethylsiloxane and poly(dimethylsiloxane-co-methylhydrosiloxane) hydrosilylation cross-linking. Silicone rubbers obtained with (aminoisoquinoline)-containing complex 3d exhibit temperature-responsive luminescence. Their emission changes irreversibly when heated from 80-100 °C (green radiation) to 120 °C or more (blue radiation).

Flexible Perovskite CsPbBr3 Light Emitting Devices Integrated with GaP Nanowire Arrays in Highly Transparent and Durable Functionalized Silicones.

The architecture of transparent contacts is of utmost importance for creation of efficient flexible light-emitting devices (LEDs) and other deformable electronic devices. We successfully combined the newly synthesized transparent and durable silicone rubbers and the semiconductor materials with original fabrication methods to design LEDs and demonstrate their significant flexibility. We developed electrodes based on a composite GaP nanowire-phenylethyl-functionalized silicone rubber membrane, improved with single-walled carbon nanotube films for a hybrid poly(ethylene oxide)-metal-halide perovskite (CsPbBr3) flexible green LED. The proposed approach provides a novel platform for fabrication of flexible hybrid optoelectronic devices.

Structural and Optical Properties of Self-Catalyzed Axially Heterostructured GaPN/GaP Nanowires Embedded into a Flexible Silicone Membrane.

Controlled growth of heterostructured nanowires and mechanisms of their formation have been actively studied during the last decades due to perspectives of their implementation. Here, we report on the self-catalyzed growth of axially heterostructured GaPN/GaP nanowires on Si(111) by plasma-assisted molecular beam epitaxy. Nanowire composition and structural properties were examined by means of Raman microspectroscopy and transmission electron microscopy. To study the optical properties of the synthesized nanoheterostructures, the nanowire array was embedded into the silicone rubber membrane and further released from the growth substrate. The reported approach allows us to study the nanowire optical properties avoiding the response from the parasitically grown island layer. Photoluminescence and Raman studies reveal different nitrogen content in nanowires and parasitic island layer. The effect is discussed in terms of the difference in vapor solid and vapor liquid solid growth mechanisms. Photoluminescence studies at low temperature (5K) demonstrate the transition to the quasi-direct gap in the nanowires typical for diluted nitrides with low N-content. The bright room temperature photoluminescent response demonstrates the potential application of nanowire/polymer matrix in flexible optoelectronic devices.

Cellulose-based hybrid glycosilicones via grafted-to metal-catalyzed hydrosilylation: "When opposites unite".

Hydrosilylation catalyzed by the rhodium(I) complex [Rh(acac)(CO)2] or platinum(0)-based Karstedt's catalyst was employed to combine hydrophilic propargylated hydroxyethyl cellulose and hydrophobic hydride-terminated polydimethylsiloxane to give polymer hybrid structures. The final polymers were characterized by FTIR, solid state 1H, 13C and 29Si NMR, contact angle, microcalorimetry and thermogravimetry measurements. The grafting degree was controlled by the catalyst choice and by the reagent load variations; an increase of the polysiloxane load and a change from Karstedt's to the rhodium catalyst led to a higher (from 2 to 7%) silicon content in the glycosilicones. The glycosilicones were insoluble in water, but swelled in organic solvents (DMSO, DMF, and chloroform). The hydrophilicity of the glycosilicones decreased with incrementing silicon content: the contact angles increased from 30 (cellulose) to 103-131° in the hybrids. The glycosilicones obtained via the hydrosilylation are less toxic toward algae Chlorella vulgaris and infusoria Paramecium caudatum than those obtained with CuAAC.

A metal-free radical technique for cross-linking of polymethylhydrosiloxane or polymethylvinylsiloxane using AIBN.

A new method was developed for the metal-free cross-linking of silicone rubbers. This process uses azobisisobutyronitrile (AIBN) to selectively react with Si-H and vinyl groups as a free-radical initiator for the thermal curing of polymethylhydrosiloxane (PMHS) and polymethylvinylsiloxane (PMVS). The AIBN-initiated curing reaction between the Si-H groups of PMHS generated Si-O-Si and Si-Si cross-links. In contrast, PMVS was cured via the formation of C-C bonds through "methyl-vinyl" and "vinyl-vinyl" mechanisms. Curing reactions were performed at 80-120 °C in air and confirmed by 13C and 29Si solid state NMR analyses and swelling trials.

Platinum-catalyzed reactions between Si-H groups as a new method for cross-linking of silicones.

The platinum-catalyzed self-cross-linking of polymethylhydrosiloxane at RT in air was performed for the first time and proved by 1H, 13C, and 29Si SSNMR and swelling measurements. Quantum chemical modeling of possible structures was investigated. Platinum (0) and (ii) complexes were used as catalysts between the Si-H groups of polymethylhydrosiloxane. Karstedt's catalyst leads to Si-O-Si and Si-Si bond formation, but cis-[PtCl2(BnCN)2] generates predominantly Si-O-Si cross-links. cis-[PtCl2(BnCN)2] allows creating high-quality silicone rubbers without visible mechanical defects. This cross-linking approach can be used to obtain new Si-H-containing silicone materials.

bis-Nitrile and bis-Dialkylcyanamide Platinum(II) Complexes as Efficient Catalysts for Hydrosilylation Cross-Linking of Siloxane Polymers.

cis- and trans-Isomers of the platinum(II) nitrile complexes [PtCl2(NCR)2] (R = NMe2, N(C5H10), Ph, CH2Ph) were examined as catalysts for hydrosilylation cross-linking of vinyl-terminated polydimethylsiloxane and trimethylsilyl-terminated poly(dimethylsiloxane-co-ethylhydrosiloxane) producing high quality silicone rubbers. Among the tested platinum species the cis-complexes are much more active catalysts than their trans-congeners and for all studied platinum complexes cis-[PtCl2(NCCH2Ph)2] exhibits the best catalytic activity (room temperature, c = 1.0 × 10(-4) mol/L, τpot-life 60 min, τcuring 6 h). Although cis-[PtCl2(NCCH2Ph)2] is less active than the widely used Karstedt's catalyst, its application for the cross-linking can be performed not only at room temperature (c = 1.0 × 10(-4) mol/L), but also, more efficiently, at 80 °C (c = 1.0 × 10(-4)-1.0 × 10(-5) mol/L) and it prevents adherence of the formed silicone rubbers to equipment. The usage of the cis- and trans-[PtCl2(NCR)2] complexes as the hydrosilylation catalysts do not require any inhibitors and, moreover, the complexes and their mixtures with vinyl- and trimethylsilyl terminated polysiloxanes are shelf-stable in air. Tested catalysts do not form colloid platinum particles after the cross-linking.

Click-Type PtII -Mediated Hydroxyguanidine-Nitrile Coupling Provides Useful Catalysts for Hydrosilylation Cross-Linking.

The nitrile complexes trans-[PtCl2 (RCN)2 ] (R=Et (NC1), tBu (NC2), Ph (NC3), p-BrC6 H4 (NC4)) and cis-[PtCl2 (RCN)2 ] (R=Et (NC5), tBu (NC6), Ph (NC7)) react with 1 equiv of the hydroxyguanidine OC4 H8 NC(=NOH)NH2 (HG) furnishing the mono-addition products trans- and cis-[PtCl2 (RCN){NH=C(R)ON=C(NH2 )NC4 H8 O}] (1-4 and 9-11; 7 examples; 54-74 % yield). Treatment of any of the nitrile complexes NC1-NC7 with HG in a 1:2 molar ratio generated the bis-addition products trans- and cis-[PtCl2 {NH=C(R)ON=C(NH2 )NC4 H8 O}2 ] (5-8 and 12-14; 7 examples; 69-89 % yield). The PtII -mediated coupling between nitrile ligands and HG proceeds substantially faster than the corresponding reactions involving amid- and ketoximes and gives redox stable products under normal conditions. Complexes 1, 6⋅4 CH2 Cl2 , 7⋅4 CH2 Cl2 , 8⋅2 CH2 Cl2 , and NC4 were studied by X-ray crystallography. Platinum(II) species 1-3, 10, 11, and especially 9, efficiently catalyze the hydrosilylation cross-linking of vinyl-terminated poly(dimethylsiloxane) and trimethylsilyl-terminated poly(dimethylsiloxane-co-ethylhydrosiloxane) giving high-quality thermally stable silicon resins with no structural defects. The usage of these platinum species as the catalysts does not require any inhibitors and, moreover, the complexes and their mixtures with vinyl- and trimethylsilyl-terminated polysiloxanes are shelf-stable in air.