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A series of luminescent bis-cyclometalated iridium complexes with 2,2′:6′,2″-terpyridine (tpy), [Ir(C^N)2(tpy)]PF6 (C^N = 2-phenylpyridinate (ppy) for 1; benzo[h]quinolinate (bzq) for 2; 1-phenylisoquinolinate (piq) for 3; and 2-phenylbenzothiazolate (pbt) for 4), have been synthesized and structurally characterized. Single-crystal X-ray diffraction analyses reveal that the tpy ligands of 1–4 are coordinated to the iridium center in a bidentate fashion, and the uncoordinated pendant pyridine rings in the tpy ligands of 1–4 form intramolecular π-π stacking interactions with a phenyl moiety of C^N ligands. In addition, the pendant pyridine ring in the tpy ligand of 1 forms an intramolecular hydrogen bonding interaction, unlike in 2–4. Of interest, the photophysical properties of 1–4 are strongly influenced by the C^N ligands; 1 shows a luminescence band at 572 nm, with a short lifetime (τ) value of 80 nsec and a lower absolute luminescence quantum yield (Φ) of 3.72%, whereas 3 exhibits an intense luminescence band at 588 nm with a long τ value of 1965 nsec and a moderate Φ value of 9.57%. The density functional theory calculations revealed that the luminescence originates from the triplet metal–ligand to ligand charge transfer (3MLL′CT) excited state.

An outstanding heterogeneous catalyst was successfully prepared by immobilization of palladium nanoparticles (Pd NPs) with polymer containing 4′‐(4‐hydroxyphenyl)‐2,2′:6′,2″‐terpyridine (HPTPy) ligand. The polymer cross‐linked with trimethylolpropane triacrylate (TMPTA) units was synthesized by polymerization of itaconic acid-HPTPy (ITC-HPTPy) monomer (so-called cross‐linked poly (ITC- HPTPy)). The cross‐linked poly (ITC-HPTPy) can stabilize the Pd NPs effectively against aggregation, thereby improving the catalytic efficiency of Pd NPs. The presence of Pd NPs on the polymer was confirmed by various physicochemical techniques. The resulting cross‐linked poly (ITC-HPTPy)-Pd was applied as a highly effective recyclable catalyst in Suzuki–Miyaura and Mizoroki–Heck coupling reactions under low Pd-loading conditions and straightforward methods, and provided the corresponding products with excellent yields (up to 98%), high catalytic activities (TOF up to 213 h −1 ). The catalyst can be separated from the reaction mixture by centrifugation and can be reused consecutive six times with slight reduction in catalytic activity. Graphic Abstract Pd NPs immobilized with polymer containing terpyridine ligand are highly active heterogeneous catalysts for Suzuki–Miyaura and Mizoroki–Heck coupling reactions.

In this study, terpyridine functionalized phosphazene based metallo-supramolecular polymers were synthesized by three step reaction method. In the first step, 4′-(4-aminophenyl)-2,2′:6′,2′′-terpyridine was synthesized with p -nitro benzaldehyde and 2-acetylpyridine. Then, the monomer containing six terpyridine (TPY) units attached to the phosphazene was prepared from 4′-(4-aminophenyl)-2,2′:6′,2′′-terpyridine and hexachlorocyclotriphosphazene by a condensation reaction. Finally, metallo-supramolecular phosphazene polymers were synthesised with these TPY functional phosphazenes and different transition metal ions (Cu, Co, Ni, and Zn ions). Prepared metallo-supramolecular polymers containing phosphazene unit were investigated by elemental analysis, different spectroscopic methods, energy dispersive X-ray spectrometry (EDX) and thermal analysis techniques. The stimuli-responsive, optoelectronic and spectroscopic properties of the synthesised metallo-supramolecular phosphazene polymers were investigated for external effects with UV–Vis spectroscopy and electro-analytic techniques. In addition, competitive ligand effect on these metallo-supramolecular polymers was examined with ethylenediaminetetraacetic acid (EDTA). The resulting metallo-supramolecular polymers containing phosphazene unit show very fast stimuli-responsive properties, such as 3 s. they also showed a single reversible redox structure resulting from the bonding of homometallic segments to polymer chain. In addition, they showed d-π transition (in the range of λ = 330–550 nm) depending on the metal (Co, Ni and Zn) ion forming the supramolecular structure. The addition of competing EDTA ligands caused the degradation of metallo-supramolecular polymer structures. These metallo-supramolecular phosphazene polymers are a good alternative smart material for opto-electronic, electrochromic, photochromic and intelligent material applications.

This is the first comprehensive review of rhenium(I) carbonyl complexes with 2,2′:6′,2″-terpyridine-based ligands (R-terpy)—encompassing their synthesis, molecular features, photophysical behavior, and potential applications. Particular attention has been devoted to demonstrating how the coordination mode of 2,2′:6′,2″-terpyridine (terpy-κ2N and terpy-κ3N), structural modifications of terpy framework (R), and the nature of ancillary ligands (X—mono-negative anion, L—neutral ligand) may tune the photophysical behavior of Re(I) complexes [Re(X/L)(CO)3(R-terpy-κ2N)]0/+ and [Re(X/L)(CO)2(R-terpy-κ3N)]0/+. Our discussion also includes homo- and heteronuclear multicomponent systems with Re(CO)3(R-terpy-κ2N) and Re(CO)2(R-terpy-κ3N) motifs. The presented structure–property relationships are of high importance for controlling the photoinduced processes in these systems and making further progress in the development of more efficient Re-based luminophores, photosensitizers, and photocatalysts for modern technologies.

A heteroleptic [Ru(terpy)2]2+ (terpy = 2,2′:6′,2″-terpyridine) complex was electrochemically polymerized to give the corresponding metal-containing conducting polymer on gold and glassy carbon electrodes. The polymerization of the Ru(II) complex was allowed by a terthiophene functionalization on one of the two terpy coordinating fragments, whereas the presence of -COOH substituents on the second terpy ligand enabled the film to immobilize a tyrosinase enzyme by cross-linking with glutaraldehyde. Then, the Ru(terpy) conducting polymer worked as a transducer as well as an immobilizing agent in the design of amperometric biosensors for the determination of epinephrine. The electrochemical behavior of enzymatic sensors containing Ru(terpy)-based conducting polymers was investigated by differential pulse voltammetry and chronoamperometry. Analytical performances and kinetic parameters were calculated, suggesting a potential application of the reported biosensors in the determination of epinephrine in pharmaceutical products.

In this work, four new transition metal complexes, [Zn(PTP)] 12 (1,4-NDA) 12 ·2H 2 O ( 1) , [Zn(PTP) (4,4′-ODA)] 2 ( 2 ), [Ni(PTP)(4,4′-ODA)] 2 ( 3 ) and [Ni(FTP)] 2 Cl 4 ( 4 ), have been synthesized by the reaction between a metal salt, Zn(II) or Ni(II), a rigid polycarboxylic ligand, naphthalene-1,4-dicarboxylic acid (1,4-NDA) or 4,4′-oxydibenzoic acid (4,4′-ODA) and a co-ligand, 4′-phenyl-2,2′:6′,2″-terpyridine (PTP) or 4′-(furan-2-yl)-2,2′:6′,2″-terpyridine (FTP). Complex 1 based on {Zn(PTP)(1,4-NDA)} n intertwined chains characterized by three different configurations which form a chiral chain structure. Complexes 2 and 3 present a structure made of discrete rings containing two central metal atoms. In Complex 4 , two complex Ni(FTP) 2+ ions are found to be connected with the μ 2 –Cl bridge to form a binuclear cluster. The third-order nonlinear optical properties of each complex thin film were evaluated by the Z-scan technique, indicating a strong third-order nonlinear reverse saturable absorption effect, with a high absorption coefficient β 3.89 × 10 −6 for 1 , 40.50 × 10 −6 for 2 , 4.76 × 10 −6 for 3 , and 1.37 × 10 −6 m W −1 for 1 , respectively. Interestingly, Complex 1 exhibits an effective nonlinear refractive effect with a refractive coefficient of 7.16 × 10 −13 m 2  W −1 . The third-order NLO susceptibilities χ (3) of each complexes were calculated.

A novel metallo-supramolecular polytopic ligand was synthesized from the attachment reaction involving an amino group-functionalized multi-wall carbon nanotube and 4-chloro-2,2′:6′,2″-terpyridine used for the preparation of metallo-supramolecular polymers with Co(II) or Ni(II) ions. Different colors were observed depending on either the ligands or the metal ions in this type of supramolecular assembly. The created supramolecular polymers were characterized by means of structure, morphology, and stimuli-responsive performance employing scanning electron microscopy, amperometric techniques, UV–Vis and Fourier transform infrared spectroscopy. UV–Vis spectroscopy and cyclic voltammetry studies confirmed that both the optical and electrochemical properties of metallo-supramolecular materials are affected by the substituent at the pyridine periphery.

A redox-active adlayer consisting of cobalt ions and terpyridine ligands, 4′,4′′′′-(1,4-phenylene)bis(2,2′:6′,2′′-terpyridine), was prepared on a Au(111) surface by a stepwise coordination method. The obtained adlayer produced a well-defined, stable redox wave associated with cobalt ions coordinated to 4′,4′′′′-(1,4-phenylene)bis(2,2′:6′,2′′-terpyridine), as compared to a tetra-2-pyridinyl-pyrazine adlayer, for which no redox wave was observed. In situ scanning tunneling microscopy revealed a structural change in the redox-active adlayer consisting of 4′,4′′′′-(1,4-phenylene)bis(2,2′:6′,2′′-terpyridine) and cobalt ions. It was found that the ability of cobalt ions to coordinate on Au(111) was clearly dependent on the chemical structure of the ligand, suggesting that ligand coordination with metal ions on the Au surface is determined by the molecular orientation and configuration of the ligand when the ligand is adsorbed on a Au substrate.

The use of divergent 4,2′:6′,4″- and 3,2′:6′,3″-terpyridine ligands as linkers and/or nodes in extended coordination assemblies has gained in popularity over the last decade. However, there is also a range of coordination polymers which feature 2,2′:6′,2″-terpyridine metal-binding domains. Of the remaining 45 isomers of terpyridine, few have been utilized in extended coordination arrays. Here, we provide an overview of coordination polymers and networks containing isomers of terpyridine and either zinc(II) and cadmium(II). Although the motivation for investigations of many of these systems is their luminescent behavior, we have chosen to focus mainly on structural details, and we assess to what extent assemblies are reproducible. We also consider cases where there is structural evidence for competitive product formation. A point that emerges is the lack of systematic investigations.