含环金属铱配合物高分子材料的制备及其氧气传感性能

通过含乙烯键的三联吡啶单体与甲基丙烯甲酯单体的共聚,制备了含配体的线性共聚物（P（MMA-co-TPY））。该共聚物继续与环金属铱二氯桥中间体反应,最终制备出含环金属铱配合物的高分子材料P（MMA-co-TPYIr）。用傅里叶变换红外光谱（FTIR）表征了材料的结构,并用紫外-可见光谱仪、荧光光谱仪研究了材料的光物理性能,最后研究了材料在溶液中的氧气传感性能。结果表明,环金属铱配合物已共价连接到高分子链上,固态下为纯红光发射,波长为638 nm,量子效率为0.035。该材料表现出了较好的氧气传感性能,并且在DMF中的效果最好,纯氮气和纯氧气氛围下的发光强度比为6,氧气检测限能达到0.34%。     

Large Two‐Photon Absorption of Terpyridine‐Based Quadrupolar Derivatives: Towards their Applications in Optical Limiting and Biological Imaging

Developing organic chromophores with large two‐photon absorption (TPA) in both organic solvents and aqueous media is crucial owing to their applications in solid‐state photonic devices and biological imaging. Herein, a series of novel terpyridine‐based quadrupolar derivatives have been synthesized. The influences of electron‐donating group, type of conjugated bridge, as well as solvent polarity on the molecular TPA properties have been investigated in detail. In contrast to the case in organic solvents, bis(thienyl)‐benzothiadiazole as a rigid conjugated bridge will completely quench molecular two‐photon emission in aqueous media. However, the combination of alkylcarbazole as the donor and bis(styryl)benzene as a conjugation bridge can enlarge molecular TPA cross‐sections in both organic solvent and aqueous media. The reasonable two‐photon emission brightness for the organic nanoparticles of chromophores 3 – 5 in the aqueous media, prepared by the reprecipitation method, enables them to be used as probes for in vivo biological imaging.     

One Ligand in Dual Roles: Self‐Assembly of a Bis‐Rhomboidal‐Shaped,Three‐Dimensional Molecular Wheel

A facile high yield, self‐assembly process that leads to a terpyridine‐based, three‐dimensional, bis‐rhomboidal‐shaped, molecular wheel is reported. The desired coordination‐driven supramolecular wheel involves eight structurally distorted tristerpyridine (tpy) ligands possessing a 60° angle between the adjacent tpy units and twelve Zn²⁺ ions. The tpy ligand plays dual roles in the self‐assembly process: two are staggered at 180° to create the internal hub, while six produce the external rim. The wheel can be readily generated by mixing the tpy ligand and Zn²⁺ in a stoichiometric ratio of 2:3; full characterization is provided by ESI‐MS, NMR spectroscopy, and TEM imaging.     

The LEGO toolbox: Supramolecular building blocks by nitroxide‐mediated controlled radical polymerization

A terpyridine‐functionalized alkoxyamine unimolecular initiator was used for the nitroxide‐mediated controlled living radical polymerization of n‐butylacrylate, N,N‐dimethylacrylamide, 4‐vinylpyridine, 2‐vinylpyridine, and isoprene. For the former three monomers, the kinetics were studied. All polymerizations resulted in well‐defined polymers having a single terpyridine ligand at the chain end and narrow polydispersity indices. The obtained polymers are valuable building blocks for metallo‐supramolecular polymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6331–6344, 2005     

Terpyridine‐modified poly(vinyl chloride): Possibilities for supramolecular grafting and crosslinking

Commercially available poly(vinyl chloride) (PVC) was covalently modified with terpyridine supramolecular binding units in a two‐step reaction. First, PVC was modified with aromatic thiols to introduce OH functionalities into the polymer backbone, which were subsequently reacted with an isocyanate‐functionalized terpyridine binding unit. The resulting functionalized material contained metal‐ion binding sites, which could be used for grafting and crosslinking reactions. A grafting experiment was performed with a small organic terpyridine ligand. The complexation of the modified PVC with several transition‐metal ions was studied with ultraviolet–visible spectroscopy and gel permeation chromatography. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2964–2973, 2003     

Enhanced third‐order nonlinear optical properties determined in thin films using the Z‐scan technique: bis(μ‐4,4′‐oxydibenzoato)bis[(4′‐phenyl‐2,2′:6′,2′′‐terpyridine)cobalt(II)]

π‐Conjugated organic materials exhibit high and tunable nonlinear optical (NLO) properties, and fast response times. 4′‐Phenyl‐2,2′:6′,2′′‐terpyridine (PTP) is an important N‐heterocyclic ligand involving π‐conjugated systems, however, studies concerning the third‐order NLO properties of terpyridine transition metal complexes are limited. The title binuclear terpyridine Co^II complex, bis(μ‐4,4′‐oxydibenzoato)‐κ³O,O′:O′′;κ³O′′:O,O′‐bis[(4′‐phenyl‐2,2′:6′,2′′‐terpyridine‐κ³N,N′,N′′)cobalt(II)], [Co₂(C₁₄H₈O₅)₂(C₂₁H₁₅N₃)₂], (1), has been synthesized under hydrothermal conditions. In the crystal structure, each Co^II cation is surrounded by three N atoms of a PTP ligand and three O atoms, two from a bidentate and one from a symmetry‐related monodentate 4,4′‐oxydibenzoate (ODA²⁻) ligand, completing a distorted octahedral coordination geometry. Neighbouring [Co(PTP)]²⁺ units are bridged by ODA²⁻ ligands to form a ring‐like structure. The third‐order nonlinear optical (NLO) properties of (1) and PTP were determined in thin films using the Z‐scan technique. The title compound shows a strong third‐order NLO saturable absorption (SA), while PTP exhibits a third‐order NLO reverse saturable absorption (RSA). The absorptive coefficient β of (1) is −37.3 × 10⁻⁷ m W⁻¹, which is larger than that (8.96 × 10⁻⁷ m W⁻¹) of PTP. The third‐order NLO susceptibility χ⁽³⁾ values are calculated as 6.01 × 10⁻⁸ e.s.u. for (1) and 1.44 × 10⁻⁸ e.s.u. for PTP.     

Base Metal-terpyridine Complex Immobilized on Stationary Phase Aimed as Reusable Hydrosilylation Catalyst

The catalytic activity of a base metal-terpyridine complex immobilized on silica gel ( M(tpy)X₂@SiO₂/H₂O : M=Mn, Fe, Co, Ni, Cu; X=Cl, Br) for hydrosilylation was investigated. Co(tpy)Br₂@SiO₂/H₂O in the presence of NaBHEt₃ exhibited the highest catalytic activity for hydrosilylation of 1-octene with diphenylsilane (Ph₂SiH₂) to form the anti-Markovnikov-type hydrosilylation compound as the main product. The reusability of Co(tpy)Br₂@SiO₂/H₂O activated by NaBHEt₃ was examined. It was found that the catalytic activity decreased with repeated use because of the peeling off of the Co complex anchor portion from the silica gel surface upon the attack of NaBHEt₃. The introduction of Co(OAc)₂ instead of CoBr₂ to silica gel formed Co(tpy)(OAc)₂- and Co(tpy)(OH)₂-immobilized silica gel, which exhibited catalytic activity for the hydrosilylation in the absence of an activator such as NaBHEt₃. The glassware in which Co(tpy)(OH)₂ was immobilized on the inner wall was prepared. It was found that the hydrosilylation catalytically occurred on the surface of a pretreated glassware and that the catalytic activity did not decrease even after 10 repeated uses.     

Synthesis,Crystal Structure and Two-photon Absorption Properties of 4′-(N,N-di(4-hydroxymethyl phenyl) amino)phenyl-2,2′:6′,2'-terpyridine

A novel donor-acceptor(D-A) triphenylamino terpyridine derivative L was facilely synthesized and fully characterized, and its single crystals were obtained and determined by X-ray diffraction analysis. It crystallizes in triclinic, space group P1 with a = 11.760(5), b =12.516(5), c = 12.850(5) , α = 67.141(5), β = 65.284(5), γ = 75.876(5)o, Mr = 621.54, V = 1575.6(11) 3, Z = 2, Dc = 1.310 g/cm3, μ = 0.245 mm-1, F(000) = 648, the final R = 0.0671 and w R = 0.1869 for 11328 observed reflections with Ⅰ 2σ(Ⅰ). Linear and nonlinear optical properties of terpyridine derivative L were systematically investigated. The maximum two-photon cross-section of L was 382.5 GM(Goeppert-Mayer), measured by two-photon excited fluorescence(TPEF) method. This result demonstrates that the increase of intramolecular charge transfer(ICT) leads to enhanced two-photon absorption(2PA), which could be achieved by introducing additional electron-donor groups to the molecular framework.     

1H, 13C, 15N NMR coordination shifts in Fe(II), Ru(II) and Os(II) cationic complexes with 2,2':6',2″-terpyridine

(1)H, (13)C and (15)N NMR studies of iron(II), ruthenium(II) and osmium(II) bis-chelated cationic complexes with 2,2':6',2″-terpyridine ([M(terpy)(2) ](2+) ; M = Fe, Ru, Os) were performed. Significant shielding of nitrogen-adjacent H(6) and deshielding of H(3'), H(4') protons were observed, both effects being mostly expressed for Fe(II) compounds. The metal-bonded nitrogens were shielded, this effect being much larger for the outer N(1), N(1″) than the inner N(1') atoms, and enhanced in the Fe(II) → Ru(II) → Os(II) series.