Green and blue electrochemically generated chemiluminescence from click chemistry--customizable iridium complexes.

Cationic cyclometalated iridium complexes containing two anionic phenylpyridine (ppy) ligands and the neutral bidentate triazole-pyridine ligand, 2-(1-substituted-1H-1,2,3-triazol-4-yl)pyridine (pytl), were investigated. The complexes display a rich and reversible electrochemical behavior, upon investigations by cyclic voltammetry in strictly aprotic conditions, that couples with excellent emission quantum yields and long lifetimes of the excited states. Therefore, in organic media, all complexes have generated intense green electrochemiluminescence (ECL) through the so-called annihilation procedure and, importantly, a modulation of the emission energy (to blue) has been easily obtained by simple fluorination of the ppy ligand. Finally, taking advantage of their remarkable solubility in water, intense ECL was also obtained from aqueous buffer solutions using the co-reactant method, thus making all the investigated complexes highly promising for their effective use as ECL labels in bioanalytical applications.

SERS chiral recognition and quantification of enantiomers through cyclodextrin supramolecular complexation.

We introduce here a simple approach in which a cyclodextrin, functionalized with thiols in the narrower rim, is assembled onto the silver surface of a SERS platform composed of polystyrene beads coated with silver nanoparticles. Trapping properties of the fabricated sensor are demonstrated through the retention of different enantiomers (R,R or/and S,S) of hydrobenzoin (HBZ), a molecule that has not been reported before in SERS because it has no affinity for coinage metal surfaces. Further, selective recognition of each enantiomer and semiquantification of its proportion in a racemic mixture are provided by the analysis of the SERS spectra of the HBZ-cyclodextrin complex, in full agreement with the surface selection rules.

Efficient photoinduced energy transfer mediated by aromatic homoconjugated bridges.

A new donor-bridge-acceptor (D-B-A) dyad consisting of ruthenium(II) and iridium(III) species separated by an homoconjugated bridge derived from 7,7-diphenylnorbornane [Ir-Nor-Ru](3+) has been synthesised. The photophysical and electrochemical properties of the heterodinuclear complex have been compared with those of the analogous homodinuclear complexes [Ru-Nor-Ru](4+) and [Ir-Nor- Ir](2+) . Transient absorption spectra on the nanosecond and sub-picosecond timescales show, for the first time, that an homoconjugated bridge can mediate efficiently in the photoinduced energy transfer from the iridium(III) to the ruthenium(II) centres according to a Dexter-type mechanism.

Cationic heteroleptic cyclometalated iridium(III) complexes containing phenyl-triazole and triazole-pyridine clicked ligands.

Novel heteroleptic iridium complexes containing the 1-substituted-4-phenyl-1H-1,2,3-triazole (phtl) cyclometalating ligand have been synthesized. The 3+2 Huisgen dipolar cycloaddition method ('click' chemistry) was utilized to prepare a class of bidentate ligands (phtl) bearing different substituents on the triazole moiety. By using various ligands (phtl-R1 and pytl-R2) (R1 = adamantane, methyl and R2 = adamantane, methyl, beta-cyclodextrin, ursodeoxycholic acid), we prepared a small library of new luminescent ionic iridium complexes [Ir(phtr-R1)2(pytl-R2)]Cl and report on their photophysical properties. The flexibility of the clicking approach allows a straightforward control on the chemical-physical properties of the complexes by varying the nature of the substituent on the ligand.

Ir(III) and Ru(II) complexes containing triazole-pyridine ligands: luminescence enhancement upon substitution with beta-cyclodextrin.

Novel 2-(1-substituted-1H-1,2,3-triazol-4-yl)pyridine (pytl) ligands have been prepared by "click chemistry" and used in the preparation of heteroleptic complexes of Ru and Ir with bipyridine (bpy) and phenylpyridine (ppy) ligands, respectively, resulting in [Ru(bpy)(2)(pytl-R)]Cl(2) and [Ir(ppy)(2)(pytl-R)]Cl (R=methyl, adamantane (ada), beta-cyclodextrin (betaCD)). The two diastereoisomers of the Ir complex with the appended beta-cyclodextrin, [Ir(ppy)(2)(pytl-betaCD)]Cl, were separated. The [Ru(bpy)(2)(pytl-R)]Cl(2) (R=Me, ada or betaCD) complexes have lower lifetimes and quantum yields than other polypyridine complexes. In contrast, the cyclometalated Ir complexes display rather long lifetimes and very high emission quantum yields. The emission quantum yield and lifetime (Phi=0.23, tau=1000 ns) of [Ir(ppy)(2)(pytl-ada)]Cl are surprisingly enhanced in [Ir(ppy)(2)(pytl-betaCD)]Cl (Phi=0.54, tau=2800 ns). This behavior is unprecedented for a metal complex and is most likely due to its increased rigidity and protection from water molecules as well as from dioxygen quenching, because of the hydrophobic cavity of the betaCD covalently attached to pytl. The emissive excited state is localized on these cyclometalating ligands, as underlined by the shift to the blue (450 nm) upon substitution with two electron-withdrawing fluorine substituents on the phenyl unit. The significant differences between the quantum yields of the two separate diastereoisomers of [Ir(ppy)(2)(pytl-betaCD)]Cl (0.49 vs. 0.70) are attributed to different interactions of the chiral cyclodextrin substituent with the Delta and Lambda isomers of the metal complex.

Photoinduced energy transfer across non-covalent bonds in the nanoscale: cyclodextrin hosts with enhanced luminescent properties for guest communication.

Two photoactive cyclodextrin hosts have been prepared and studied in participation on photophysical processes, one with a ruthenium tris(bipyridyl) core which forms a trimeric host and the other with an appended anthracene unit. An acetylide functionalized bipyridyl cyclodextrin, , was prepared by palladium coupling of mono-6-propargyl permethylated beta-CD and 4-bromo-2,2'-bipyridine. The ruthenium complex, [Ru(3)]Cl(2), shows luminescence from the (3)MLCT centered at 650 nm with a quantum yield of 0.044 and a lifetime at room temperature of 1.1 micros in aerated aqueous solution. The enhanced luminescence properties have been attributed to extra delocalisation afforded by the three propargyl units appended to the complex and the stabilization of the MLCT state. An anthracene functionalised cyclodextrin was prepared from mono-6-O-p-toluenesulfonyl permethylated beta-cyclodextrin and 9-anthracene methanol. It shows fluorescence at room temperature with a maximum at 400 nm with a lifetime of 7 ns. Transient absorption spectroscopy has been used to elucidate the excited state properties of [Ru(3)]Cl(2) and hosts. A broad band centered around 600 nm in the [Ru(3)]Cl(2) transient spectrum corresponds to the absorption of the pi-radical anion of the ethynyl fragment of ligand and in a signal at 595 nm was observed, corresponding to the absorption of the anthracene excited singlet state. We used a bisadamantyl guest to assemble the two hosts and studied the energy transfer from the ruthenium core to the anthracene unit by steady state emission spectroscopy. The photoinduced energy transfer process in assemblies of host with ruthenium or osmium metalloguests, [Ru(biptpy)(tpy)](NO(3))(2) and [Os(biptpy)(tpy)](NO(3))(2), was studied by femtosecond transient spectroscopy and steady state emission spectroscopy. The singlet state of the anthracene pendant unit acted as a donor to the MLCT of the Ru(II) or Os(II) metalloguests. An energy transfer rate from the singlet anthracene excited state to the (1)MLCT of the ruthenium centre of 4.8 x 10(8) s(-1) was estimated in the case of the ruthenium guest. The photoinduced triplet energy transfer ( approximately 6 x 10(6) s(-1)) from a longer lived luminescent guest Rubph to the anthracene unit was studied by transient absorption spectroscopy.