Further Insights into the Impact of Ligand-Localized Excited States on the Photophysics of Phenanthroline-Based Rhenium(I) Tricarbonyl Complexes.

The present work shows the pivotal role of N-donor substituents attached to 1,10-phenanthroline at the 4,7-positions in perturbation of ground- and excited-state properties of fac-[ReCl(CO)3(R2phen)]. Excited-state processes occurring upon photoexcitation in the designed systems were thoroughly explored with a wide range of steady-state and time-resolved spectroscopic techniques, including transient absorption, as well as experimental results were complemented by theoretical studies based on the density functional theory (DFT). It was demonstrated that the attachment of six-membered heterocyclic amines (piperidine─ppr, morpholine─mor, and thiomorpholine─tmor) is a very effective tool for extending absorptivity and excited-state lifetimes of resulting fac-[ReCl(CO)3(R2phen)] due to the contribution of the excited state localized on the phenanthroline-based ligand. Both absorption and emission properties of these systems were attributed to configurationally mixed MLCT/IL excited states. Re(I) complexes with phenoxazine (pxz) and phenothiazine (ptz) substituents were shown to possess charge-separated excited states, clearly evidenced by the simultaneous presence of signals typical of phen-* and pxz+* or ptz+* in transient absorption spectra. Both complexes are rare examples of NIR light-emitting coordination compounds. The decoration of the phen framework with less polar 9,9-dimethyl-9,10-dihydroacridine (dmac) groups resulted in the formation of [ReCl(CO)3(R2phen)] with mixed 3MLCT/3ILCT triplet excited state.

Pyrenyl-Substituted Imidazo[4,5-f][1,10]phenanthroline Rhenium(I) Complexes with Record-High Triplet Excited-State Lifetimes at Room Temperature: Steric Control of Photoinduced Processes in Bichromophoric Systems.

Photochemical applications based on intermolecular photoinduced energy triplet state transfer require photosensitizers with strong visible absorptivity and extended triplet excited-state lifetimes. Using a bichromophore approach, two Re(I) tricarbonyl complexes with 2-(1-pyrenyl)-1H-imidazo[4,5-f][1,10]phenanthroline (pyr-imphen) and 1-(4-(methyl)phenyl)-2-(1-pyrenyl)-imidazo[4,5-f][1,10]phenanthroline (pyr-tol-imphen) showing extraordinary long triplet excited states at room temperature (>1000 µs) were obtained, and their ground- and excited-state properties were thoroughly investigated by a wide range of spectroscopic methods, including femtosecond transient absorption (fs-TA). It is worth noting that the designed [ReCl(CO)3(pyr-imphen)] (1) and [ReCl(CO)3(pyr-tol-imphen)] (2) complexes form a unique pair differing in the mutual chromophore arrangement due to introduction of a 4-(methyl)phenyl substituent into the imidazole ring at the H1-position, imposing an increase in the dihedral angle between the pyrene and {ReCl(CO)3(imphen)} chromophores. The magnitude of the electronic coupling between the pyrene and {ReCl(CO)3(imphen)} chromophores was found to be an efficient tool to tune the photophysical properties of 1 and 2. The usefulness of designed Re(I) compounds as triplet photosensitizers was successfully verified by examination of their abilities for 1O2 generation and triplet-triplet annihilation upconversion. The phosphorescence lifetimes, ∼1800 µs for 1 and ∼1500 µs for 2, are the longest lifetimes reported for Re(I) diimine carbonyl complexes in solution at room temperature.

Photoinduced Processes in Rhenium(I) Terpyridine Complexes Bearing Remote Amine Groups: New Insights from Transient Absorption Spectroscopy.

Photophysical properties of two Re(I) complexes [ReCl(CO)3(R-C6H4-terpy-κ2N)] with remote amine groups, N-methyl-piperazinyl (1) and (2-cyanoethyl)methylamine (2), were investigated. The complexes show strong absorption in the visible region corresponding to metal-to-ligand charge transfer (1MLCT) and intraligand-charge-transfer (1ILCT) transitions. The energy levels of 3MLCT and 3ILCT excited-states, and thus photoluminescence properties of 1 and 2, were found to be strongly affected by the solvent polarity. Compared to the parent chromophore [ReCl(CO)3(C6H5-terpy-κ2N)] (3), both designed complexes show significantly prolonged (by 1-2 orders of magnitude) phosphorescence lifetimes in acetonitrile and dimethylformamide, contrary to their lifetimes in less polar chloroform and tetrahydrofuran, which are comparable to those for 3. The femtosecond transient absorption (fsTA) measurements confirmed the interconversion between the 3MLCT and 3ILCT excited-states in polar solvents. In contrast, the emissive state of 1 and 2 in less polar environments is of predominant 3MLCT nature.

From Red to Green Luminescence via Surface Functionalization. Effect of 2-(5-Mercaptothien-2-yl)-8-(thien-2-yl)-5-hexylthieno[3,4-c]pyrrole-4,6-dione Ligands on the Photoluminescence of Alloyed Ag-In-Zn-S Nanocrystals.

A semiconducting molecule containing a thiol anchor group, namely 2-(5-mercaptothien-2-yl)-8-(thien-2-yl)-5-hexylthieno[3,4-c]pyrrole-4,6-dione (abbreviated as D-A-D-SH), was designed, synthesized, and used as a ligand in nonstoichiometric quaternary nanocrystals of composition Ag1.0In3.1Zn1.0S4.0(S6.1) to give an inorganic/organic hybrid. Detailed NMR studies indicate that D-A-D-SH ligands are present in two coordination spheres in the organic part of the hybrid: (i) inner in which the ligand molecules form direct bonds with the nanocrystal surface and (ii) outer in which the ligand molecules do not form direct bonds with the inorganic core. Exchange of the initial ligands (stearic acid and 1-aminooctadecane) for D-A-D-SH induces a distinct change of the photoluminescence. Efficient red luminescence of nanocrystals capped with initial ligands (λmax = 720 nm, quantum yield = 67%) is totally quenched and green luminescence characteristic of the ligand appears (λmax = 508 nm, quantum yield = 10%). This change of the photoluminescence mechanism can be clarified by a combination of electrochemical and spectroscopic investigations. It can be demonstrated by cyclic voltammetry that new states appear in the hybrid as a consequence of D-A-D-SH binding to the nanocrystals surface. These states are located below the nanocrystal LUMO and above its HOMO, respectively. They are concurrent to deeper donor and acceptor states governing the red luminescence. As a result, energy transfer from the nanocrystal HOMO and LUMO levels to the ligand states takes place, leading to effective quenching of the red luminescence and appearance of the green one.

Highly Luminescent Ag-In-Zn-S Quaternary Nanocrystals: Growth Mechanism and Surface Chemistry Elucidation.

The presented research is focused on the synthesis of alloyed Ag-In-Zn-S colloidal nanocrystals from a mixture of simple metal precursors such as AgNO3, InCl3, zinc stearate combined with 1-dodecanethiol (DDT), 1-octadecene (ODE), and sulfur dissolved in oleylamine (OLA). In particular, the focus is on the effect of the solvent (ODE vs 1,2-dichlorobenzene (DCB)) and the type of sulfur precursor (S/OLA vs S/ n-octylamine (OCA)) on the metal precursors reactivates and on the chemical composition, crystal structure, and luminescent properties of the resulting nanocrystals. The replacement of ODE by DCB as a solvent lowers the reactivity of metal precursors and results in a 3-fold decrease of the photoluminescence quantum yields (Q.Y.) values (from 67% to 21%). This negative effect can be fully compensated by the use of S/OCA as a source of sulfur instead of S/OLA (Q.Y. increases from 21% to 64%). NMR studies of the isolated organic phase indicate that the S/OLA precursor generates two types of ligands being products of ( Z)-1-amino-9-octadecene (OLA) hydrogenation. These are "surface bound" 1-aminooctadecane (C18H37NH2) and crystal bound, i.e., alkyl chain covalently bound to the nanocrystal surface via surfacial sulfur (C18H37-NH-S crystal). Highly luminescent Ag-In-Zn-S nanocrystals exhibit a cation-enriched (predominantly indium) surface and are stabilized by a 1-aminooctadecane ligand, which shows more flexibility than OLA. These investigations were completed by hydrophilization of nanocrystals obtained via exchange of the primary ligands for 11-mercaptoundecanoic acid, (MUA) with only a 2-fold decrease of photoluminescence Q.Y. in the most successful case (from 67% to 31%). Finally, through ligand exchange, an electroactive inorganic/organic hybrid was obtained, namely, Ag-In-Zn-S/7-octyloxyphenazine-2-thiol, in which its organic part fully retained its electrochemical activity.

Luminescent-Substituted Fluoranthenes-Synthesis, Structure, Electrochemistry, and Optical Properties.

Six novel fluoranthene derivatives, namely, three terminally substituted and three bis(fluoranthene) units with fluorene, bithiophene, and carbazole spacers, were obtained through [2+2+2] cycloaddition and characterized completely. Based on the conducted studies, the obtained derivatives can be classified as donor-acceptor (D-A) and acceptor-donor-acceptor (A-D-A) systems, in which the fluoranthene unit acts as an electron-withdrawing unit. The optical results revealed that novel fluoranthene derivatives absorb light in the range λ=236-417 nm, which originates from a π→π* transition within the conjugated system. The compounds exhibit fluorescence that range from deep blue to green, which mainly arises from intramolecular charge transfer (ICT) states. High Stoke shifts and high quantum yields in solution (ϕ=0.22-0.57) and in the solid state (ϕ=0.18-0.44) have been observed for fluoranthene derivatives. All the derivatives display multistep oxidation processes at low potentials. The electronic structure of the presented compounds is additionally supported by time-dependent DFT computations.

Slow Magnetic Relaxation in Cobalt(II) Field-Induced Single-Ion Magnets with Positive Large Anisotropy.

Three pentacoordinate complexes of the type [Co( pypz)X2], where pypz is a tridentate ligand 2,6-bis(pyrazol-1-yl)pyridine and X = Cl- (1), NCS- (2), and NCO- (3), have been synthesized, and their structures have been determined by X-ray analysis. The DC magnetic data show a sizable magnetic anisotropy, which was confirmed by high-field high-frequency electron paramagnetic resonance (HF EPR) measurements. Well-resolved HF EPR spectra of high spin cobalt (II) were observed over the microwave frequency range 100-650 GHz. The experimental spectra of both complexes were simulated with axial g tensor components, a very large positive D value, and different E/ D ratios. To determine the exact D value for 2 (38.4 cm-1) and 3 (40.92 cm-1), the far-infrared magnetic spectroscopy method was used. Knowledge of the zero field splitting parameters and their signs is crucial in interpreting the single-molecule magnet or single chain magnet behavior. The AC susceptibility data confirm that these complexes exhibit a slow magnetic relaxation under small applied DC field with two (1 and 3) or three (2) relaxation modes.

Multifaceted strategy for the synthesis of diverse 2,2'-bithiophene derivatives.

New catalytically or high pressure activated reactions and routes, including coupling, double bond migration in allylic systems, and various types of cycloaddition and dihydroamination have been used for the synthesis of novel bithiophene derivatives. Thanks to the abovementioned reactions and routes combined with non-catalytic ones, new acetylene, butadiyne, isoxazole, 1,2,3-triazole, pyrrole, benzene, and fluoranthene derivatives with one, two or six bithiophenyl moieties have been obtained. Basic sources of crucial substrates which include bithiophene motif for catalytic reactions were 2,2'-bithiophene, gaseous acetylene and 1,3-butadiyne.

Ag-In-Zn-S alloyed nanocrystals as photocatalysts of controlled light-mediated radical polymerization.

We report on the first case of the use of nonstoichiometric ternary (Ag-In-Zn-S) semiconductor nanocrystals as photoinitiators and photocatalysts of methyl methacrylate (MMA) polymerization. Two types of nanocrystals were tested, differing in their composition and characterized by red (λmax = 731 nm) and green (λmax = 528 nm) photoluminescence, respectively. Exploiting their reducing properties and capability of free radical generation we demonstrate that under ultraviolet (UV) radiation they effectively photoinitiate radical polymerization of MMA whereas under visible light (blue or green) they act as photocatalysts of living radical polymerization.

In Vitro and In Vivo Biological Activities of Dipicolinate Oxovanadium(IV) Complexes.

The work is focused on anticancer properties of dipicolinate (dipic)-based vanadium(IV) complexes [VO(dipic)(N∩N)] bearing different diimines (2-(1H-imidazol-2-yl)pyridine, 2-(2-pyridyl)benzimidazole, 1,10-phenanthroline-5,6-dione, 1,10-phenanthroline, and 2,2'-bipyridine), as well as differently 4,7-substituted 1,10-phenanthrolines. The antiproliferative effect of V(IV) systems was analyzed in different tumors (A2780, HCT116, and HCT116-DoxR) and normal (primary human dermal fibroblasts) cell lines, revealing a high cytotoxic effect of [VO(dipic)(N∩N)] with 4,7-dimethoxy-phen (5), 4,7-diphenyl-phen (6), and 1,10-phenanthroline (8) against HCT116-DoxR cells. The cytotoxicity differences between these complexes can be correlated with their different internalization by HCT116-DoxR cells. Worthy of note, these three complexes were found to (i) induce cell death through apoptosis and autophagy pathways, namely, through ROS production; (ii) not to be cytostatic; (iii) to interact with the BSA protein; (iv) do not promote tumor cell migration or a pro-angiogenic capability; (v) show a slight in vivo anti-angiogenic capability, and (vi) do not show in vivo toxicity in a chicken embryo.

Indium(II) Chloride as a Precursor in the Synthesis of Ternary (Ag-In-S) and Quaternary (Ag-In-Zn-S) Nanocrystals.

A new indium precursor, namely, indium(II) chloride, was tested as a precursor in the synthesis of ternary Ag-In-S and quaternary Ag-In-Zn-S nanocrystals. This new precursor, being in fact a dimer of Cl2In-InCl2 chemical structure, is significantly more reactive than InCl3, typically used in the preparation of these types of nanocrystals. This was evidenced by carrying out comparative syntheses under the same reaction conditions using these two indium precursors in combination with the same silver (AgNO3) and zinc (zinc stearate) precursors. In particular, the use of indium(II) chloride in combination with low concentrations of the zinc precursor yielded spherical-shaped (D = 3.7-6.2 nm) Ag-In-Zn-S nanocrystals, whereas for higher concentrations of this precursor, rodlike nanoparticles (L = 9-10 nm) were obtained. In all cases, the resulting nanocrystals were enriched in indium (In/Ag = 1.5-10.3). Enhanced indium precursor conversion and formation of anisotropic, longitudinal nanoparticles were closely related to the presence of thiocarboxylic acid type of ligands in the reaction mixture. These ligands were generated in situ and subsequently bound to surfacial In(III) cations in the growing nanocrystals. The use of the new precursor of enhanced reactivity facilitated precise tuning of the photoluminescence color of the resulting nanocrystals in the spectral range from ca. 730 to 530 nm with photoluminescence quantum yield (PLQY) varying from 20 to 40%. The fabricated Ag-In-S and Ag-In-Zn-S nanocrystals exhibited the longest, reported to date, photoluminescence lifetimes of ∼9.4 and ∼1.4 µs, respectively. It was also demonstrated for the first time that ternary (Ag-In-S) and quaternary (Ag-In-Zn-S) nanocrystals could be applied as efficient photocatalysts, active under visible light (green) illumination, in the reaction of aldehydes reduction to alcohols.

Organic-to-Aqueous Phase Transfer of Alloyed AgInS2-ZnS Nanocrystals Using Simple Hydrophilic Ligands: Comparison of 11-Mercaptoundecanoic Acid, Dihydrolipoic Acid and Cysteine.

The exchange of primary hydrophobic ligands for hydrophilic ones was studied for two types of alloyed AgInS2-ZnS nanocrystals differing in composition and by consequence exhibiting two different emission colors: red (R) and green (G). Three simple hydrophilic ligands were tested, namely, 11-mercaptoundecanoic acid, dihydrolipoic acid and cysteine. In all cases, stable aqueous colloidal dispersions were obtained. Detailed characterization of the nanocrystal surface before and after the ligand exchange by NMR spectroscopy unequivocally showed that the exchange process was the most efficient in the case of dihydrolipoic acid, leading to the complete removal of the primary ligands with a relatively small photoluminescence quantum yield drop from 68% to 40% for nanocrystals of the R type and from 48% to 28% for the G ones.

Synthesis of unsymmetrical alkyl acetals via addition of primary alcohols to allyl ethers mediated by ruthenium complexes.

ABSTRACT: Ru-catalyzed synthesis of mixed alkyl-alkyl acetals via addition of primary alcohols to allyl ethers has been extended to include long-chain and/or functionalized substrates. The catalytic systems for these reactions were generated from RuCl2(PPh3)3 and [RuCl2(1,5-COD)]x and phosphines [PPh3 or P(p-chlorophenyl)3] or SbPh3. Of particular importance is the almost quantitative elimination of transacetalization. The addition proceeds through allyl complexes, not via isomerization of allyl ethers--subsequent addition of ROH to vinyl ethers.