Dual Role of a Novel Heteroleptic Cu(I) Complex in Visible-Light-Driven CO2 Reduction.

A novel mononuclear Cu(I) complex was synthesized via coordination with a benzoquinoxalin-2'-one-1,2,3-triazole chelating diimine and the bis[(2-diphenylphosphino)phenyl] ether (DPEPhos), to target a new and efficient photosensitizer for photocatalytic CO2 reduction. The Cu(I) complex absorbs in the blue-green region of the visible spectrum, with a broad band having a maximum at 475 nm (ϵ =4500 M-1 cm-1), which is assigned to the metal-to-ligand charge transfer (MLCT) transition from the Cu(I) to the benzoquinoxalin-2'-one moiety of the diimine. Surprisingly, photo-driven experiments for the CO2 reduction showed that this complex can undergo a photoinduced electron transfer with a sacrificial electron donor and accumulate electrons on the diimine backbone. Photo-driven experiments in a CO2 atmosphere revealed that this complex can not only act as a photosensitizer, when combined with an Fe(III)-porphyrin, but can also selectively produce CO from CO2. Thus, owing to its charge-accumulation properties, the non-innocent benzoquinoxalin-2-one based ligand enabled the development of the first copper(I)-based photocatalyst for CO2 reduction.

Selectivity control towards CO versus H2 for photo-driven CO2 reduction with a novel Co(II) catalyst.

Developing efficient catalysts for reducing carbon dioxide, a highly stable combustion waste product, is a relevant task to lower the atmospheric concentration of this greenhouse gas by upcycling. Selectivity towards CO2-reduction products is highly desirable, although it can be challenging to achieve since the metal-hydrides formation is sometimes favored and leads to H2 evolution. In this work, we designed a cobalt-based catalyst, and we present herein its physicochemical properties. Moreover, we tailored a fully earth-abundant photocatalytic system to achieve specifically CO2 reduction, optimizing efficiency and selectivity. By changing the conditions, we enhanced the turnover number (TON) of CO production from only 0.5 to more than 60 and the selectivity from 6% to 97% after four hours of irradiation at 420 nm. Further efficiency enhancement was achieved by adding 1,1,1,3,3,3-hexafluoropropan-2-ol, producing CO with a TON up to 230, although at the expense of selectivity (54%).

Metal-to-Metal Distance Modulated Au(I)/Ru(II) Cyclophanyl Complexes: Cooperative Effects in Photoredox Catalysis.

The modular synthesis of Au(I)/Ru(II) decorated mono- and heterobimetallic complexes with π-conjugated [2.2]paracyclophane is described. [2.2]Paracyclophane serves as a rigid spacer which holds the metal centers in precise spatial orientations and allows metal-to-metal distance modulation. A broad set of architectural arrangements of pseudo -geminal, -ortho, -meta, and -para substitution patterns were employed. Metal-to-metal distance modulation of Au(I)/Ru(II) heterobimetallic complexes and the innate transannular π-communication of the cyclophanyl scaffold provides a promising platform for the investigations of structure-activity relationship and cooperative effects. The Au(I)/Ru(II) heterobimetallic cyclophanyl complexes are stable, easily accessible, and exhibit promising catalytic activity in the visible-light promoted arylative Meyer-Schuster rearrangement.

Time-Resolved Spectroscopy and Electronic Structure of Mono-and Dinuclear Pyridyl-Triazole/DPEPhos-Based Cu(I) Complexes.

Chemical and spectroscopic characterization of the mononuclear photosensitizers [(DPEPhos)Cu(I)(MPyrT)]0/+ (CuL, CuLH) and their dinuclear analogues (Cu2 L', Cu2 L'H2 ), backed by (TD)DFT and high-level GW-Bethe-Salpeter equation calculations, exemplifies the complex influence of charge, nuclearity and structural flexibility on UV-induced photophysical pathways. Ultrafast transient absorption and step-scan FTIR spectroscopy reveal flattening distortion in the triplet state of CuLH as controlled by charge, which also appears to have a large impact on the symmetry of the long-lived triplet states in Cu2 L' and Cu2 L'H2 . Time-resolved luminescence spectroscopy (solid state), supported by transient photodissociation spectroscopy (gas phase), confirm a lifetime of some tens of µs for the respective triplet states, as well as the energetics of thermally activated delayed luminescence, both being essential parameters for application of these materials based on earth-abundant copper in photocatalysis and luminescent devices.

Cyan-Emitting Cu(I) Complexes and Their Luminescent Metallopolymers.

Copper complexes have shown great versatility and a wide application range across the natural and life sciences, with a particular promise as organic light-emitting diodes. In this work, four novel heteroleptic Cu(I) complexes were designed in order to allow their integration in advanced materials such as metallopolymers. We herein present the synthesis and the electrochemical and photophysical characterisation of these Cu(I) complexes, in combination with ab initio calculations. The complexes present a bright cyan emission (λem ~ 505 nm) in their solid state, both as powder and as blends in a polymer matrix. The successful synthesis of metallopolymers embedding two of the novel complexes is shown. These copolymers were also found to be luminescent and their photophysical properties were compared to those of their polymer blends. The chemical nature of the polymer backbone contributes significantly to the photoluminescence quantum yield, paving a route for the strategic design of novel luminescent Cu(I)-based polymeric materials.

New Photosensitizers Based on Heteroleptic CuI Complexes and CO2 Photocatalytic Reduction with [NiII (cyclam)]Cl2.

Earth-abundant metal complexes have been attracting increasing attention in the field of photo(redox)catalysis. In this work, the synthesis and full characterisation of four new heteroleptic CuI complexes are reported, which can work as photosensitizers. The complexes bear a bulky diphosphine (DPEPhos=bis[(2-diphenylphosphino)phenyl] ether) and a diimine chelating ligand based on 1-benzyl-4-(quinol-2'yl)-1,2,3-triazole. Their absorption has a relative maximum in the visible-light region, up to 450 nm. Thus, their use in photocatalytic systems for the reduction of CO2 with blue light in combination with the known catalyst [NiII (cyclam)]Cl2 was tested. This system produced CO as the main product through visible light (λ=420 nm) with a TON up to 8 after 4 hours. This value is in line with other photocatalytic systems using the same catalyst. Nevertheless, this system is entirely noble-metal free.

Chasing BODIPY: Enhancement of Luminescence in Homoleptic Bis(dipyrrinato) ZnII Complexes Utilizing Symmetric and Unsymmetrical Dipyrrins.

Dipyrromethene metal complexes are fascinating molecules that have applications as light-harvesting systems, luminophores, and laser dyes. Recently, it has been shown that structurally rigid bis(dipyrrinato) zinc(II) complexes exhibit high fluorescence with comparable quantum yields to those of boron dipyrromethenes or BODIPYs. Herein, eight new bis(dipyrrinato) ZnII complexes, obtained from symmetric and unsymmetrical functionalization of the dipyrromethene structure through a Knoevenagel reaction, are reported. It was possible not only to vary the maximum visible absorption from 490 to 630 nm, but also to enhance the emission quantum yield up to 66 %, which is extraordinarily high for homoleptic bis(dipyrrinato) zinc complexes. These results pave the way for designing highly luminescent bis(dipyrrinato) zinc complexes.

Click-Derived Triazolylidenes as Chelating Ligands: Achievement of a Neutral and Luminescent Iridium(III)-Triazolide Complex.

Versatility in the synthesis of triazole derivatives was exploited to obtain convenient mesoionic carbenes working as chelating or cyclometalating ligands for the preparation of cationic or neutral iridium(III) complexes. We present the synthesis and characterization of three new cationic cyclometalating iridium(III) complexes (1-3-BF4) and a neutral one (4), equipped with functionalized triazolylidene ligands. All the complexes are obtained in good yields, present irreversible or quasi-reversible oxidation and reduction processes, and display good photophysical stability. The complexes emit from 3MLCT or 3LC states, depending on the nature of the ancillary ligand. Compounds 1-3-BF4 display very low photoluminescence quantum yields (PLQY ≈ 1% in acetonitrile solution). Density functional theory calculations show that the luminescence of these three complexes is quenched by the presence of low-lying 3MC states, leading to a reversible detachment of the neutral ancillary ligands from the metal coordination sphere. On the contrary, this nonradiative deactivation pathway is not present in the case of the neutral complex 4, which in fact shows PLQYs above 10% and is the best emitter of the series. Moreover, complex 4 represents the first reported example of a photochemically and thermally stable neutral triazolide iridium(III) complex.

Surprisingly facile CO2 insertion into cobalt alkoxide bonds: A theoretical investigation.

Exploiting carbon dioxide as co-monomer with epoxides in the production of polycarbonates is economically highly attractive. More effective catalysts for this reaction are intensively being sought. To promote better understanding of the catalytic pathways, this study uses density functional theory calculations to elucidate the reaction step of CO2 insertion into cobalt(III)-alkoxide bonds, which is also the central step of metal catalysed carboxylation reactions. It was found that CO2 insertion into the cobalt(III)-alkoxide bond of [(2-hydroxyethoxy)Co(III)(salen)(L)] complexes (salen = N,N"-bis(salicyliden-1,6-diaminophenyl)) is exothermic, whereby the exothermicity depends on the trans-ligand L. The more electron-donating this ligand is, the more exothermic the insertion step is. Interestingly, we found that the activation barrier decreases with increasing exothermicity of the CO2 insertion. Hereby, a linear Brønsted-Evans-Polanyi relationship was found between the activation energy and the reaction energy.

Luminescent dinuclear Cu(I) complexes containing rigid tetraphosphine ligands.

The synthesis and the photophysics of three dinuclear copper(I) complexes containing bis(bidentate)phosphine ligands are described. The steric constraint imposed by tetrakis(di(2-methoxyphenyl)phosphanyl)cyclobutane) (o-MeO-dppcb) in combination with 2,9-dimethyl-1,10-phenanthroline in one of the complexes leads to interesting photophysical properties. The compound shows an intense emission at room temperature in deoxygenated acetonitrile solution (Φ = 49%) and a long excited-state lifetime (13.8 µs). Interestingly, at low temperature, 77 K, the emission maximum shifts to lower energy, and the excited-state lifetime increases. This observation leads to the conclusion that a mixing between the excited triplet and singlet states is possible and that the degree of mixing and population of state strongly depends on temperature, as the energy difference is quite small. The electroluminescent properties of this compound were therefore tested in light-emitting electrochemical cells (LEECs), proving that the bright emission can also be obtained by electrically driven population of the singlet state.

Thermally Activated Delayed Fluorescence (TADF) Materials Based on Earth-Abundant Transition Metal Complexes: Synthesis, Design and Applications.

Materials exhibiting thermally activated delayed fluorescence (TADF) based on transition metal complexes are currently gathering significant attention due to their technological potential. Their application extends beyond optoelectronics, in particular organic light-emitting diodes (OLEDs) and light-emitting electrochemical cells (LECs), and include also photocatalysis, sensing, and X-ray scintillators. From the perspective of sustainability, earth-abundant metal centers are preferred to rarer second- and third-transition series elements, thus determining a reduction in costs and toxicity but without compromising the overall performances. This review offers an overview of earth-abundant transition metal complexes exhibiting TADF and their application as photoconversion materials. Particular attention is devoted to the types of ligands employed, helping in the design of novel systems with enhanced TADF properties.

Reaching strong absorption up to 700 nm with new benzo[g]quinoxaline-based heteroleptic copper(I) complexes for light-harvesting applications.

Heteroleptic copper(I) complexes, with a diimine as a chromophoric unit and a bulky diphosphine as an ancillary ligand, have the advantage of a reduced pseudo Jahn-Teller effect in their excited state over the corresponding homoleptic bis(diimine) complexes. Nevertheless, their lowest absorption lies generally between 350 to 500 nm. Aiming at a strong absorption in the visible by stable heteroleptic Cu(I) complexes, we designed a novel diimine based on 4-(benzo[g]quinoxal-2'-yl)-1,2,3-triazole derivatives. The large π-conjugation of the benzoquinoxaline moiety shifted bathochromically the absorption with regard to other diimine-based Cu(I) complexes. Adding another Cu(I) core broadened the absorption and extended it to considerably longer wavelengths. Moreover, by fine-tuning the structure of the dichelating ligand, we achieved a panchromatic absorption up to 700 nm with a high molar extinction coefficient of 8000 M-1 cm-1 at maximum (λ = 570 nm), making this compound attractive for light-harvesting antennae.

Selective Positioning of Different Cell Types on 3D Scaffolds via DNA Hybridization.

Three-dimensional (3D) microscaffolds for cell biology have shown their potential in mimicking physiological environments and simulating complex multicellular constructs. However, controlling the localization of cells precisely on microfabricated structures is still complex and usually limited to two-dimensional assays. Indeed, the implementation of an efficient method to selectively target different cell types to specific regions of a 3D microscaffold would represent a decisive step toward cell-by-cell assembly of complex cellular arrangements. Here, we use two-photon lithography (2PL) to fabricate 3D microarchitectures with functional photoresists. UV-mediated click reactions are used to functionalize their surfaces with single-stranded DNA oligonucleotides, using sequential repetition to decorate different scaffold regions with individual DNA addresses. Various immortalized cell lines and stem cells modified by grafting complementary oligonucleotides onto the phospholipid membranes can then be immobilized onto complementary regions of the 3D structures by selective hybridization. This allows controlled cocultures to be established with spatially separated arrays of eukaryotic cells in 3D.

Intriguing Heteroleptic ZnII bis(dipyrrinato) Emitters in the Far-Red Region With Large Pseudo-Stokes Shift for Bioimaging.

Novel heteroleptic ZnII bis(dipyrrinato) complexes were prepared as intriguing emitters. With our tailor-made design, we achieved far-red emissive complexes with a photoluminescence quantum yield up to 45% in dimethylsulfoxide and 70% in toluene. This means that heteroleptic ZnII bis(dipyrrinato) complexes retain very intense emission also in polar solvents, in contrast to their homoleptic counterparts, which we prepared for comparing the photophysical properties. It is evident from the absorption and excitation spectra that heteroleptic complexes present the characteristic features of both ligands: the plain dipyrrin (Lp) and the π-extended dipyrrin (Lπ). On the contrary, the emission comes exclusively from the π-extended dipyrrin Lπ, suggesting an interligand nonradiative transition that causes a large pseudo-Stokes shift (up to 4,600 cm-1). The large pseudo-Stokes shifts and the emissive spectral region of these novel heteroleptic ZnII bis(dipyrrinato) complexes are of great interest for bioimaging applications. Thus, their high biocompatibiliy with four different cell lines make them appealing as new fluorophores for cell imaging.

How does long-term parenteral nutrition impact the bone mineral status of children with intestinal failure?

Patients on long-term parenteral nutrition (PN) are at significantly increased risk for the development of metabolic bone disease (MBD); this condition is characterized by incomplete mineralization of osteoid with consequent disturbances ranging from osteopenia to severe bone disease with fractures. The aim of the study was: (1) to evaluate the prevalence of MBD, (2) to identify the PN- or intestinal failure (IF)-related factors and (3) to assess annual changes of bone mineral status. Since September 2005 all patients affected by IF and treated with PN started a BMD evaluation program using dual-energy X-ray absorptiometry (DXA). Twenty-four IF patients were included [15 with short bowel syndrome (SBS), 5 with severe protracted diarrhea and 4 with chronic intestinal pseudostruction]. The bone mineral density (BMD) Z-score was significantly lower in patients than in the control group. In our series SBS patients showed a BMD Z-score significantly higher in comparison with the medical causes of IF. No significant correlations were found between bone mineral status and PN duration and nutrient intake. Nine IF patients were submitted to a second DXA evaluation after 1 year from the baseline. All bone mineral variables were significantly increased at the second DXA evaluation. The high prevalence of MBD in IF patients undergoing long-term treatment with PN requires that these patients undergo careful and periodic monitoring of their bone mineral status; patients with congenital gut dysfunctions, such as epithelium defects and motility anomalies, are at major risk of developing this complication, probably due to the association with extra-intestinal causes of bone loss.

Iridium metal complexes containing N-heterocyclic carbene ligands for blue-light-emitting electrochemical cells.

A new series of cationic blue-emitting, heteroleptic iridium(III)-based metal complexes were systematically synthesized using two 4,6-difluorophenylpyridine ligands as well as one methyl- or n-butyl-substituted bisimidazolium salt carbene-type ligand. In degassed CH(2)Cl(2), all complexes display highly efficient, blue phosphorescence (λ(max) ∼ 452 nm; emission quantum yield ∼ 0.30) at room temperature and also show blue emission in a thin film. The measured photophysical properties of the complexes have been rationalized with the help of quantum-chemical calculations. Because of the high solubility of the complexes, solution-processed devices, light-emitting electrochemical cells (LEECs), were made. The results showed that true blue emission and short turn-on time is achieved when an ionic conductor, tetrabutylammonium trifluoromethanesulfonate, was used as the matrix for the film containing the emitters. These iridium complexes and the described devices are the bluest materials ever reported and the first case of LEECs based on carbene ligands.

Turning weak emitters into outstanding luminescent materials using rigid host media.

The incorporation into rigid silica host structures leads successfully to a significant luminescence enhancement of two zinc(ii) dipyrrins, known to be weak emitters in solution. One of these complexes shows a fluorescence efficiency of 55% and prolonged photo-stability once entrapped in silica, demonstrating high potential for applications in energy conversion.

Electron-transfer processes in metal-free tetraferrocenylporphyrin. Understanding internal interactions to access mixed-valence States potentially useful for quantum cellular automata.

Redox properties of H(2)TFcP [TFcP(2-) = 5,10,15,20-tetraferrocenylporphyrin(2-)] were investigated using cyclic voltammetry, differential pulse voltammetry, and square-wave voltammetry methods in a large variety of solvents and electrolytes. When DMF, THF, and MeCN were used with TBAP as the supporting electrolyte, the first oxidation wave was assigned to a single four-electron oxidation process reflecting simultaneous oxidation of all iron(II) centers into iron(III) centers in H(2)TFcP. When an o-DCB (1,2-dichlorobenzene)/TBAP combination was used in electrochemical experiments, four ferrocene substituents underwent two very diffuse, "two-electron" stepwise oxidations. The use of a weakly coordinating TFAB ([NBu(4)][B(C(6)F(5))(4)]) electrolyte in o-DCB or DCM results in four single-electron oxidation processes for ferrocene substituents in which the first and second single-electron waves have a relatively large separation, while the second, third, and fourth oxidation processes are more closely spaced; similar results were observed when a DCM/TBAP system and an imidazolium cation-based ionic liquid ((bmim)Tf(2)N = N-butyl-N'-methylimidazolium bis(trifluoromethanesulfonyl)imide) were used. Spectroelectrochemical oxidation of H(2)TFcP in o-DCB or DCM with TFAB as the supporting electrolyte allowed for characterization of the mixed-valence [H(2)TFcP](+), [H(2)TFcP](2+), and [H(2)TFcP](3+) compounds by UV-vis spectroscopy in addition to the "all-Fe(III)" [H(2)TFcP](4+). The chemical oxidation of H(2)TFcP was tested using a variety of oxidants which resulted in formation of mixed-valence [H(2)TFcP](+) and [H(2)TFcP](2+) as well as [H(2)TFcP](4+), which were characterized by UV-vis-NIR, MCD, IR, Mossbauer, and XPS spectroscopy. The intervalence-charge-transfer bands observed in the near-IR region in [H(2)TFcP](+) and [H(2)TFcP](2+) complexes were analyzed using Hush formalism and found to be of class II (in Robin-Day classification) character with localized ferrous and ferric centers. Class II behavior of [H(2)TFcP](+) and [H(2)TFcP](2+) complexes was further confirmed by Mossbauer, IR, and XPS data.

Metal-supported and -assisted stereoselective cooperative photoredox catalysis.

In this perspective, we review those stereoselective photocatalytic reactions that use synergy between photoredox catalysts and transition metal catalysts. In particular, we highlight the orchestrated interaction between two and more metals which not only enhance the turnover numbers, but also lead to increased selectivities. Aspects of green chemistry and sustainable developments are included. In this review, C-C, C-O, C-N and C-S forming reactions are discussed and a perspective on future developments is given.