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.

Fully earth‐abundant and highly efficient systems for producing syngas CO/H2 through photocatalytic reduction from CO2 are essential to approach a sustainable way of closing the carbon cycle. Herein, the synthesis and characterization of a new iron complex, FeIIL(NCS)2py, coordinated to an N,N,N‐pincer ligand 2,6‐bis(4’‐phenyl‐1’,2’,3’‐triazol‐1’‐yl‐methyl)pyridine (L), two isothiocyanate groups (NCS) and one pyridine is reported. Its catalytic activity in the photo‐driven reduction of carbon dioxide has been investigated and compared with its CoII analogue (CoL(NCS)2py) and their homoleptic complexes ML2. In this work, the catalysts are used in combination with the heteroleptic complex [CuI(dmp)(DPEphos)], where dmp is 2,9‐dimethyl‐1,10‐phenanthroline and DPEPhos is bis[(2‐diphenylphosphino)phenyl] ether, to reach entirely earth‐abundant systems. The new iron heteroleptic complex FeIIL(NCS)2py showed considerable activity with a TONCO of 576 obtained after 4 h (TOF=144 h−1) through visible light (λ=420 nm) and a quantum yield of 7.1 %.

The synthesis, structural, and magnetic characterization of [Fe III 4 Ln III 4 (teaH) 8 (N 3 ) 8 (H 2 O)] (Ln = Gd and Y) and the previously reported isostructural Dy analogue are discussed. The commonly held belief that both Fe III and Gd III can be regarded as isotropic ions is shown to be an oversimplification. This conclusion is derived from the magnetic data for the Y III analogue in terms of the zero-field splitting seen for Fe III and from the fact that the magnetic data for the new Gd III analogue can only be fit employing an additional anisotropy term for the Gd III ions. Furthermore, the Fe 4 Gd 4 ring shows slow relaxation of magnetization. Our analysis of the experimental magnetic data employs both density functional theory as well as the finite-temperature Lanczos method which finally enables us to provide an almost perfect fit of magnetocaloric properties.

The Cover Feature shows the photo‐driven conversion of CO2 as a water lily pond, where the central role is given by the new iron catalyst, here represented by the white lily. The red flowers symbolize copper‐based photosensitizers, which receive spotlight radiation. In their Research Article, C. Bizzarri and co‐workers describe that photoinduced electron transfer processes are necessary to reduce the catalyst, which is able to reduce carbon dioxide and protons to carbon monoxide and molecular hydrogen, respectively. The selectivity of the CO2 conversion is up to 70%. The developed systems are fully earth‐abundant and produce CO with a maximum apparent quantum yield of 7%. More information can be found in the Research Article by C. Bizzarri and co‐workers.

ChemInform Abstract Irradiation of CuCl2-and CuCl32-in the UV region corresponding to the charge-transfer-to-solvent (CTTS) at 274 nm, in neutral aqueous solutions 5 M Cl-ion at room temp., results in luminescence emission centered at 470-480 nm. The quantum yield of emission is measured to be 3.6•10-3 (lifetime 105 ns). Hydrogen quenches the luminescence according to a linear Stern-Volmer relationship. The emission is reduced by a decrease in Cl-concentration and by a decrease in ionic strength. Photooxidation of the chlorocuprate(I) complexes by continuous irradiation of the CTTS band, according to the overall reaction shown in the scheme, is inhibited by increased ionic strength and Cl-ion concentration. A mechanism is proposed in which hydrated electron formation competes with the decay of the CTTS excited state to a spin-forbidden state.