Heterobimetallic contacts in statistical co-crystals of homoleptic coordination compounds with ligand-encoded H⋯F bonds: structure, photophysics and mechano-responsive properties.

In this work, the structural and photophysical characterization of statistical co-crystals based on two homoleptic Pt(II) and Pd(II) complexes as well as their mechano-responsive properties are reported. Ligand-dominated H⋯F bonds, which reinforce metal-metal interactions in the crystalline state, support emission from MMLCT states. All co-crystals show a distinct red-shift upon grinding, showcasing their inherent mechano-responsive characteristics stemming from (hetero-)bimetallic contacts.

Hysteretic Piezochromism in a Lead Iodide-Based Two-Dimensional Inorganic-Organic Hybrid Perovskite.

Two-dimensional inorganic-organic hybrid perovskites are in the limelight due to their potential applications in photonics and optoelectronics. They are environmentally stable, and their various chemical compositions offer a wide range of bandgap energies. Alternatively, crystal deformation enables in situ control over their optical properties.

Antiprotozoal Pt(II) Complexes as Luminophores Bearing Monodentate P/As/Sb-Based Donors: An X-ray Diffractometric, Photoluminescence, and Sb- Spectroscopic Study with TD-DFT-Guided Interpretation and Predictive Extrapolation toward Bi.

In this study, it is demonstrated that the radiative rate constant of phosphorescent metal complexes can be substantially enhanced using monodentate ancillary ligands containing heavy donor atoms. Thus, the chlorido coligand from a Pt(II) complex bearing a monoanionic tridentate C^N*N luminophore ([]) was replaced by triphenylphosphane (PPh) and its heavier pnictogen congeners (i.e.

Searching for Laves Phase Superstructures: Structural and Al NMR Spectroscopic Investigations in the Hf-V-Al System.

Laves phases exhibit a plethora of different structures and a multitude of physical properties. Investigations in the ternary system Hf-V-Al led to the discovery of numerous members of the solid solution Hf(VAl), which adopt the hexagonal MgZn type (C14) for medium to high amounts of Al ( = 0.2-1) and the cubic MgCu type (C15) for small Al amounts ( = 0.

Triclinic LaZnP with P, P, and P units: a combined study by P solid-state NMR spectroscopy and single crystal X-ray diffraction.

The ternary polyphosphide LaZnP was synthesized from the elements by using a salt flux or a ceramic method in sealed quartz ampoules. The obtained samples were investigated by X-ray powder and single crystal diffraction: own type, 1̄, = 775.33(13), = 827.

Neutral and Cationic Re(I) Complexes with Pnictogen-Based Coligands and Tunable Functionality: From Phosphorescence to Photoinduced CO Release.

In this work, we have explored Re(I) complexes featuring triphenylpnictogen (, = , , or )-based coligands and bidentate (neutral or monoanionic) luminophores derived from 1,10-phenantroline (), as well as from 2-(3-(-butyl)-1-1,2,4-triazol-5-yl)pyridine (). The effect of the increasingly heavy elements on the structural parameters, photoexcited-state properties, and electrochemical behavior as well as the hybridization defects and polarization of the atoms was related to the charges of the main luminophores (i.e.

One Dianionic Luminophore with Three Coordination Modes Binding Four Different Metals: Toward Unexpectedly Phosphorescent Transition Metal Complexes.

This work reports on a battery of coordination compounds featuring a versatile dianionic luminophore adopting three different coordination modes (mono, bi, and tridentate) while chelating Pd(II), Pt(II), Au(III), and Hg(II) centers. An in-depth structural characterization of the ligand precursor (H L) and six transition metal complexes ([HLPdCNtBu], [LPtCl], [LPtCNtBu], [LPtCNPhen], [HLHgCl], and [LAuCl]) is presented. The influence of the cations and coordination modes of the luminophore and co-ligands on the photophysical properties (including photoluminescence quantum yields (Φ ), excited state lifetimes (τ), and average (non-)radiative rate constants) are evaluated at various temperatures in different phases.

The Effect of Monodentate Co-Ligands on the Properties of Pt(II) Complexes Bearing a Tridentate C^N*N-Luminophore.

In this study, the insertion of different monodentate co-ligands on Pt(II) complexes bearing a monoanionic C^N*N luminophore as a tridentate chelator was achieved beyond the previously reported chlorido- ([]) and cyanido-decorated ([]) analogues. To investigate the impact of the auxiliary ligand on the photophysical properties, we introduced a neutral carbonyl-ligand and observed a lower photoluminescence quantum yield () than with a cyanido moiety. However, the direct substitution of the chlorido co-ligand by a NO-related derivative was not successful.

Salt-flux growth of HoCuMg single crystals.

Polycrystalline samples of the magnesium-rich intermetallic compounds RECuMg (RE = Dy, Ho, Er, Tm) were synthesized by reaction of the elements in sealed tantalum ampoules heated in a high-frequency induction furnace. Phase purity of the RECuMg phases was ascertained by powder X-ray diffraction patterns. Well-shaped single crystals of HoCuMg could be grown in a NaCl/KCl salt flux and the crystal structure was refined from single crystal X-ray diffraction data: TbCuMg structure-type, space group , = 1361.

Room-Temperature Phosphorescence from Pd(II) and Pt(II) Complexes as Supramolecular Luminophores: The Role of Self-Assembly, Metal-Metal Interactions, Spin-Orbit Coupling, and Ligand-Field Splitting.

The synthesis as well as the structural and photophysical characterization of two isoleptic bis-cyclometalated Pt(II) and Pd(II) complexes, namely [] and [], bearing a tailored dianionic tetradentate ligand () are reported. The isostructural character and intermolecular interactions of [] and [] were assessed by NMR spectroscopy and X-ray diffraction analysis. Both complexes show fully ligand-controlled aggregation, demonstrating that a judicious molecular design can tune the photophysical properties.

Soundscape Awareness Intervention Reduced Neuropsychiatric Symptoms in Nursing Home Residents With Dementia: A Cluster-Randomized Trial With MoSART.

Objectives: Auditory environments as perceived by an individual, also called soundscapes, are often suboptimal for nursing home residents. Poor soundscapes have been associated with neuropsychiatric symptoms (NPS). We evaluated the effect of the Mobile Soundscape Appraisal and Recording Technology sound awareness intervention (MoSART+) on NPS in nursing home residents with dementia.

Rhenium(I) Complexes with Neutral Monodentate Coligands and Monoanionic 2-(1,2,4-Triazol-5-yl)pyridine-Based Chelators as Bidentate Luminophores with Tunable Color and Photosensitized Generation of O: An Integrated Case Study Involving Photophysics and Theory.

In this work, we describe the synthesis as well as structural, photophysical, and theoretical investigation of a new coordination chemical concept involving rhenium(I) complexes bearing monoanionic 1,2,4-triazolylpyridine-based bidentate chromophores. The X-ray diffractometric analysis of single crystals revealed particular packing features: the trifluoromethylated exemplar displayed two kinds of arrangements of the coordination centers, where the bidentate ligands at the edges of the unit cell are staggered parallel to each other, whereas those inside show antiparallel stacking with respect to the external ligands. On the other hand, the complexes bearing an adamantyl substituent yield a linear arrangement, where the bulky moiety of one luminophore points to the pyridine center of the adjacent ligand of the neighboring complex while including methanol molecules hydrogen-bonded to the triazolato unit.

Room-temperature luminescence from Pd(II) and Pt(II) complexes: from mechanochromic crystals to flexible polymer matrices.

A series of Pd(II) (PdLOMe, PdLOHex) and Pt(II) (PtLOMe, PtLOHex) complexes bearing tetradentate ligands as dianionic luminophores were synthesized. Hence, the cyclometallating chelators were alternatively decorated with two -hexyloxy (LOHex) or two methoxy (LOMe) moieties to promote crystallization and processability. The new compounds were unambiguously characterized by means of multiple NMR spectroscopies and mass spectrometry as well as by single crystal X-ray diffractometric analysis (PtLOMe and PdLOMe).

Soundscape Optimization in Nursing Homes Through Raising Awareness in Nursing Staff With MoSART.

Introduction: Soundscapes in nursing homes are often suboptimal for residents. This can cause them feeling anxious and unsafe, or develop behavioral and psychological problems. Residents with dementia cannot adapt nursing home environments to their needs due to cognitive and physical limitations.

Ligand-controlled and nanoconfinement-boosted luminescence employing Pt(ii) and Pd(ii) complexes: from color-tunable aggregation-enhanced dual emitters towards self-referenced oxygen reporters.

In this work, we describe the synthesis, structural and photophysical characterization of four novel Pd(ii) and Pt(ii) complexes bearing tetradentate luminophoric ligands with high photoluminescence quantum yields ( ) and long excited state lifetimes () at room temperature, where the results were interpreted by means of DFT calculations. Incorporation of fluorine atoms into the tetradentate ligand favors aggregation and thereby, a shortened average distance between the metal centers, which provides accessibility to metal-metal-to-ligand charge-transfer (MMLCT) excimers acting as red-shifted energy traps if compared with the monomeric entities. This supramolecular approach provides an elegant way to enable room-temperature phosphorescence from Pd(ii) complexes, which are otherwise quenched by a thermal population of dissociative states due to a lower ligand field splitting.

Naphthalonitriles featuring efficient emission in solution and in the solid state.

In this work, a series of γ-substituted diphenylnaphthalonitriles were synthesized and characterized. They show efficient emission in solution and in the aggregated state and their environment responsiveness is based on having variable substituents at the -position of the two phenyl moieties. The excited state properties were fully investigated in tetrahydrofuran (THF) solutions and in THF/HO mixtures.

Compensation of Hybridization Defects in Phosphorescent Complexes with Pnictogen-Based Ligands-A Structural, Photophysical, and Theoretical Case-Study with Predictive Character.

In this work, for the first time, the comparative use of P-, As-, and Sb-based ligands in phosphorescent coordination compounds is reported toward new coordination chemical concepts in the design and realization of tailored triplet emitters with nonconventional elements. By means of spectroscopic, X-ray diffractometric, and quantum-chemical methods, we reconstructed the nature of the chemical bonds as well as the influence of the increasingly heavy elements on the photoexcited state properties, which were correlated with the hybridization and polarizability of the pnictogen atoms (). In particular, we elucidated the structural and photophysical properties of a series of homologous Pt(II) complexes with monodentate ancillary ligands based on group 15 elements, namely P, As, and Sb.

Sounds in nursing homes and their effect on health in dementia: a systematic review.

Objectives: Nursing home residents with dementia are sensitive to detrimental auditory environments. This paper presents the first literature review of empirical research investigating (1) the (perceived) intensity and sources of sounds in nursing homes, and (2) the influence of sounds on health of residents with dementia and staff.

Design: A systematic review was conducted in PubMed, Web of Science and Scopus.

Validation of a modified ambiance scale in nursing homes.

Objectives: We translated and modified an ambiance scale for use by (in)formal caregivers in Dutch nursing homes. We tested validity and reliability of the modified Ambiance Scale.

Method: Convenience sampling was used to enrol (in)formal caregivers in three nursing homes in the Netherlands.

B and Y solid state MAS NMR spectroscopic investigations of the layered borides YTB (T = Mo, W, Re).

The YCrB4 type borides YTB4 (T = Mo, W, Re) were synthesized from the elements by arc-melting and subsequent annealing. The structures were refined from single crystal X-ray diffractometer data: Pbam, a = 602.84(8), b = 1164.

A Dimeric η ,η -Germole Dianion Bridged Titanium(III) Complex with a Multicenter Ti-Ge-Ge-Ti Bond.

Dimeric germole dianion bridged Ti and Zr complexes have been synthesized. In these complexes, the germole dianion adopts a formal η ,η coordination to the two metal centers. The bonding situation in these bridged dimers is dominated by a covalent Ge-Ge interaction that results, for example, in a strong antiferromagnetic coupling of the d Ti centers.

Synthesis and activation potential of an open shell diphosphine.

A paramagnetic W alkyne complex bearing free terminal diphenylphosphino groups at the side-on coordinated alkyne was synthesized using a stepwise template strategy. This moderately stable metal supported open shell diphosphine shows an unprecedented spontaneous splitting of nitric oxide providing a W-η-C{P(NH)Ph}{P(O)Ph} complex featuring an amino phosphonium and a phosphine oxide substituent.

Structurally related hydrazone-based metal complexes with different antitumor activities variably induce apoptotic cell death.

Three new complexes bearing the tridentate hydrazone-based ligand 2-(2-(1-(pyridin-2-yl)ethylidene)hydrazinyl)pyridine (L) were synthesized and structurally characterized. Biological tests indicate that the Zn(ii) complex [ZnCl(L)] is of low cytotoxicity against the hepatocellular carcinoma cell line HepG2. In contrast, the Cu(ii) and Mn(ii) complexes [CuCl(L)] and [MnCl(L)] are highly cytotoxic with EC values of 1.

Phosphorescent Pt(ii) complexes bearing a monoanionic C^N^N luminophore and tunable ancillary ligands.

A versatile design strategy is presented towards new monoanionic pincer luminophores, showing that cyclometallating C^N^N ligands can yield phosphorescent Pt(ii) complexes even if a neutral 1,2,3-triazole ring is inserted by click chemistry. The overall charge, intermolecular interactions and excited state properties can be manipulated and controlled by varying the nature of the ancillary ligand, and its effect on the structural and the triplet state characteristics can be thoroughly investigated and correlated by means of theory and spectroscopy.

Metal-Mediated Assembly of 1,N(6)-Ethenoadenine: From Surfaces to DNA Duplexes.

The design of multinuclear metal complexes requires a match of the ligand-to-metal vectors and the preferred coordination geometries of the metal ions. Only a few ligands are known with a parallel orientation of N→M vectors that brings the metal ions into close proximity. We establish here the adenine derivative 1,N(6)-ethenoadenine (εA) as an ideal bis(monodentate) ligand.