Coinage Metal Bis(amidinate) Complexes as Building Blocks for Self-Assembled One-Dimensional Coordination Polymers.

The pyridyl functionalized amidinate [{PyC≡CC(NDipp)2 }Li(thf)2 ]n was used to synthesize a series of bis-amidinate complexes [{PyC≡CC(NDipp)2 }2 M2 ] (M=Cu, Ag, Au) with fully supported metallophilic interactions. These metalloligands were then used as building blocks for the synthesis of one-dimensional heterobimetallic coordination polymers using Zn(hfac)2 (hfac=hexaflouroacetylacetonate) for self-assembly. Interestingly, the three coordination polymers [{PyC≡CC(NDipp)2 }2 M2 ][Zn(hfac)2 ] (M=Cu, Ag, Au), exhibit a zig zag shape in the solid state. To achieve linear coordination geometry other connectors such as M'(acac) (M'=Ni, Co) (acac=acetylacetonate) were investigated. The thus obtained compounds [{PyC≡CC(NDipp)2 }2 Cu2 ][M'(acac)2 ] (M'=Ni, Co) are indeed linear heterobimetallic coordination polymers featuring a metalloligand backbone with fully supported metallophilic interactions.

Luminescent early-late-hetero-tetranuclear group IV - Au(I) bisamidinate complexes.

The versatile metalloligand [{HCCC(NDipp)2}2Au2] (dipp = 2,6-diisopropylphenyl) was converted into early-late heterotetrametallic complexes [{ClCp2MCCC(NDipp)2}2Au2] (M = Ti, Zr). These compounds show photoluminescence with either remarkably different (Ti) or similar (Zr) features as compared to related solely coinage metal containing acetylide amidinate complexes.

Alkali Metal Complexes of a Bis(diphenylphosphino)methane Functionalized Amidinate Ligand: Synthesis and Luminescence.

A novel bis(diphenylphosphino)methane (DPPM) functionalized amidine ligand (DPPM-C(N-Dipp)2 H) (Dipp=2,6-diisopropylphenyl) was synthesized. Subsequent deprotonation with suitable alkali metal bases resulted in the corresponding complexes [M{DPPM-C(N-Dipp)2 }(Ln )] (M=Li, Na, K, Rb, Cs; L=thf, Et2 O). The alkali metal complexes form monomeric species in the solid state, exhibiting intramolecular metal-π-interactions. In addition, a caesium derivative [Cs{PPh2 CH2 -C(N-Dipp)2 }]6 was obtained by cleavage of a diphenylphosphino moiety, forming an unusual six-membered ring structure in the solid state. All complexes were fully characterized by single crystal X-ray diffraction, NMR spectroscopy, IR spectroscopy as well as elemental analysis. Furthermore, the photoluminescent properties of the complexes were thoroughly investigated, revealing differences in emission with regards to the respective alkali metal. Interestingly, the hexanuclear [Cs{PPh2 CH2 -C(N-Dipp)2 }]6 metallocycle exhibits a blue emission in the solid state, which is significantly red-shifted at low temperatures. The bifunctional design of the ligand, featuring orthogonal donor atoms (N vs. P) and a high steric demand, is highly promising for the construction of advanced metal and main group complexes.

ß1-Blockers Enhance Inotropy of Endogenous Catecholamines in Chronic Heart Failure.

Although ß1-blockers impressively reduce mortality in chronic heart failure (CHF), there are concerns about negative inotropic effects and worsening of hemodynamics in acute decompensated heart failure. May receptor theory dispel these concerns and confirm clinical practice to use ß1-blockers? In CHF, concentrations of catecholamines at the ß1-adrenoceptors usually exceed their dissociation constants (K Ds). The homodimeric ß1-adrenoceptors have a receptor reserve and display negative cooperativity. We considered the binomial distribution of occupied receptor dimers with respect to the interaction of an exogenous ß1-blocker and elevated endogenous agonist concentrations > [K Ds], corresponding to an elevated sympathetic tone. Modeling based on binomial distribution suggests that despite the presence of a low concentration of the antagonist, the activation of the dimer receptors is higher than that in its absence. Obviously, the antagonist improves the ratio of the dimer receptors with only single agonist activation compared with the dimer receptors with double activation. This leads to increased positive inotropic effects of endogenous catecholamines due to a ß1-blocker. To understand the positive inotropic sequels of ß1-blockers in CHF is clinically relevant. This article may help to eliminate the skepticism of clinicians about the use of ß1-blockers because of their supposed negative inotropic effect, since, on the contrary, a positive inotropic effect can be expected for receptor-theoretical reasons.

Thermally Activated Delayed Fluorescence and Phosphorescence Quenching in Iminophosphonamide Copper and Zinc Complexes.

The synthesis of copper and zinc complexes of four variably substituted iminophosphonamide ligands is presented. While the copper complexes form ligand-bridged dimers, the zinc compounds are monomeric. Due to different steric demand of the ligand the arrangement of the ligands within the dimeric complexes varies. Similar to the structurally related iminophosphonamide complexes of alkali metals and calcium, the steady-state and time-resolved photoluminescence (PL) of four of the seven compounds studied here as solids in a temperature range of 5-295 K can be described within the scheme of thermally activated delayed fluorescence (TADF). Accordingly, they exhibit bright blue-green phosphorescence at low temperatures (<100 K), which turns into delayed fluorescence by increasing the temperature. However, unusually, the fluorescence is practically absent in two copper complexes which otherwise still conform to the TADF scheme. In these cases, the excited singlet states decay essentially non-radiatively and their thermal population from the corresponding low-lying triplet states efficiently quenches PL (phosphorescence). Three other copper and zinc complexes only exhibit prompt fluorescence, evidencing a wide variation of photophysical properties in this class of compounds. The excited states of the copper complex with especially pronounced phosphorescence quenching were also investigated by low-temperature time-resolved infrared spectroscopy and quantum chemical calculations.

Enantiopure Calcium Iminophosphonamide Complexes: Synthesis, Photoluminescence, and Catalysis.

The synthesis of calcium complexes ligated by three different chiral iminophosphonamide ligands, L-H (L=[Ph2 P{N(R)CH(CH3 )Ph}2 ]), L'-H (L'=[Ph2 P{NDipp}{N(R)CH(CH3 )Ph}]), (Dipp=2,6-i Pr2 C6 H3 ), and L''-H (L''=[Ph2 P{N(R)CH(CH3 )naph}2 ]), (naph=naphthyl) is presented. The resulting structures [L2 Ca], [L'2 Ca], and [L''2 Ca] represent the first examples of enantiopure homoleptic calcium complexes based on this type of ligands. The calcium complexes show blue-green photoluminescence (PL) in the solid state, which is especially bright at low temperatures. Whereas the emission of [L''2 Ca] is assigned to the fluorescence of naphthyl groups, the PL of [L2 Ca] and [L'2 Ca] is contributed by long-lived phosphorescence and thermally activated delayed fluorescence (TADF), with a strong variation of the PL lifetimes over the temperature range of 5-295 K. Furthermore, an excellent catalytic activity was found for these complexes in hydroboration of ketones at room temperature, although no enantioselectivity was achieved.

Molecular gold strings: aurophilicity, luminescence and structure-property correlations.

This review covers the compound class of one-dimensional gold strings. These compounds feature a formally infinite repetition of gold complexes as monomers/repeating units that are held together by aurophilic interactions, i.e. direct gold-gold contacts. Their molecular structures are primarily determined in the solid state using single crystal X-ray diffraction. The chemical composition of the employed gold complexes is diverse and furthermore plays a key role in terms of structure characteristics and the resulting properties. One of the most common features of gold strings is their photoluminescence upon UV excitation. The emission energy is often dependent on the distance of adjacent gold ions and the electronic structure of the whole string. In terms of gold strings, these parameters can be fine-tuned by external stimuli such as solvent, pH value, pressure or mechanical stress. This leads to direct structure-property correlations, not only with regard to the photophysical properties, but also electric conductivity for potential application in nanoelectronics. Concerning these correlations, gold strings, consisting of self-assembled individual complexes as building blocks, are the ideal compound class to look at, as perturbations by an inhomogeneity in the ligand sphere (such as the end of a molecule) can be neglected. Therefore, the aim of this review is to shed light on the past achievements and current developments in this area.

Efficient Blue Phosphorescence in Gold(I)-Acetylide Functionalized Coinage Metal Bis(amidinate) Complexes.

The synthesis of linear symmetric ethynyl- and acetylide-amidinates of the coinage metals is presented. Starting with the desilylation of the complexes [{Me3 SiC≡CC(NDipp)2 }2 M2 ] (Dipp=2,6-diisopropylphenyl) (M=Cu, Au) it is demonstrated that this compound class is suitable to serve as a versatile metalloligand. Deprotonation with n-butyllithium and subsequent salt metathesis reactions yield symmetric tetranuclear gold(I) acetylide complexes of the form [{(PPh3 )AuC≡CC(NDipp)2 }2 M2 ] (M=Cu, Au). The corresponding Ag complex [{(PPh3 )AuC≡CC(NDipp)2 }2 Ag2 ] was obtained by a different route via metal rearrangement. All compounds show bright blue or blue-green microsecond long phosphorescence in the solid state, hence their photophysical properties were thoroughly investigated in a temperature range of 20-295 K. Emission quantum yields of up to 41 % at room temperature were determined. Furthermore, similar emissions with quantum yields of 15 % were observed for the two most brightly luminescent complexes in thf solution.

Electrocorticographic and neurochemical findings after local cortical valproate application in patients with pharmacoresistant focal epilepsy.

Because oral pharmacological treatment of neocortical focal epilepsy is limited due to common systemic side effects and relatively low drug concentrations reached at the epileptic foci locally, application of antiepileptic agents directly onto the neocortical focus may enhance treatment tolerability and efficacy. We describe the effects of cortically applied sodium valproate (VPA) in two patients with pharmacoresistant neocortical focal epilepsy who were selected for epilepsy surgery after a circumscribed epileptic focus had been determined by invasive presurgical evaluation using subdural electrodes. Local VPA modified epileptic activity as electrocorticographically recorded from the chronic focus in both patients. In addition, VPA induced local increase of the inhibitory neurotransmitter γ-aminobutyric acid (GABA) in cortical tissue samples, whereas the excitatory glutamate was possibly decreased. In this clinical pilot study, we could show antiepileptic effects of cortically applied VPA in humans by electrocorticographic and neurochemical parameters.

Investigating the Photochemistry of Spiropyran Metal Complexes with Online LED-NMR.

As one of the best studied photoswitches, spiropyrans (SPs) have attracted significant interest in the scientific community. Among the many stimuli to alter the isomerization into the merocyanine (MC) isomer, such as temperature, pH, solvent polarity, redox potential, or mechanical force, the ability of the MC form to act as a ligand site for metal complexation has recently raised new attention. We herein synthesize hitherto undescribed coordination compounds of 8-methoxy-1',3',3'-trimethyl-6-nitrospiro-[chromene-2,2'-indoline] with s-block ([Ca(MC)4](ClO4)2), d-block ([Zn(MC)2(MeCN)2](ClO4)2, [Ni(MC)2(MeCN)2](ClO4)2), as well as f-block ([La(NO3)3(MC)2]) metals. All complexes are structurally described by X-ray crystallography and systematically investigated in solution via Job's method of continuous variations (Job plots), as well as online NMR spectroscopic kinetic experiments with in situ irradiation of the analyte solution inside the NMR spectrometer (LED-NMR). We can unambiguously identify the photoresponsive nature of the complexes in solution, which is a crucial step toward the application of these promising molecules in material science.

Alkali metal complexes of an enantiopure iminophosphonamide ligand with bright delayed fluorescence.

The enantiomerically pure ligand P,P-diphenyl-N,N'-bis((R)-1-phenylethyl)phosphinimidic amide (1; (R)-HPEPIA) was synthesized and subsequently deprotonated with alkali metal precursors to yield dimeric complexes [M2{(R)-PEPIA}2] (M = Li (2), Na (3), K (4), Rb (5)). The cesium compound [M{(R)-PEPIA}] (6) crystallized as a cocrystal composed of dimeric ([Cs2{(R)-PEPIA}2] (6d ) and 1D-polymeric ([Cs{(R)-PEPIA}] n ) (6p ) species in a 1 : 1 ratio. The coordination polymer 6p features a unique sinus-shaped configuration of repeating -Cs-N-P-N-Cs-N-P-N- units. Unusual photoluminescence (PL) properties were found for solid 1-6: in contrast to the fluorescent ligand 1, the alkali metal complexes show phosphorescence at low temperatures (<100 K) and thermally activated delayed fluorescence (TADF) above ∼150 K. The latter provides for PL quantum yields up to 36% (3) at ambient temperature. DFT calculations support that both 1 and 2-6d have similar singlet and triplet excited states with energy separations of a few tens of meV. The strongly enhanced intersystem crossing (ISC) in the metal complexes, resulting in TADF, is attributed to their dimeric structure. This suggests that the fluorophore dimerization may serve as a tool to effect ISC for the design of TADF emitters.

Phosphine-substituted 1,2,3-triazoles as P,C- and P,N-ligands for photoluminescent coinage metal complexes.

A series of homo- and hetero-polynuclear coinage metal complexes based on a phosphine-substituted 1,2,3-triazole system is presented. Besides the P,N-ligand 1-benzyl-4-(diphenylphosphanyl)-1H-1,2,3-triazole (LPN), the P,C-donor ligand 1-benzyl-4-(diphenylphosphanyl)-3-methyl-1H-1,2,3-triazolium (LPCH+), featuring a potential mesoionic carbene moiety, was obtained by methylation of LPN. Starting from the monogold chloride complexes AuCl(LPN/LPC), the syntheses of a heterotrinuclear Au2Cu complex as well as a digold carbene complex are described. The multinuclear complexes show metallophilic interactions. Their photophysical properties were investigated by temperature-dependent photoluminescence (PL) measurements. In particular, the digold complex shows interesting PL properties including narrow exciton peaks arising in the excitation and emission spectra below 50 K. These might be related to the molecular 'chains' in the crystal structure of the digold complex, formed by phenyl ligand stacking.

Synthesis, Spectroscopy, and Redox Studies of Ferrocene-Functionalized Coinage Metal Alkyne Complexes.

Ethynylferrocene (FcC≡CH) was utilized as a redox-active metalloligand for the synthesis of polynuclear coinage metal complexes. The reaction of [FcC≡CLi] with tri- tert-butylphosphine metal chlorides [tBu3P-MCl] (M = Au, Ag, Cu) yielded different heteronuclear ferrocene-funtionalized alkyne complexes featuring metallophilic interactions. Furthermore, the redox properties of the ferrocenyl-functionalized tetracopper complex were investigated by cyclic voltammetry and UV-vis-near-IR spectroelectrochemistry. They indicate the compounds' redox-rich nature and a weak electronic coupling between the redox-active ferrocenyl units over a large distance.

Size Matters: From Two-Dimensional AuI -TlI Metallopolymers to Molecular Complexes by Simple Variation of the Steric Demand.

Bis(acetylido) aurates(I) and thallium(I) trifluoromethylsulfonates were used to synthesize AuI -TlI metallopolymers, displaying novel and unusual structural motifs of the metal-metal backbones in the solid state: a discrete molecular cluster, 1D chains of interconnected dimers, tetramers, or dodecamers of Au-Tl units, and a 2D-plane network, consisting of alternating edge-linked (AuTl)6 and (AuTl)4 cycles. The formation of the different architectures was primarily controlled by the steric demand of the acetylide-substituent groups. Thus, the bulkiest 2,6-diisopropylphenyl derivative yielded a molecular cluster [Tl2 Au3 ]. Most compounds showed bright visible photoluminescence with quantum yields of up to 25 % at ambient temperature. The color of the emitted light significantly differs with the network structure. Furthermore, theoretical studies of singlet excitations in the molecular cluster, as well as NMR and mass-spectrometric investigations of the fragmentation of the metallopolymers in solution are described in detail.

Access to divalent lanthanide NHC complexes by redox-transmetallation from silver and CO2 insertion reactions.

Through a redox-transmetallation procedure, divalent NHC-LnII (NHC = N-heterocyclic carbene; Ln = Eu, Yb) complexes were obtained from the corresponding NHC-AgI. The lability of the NHC-LnII bond was investigated and treatment with CO2 led to insertion reactions without oxidation of the metal centre. The EuII complex [EuI2(IMes)(THF)3] (IMes = 1,3-dimesitylimidazol-2-ylidene) exhibits photoluminescence with a quantum yield reaching 53%.

Spatially-Resolved Multiple Metallopolymer Surfaces by Photolithography.

A tetrazole-based photoligation protocol for the spatially-resolved encoding of various defined metallopolymers onto solid surfaces is introduced. By using this approach, fabrication of bi- and trifunctional metallopolymer surfaces with different metal combinations were achieved. Specifically, α-ω-functional copolymers containing bipyridine as well as triphenylphosphine ligands were synthesized through reversible addition-fragmentation chain transfer (RAFT) polymerization, and subsequently metal loaded to afford metallopolymers of the widely-used metals gold, palladium, and platinum. Spatially-resolved surface attachment was achieved by means of a nitrile imine-mediated tetrazole-ene cycloaddition (NITEC) based photoligation protocol, exploiting tethered tetrazoles and metallopolymers equipped with a maleimide chain terminus. Metallopolymer coated surfaces with three different metals were prepared and characterized by time-of-flight secondary ion mass spectrometry (ToF-SIMS) and spatially-resolved X-ray photoelectron spectroscopy (XPS) mapping, supporting the preserved chemical composition of the surface-bound metallopolymers. The established photochemical technology platform for arbitrary spatially-resolved metallopolymer surface designs enables the patterning of multiple metallopolymers onto solid substrates. This allows for the assembly of designer metallopolymer substrates.

Intensely Photoluminescent Diamidophosphines of the Alkaline-Earth Metals, Aluminum, and Zinc.

The positively charged and weakly polarizable s-block metals commonly do not usually have phosphine ligands in molecular complexes. Herein, we report mono- and dinuclear small diamidophosphine complexes of the alkaline-earth metals Mg, Ca, and Sr, which were prepared from simple precursors and a phosphine-functionalized diamine ligand N,N-bis(2-(diphenyl-phosphino)phenyl)ethane-1,2-diamine (PNHNHP). The alkaline-earth metal based complexes [(PNNP)Mg]2 and [(PNNP)M(thf)3 ] (M=Ca, Sr), exhibit unusual coordination spheres and show bright fluorescence, both in the solid state and in solution. For comparison, the even stronger luminescent Al and Zn complexes [(PNNP)Zn]2 and [(PNNP)AlCl] were prepared. Emission lifetimes in the nanosecond range and high photoluminescence quantum yields up to 93 % are observed at room temperature.

Dimolybdenum Paddlewheel as Scaffold for Heteromultimetallic Complexes: Synthesis and Photophysical Properties.

A diphenylphosphine functionalized benzoic acid was applied for the synthesis of a homoleptic dimolybdenum-based metalloligand, exhibiting four symmetrically placed phosphine donor sites. This allowed subsequent treatment with gold(I), rhodium(I), and iridium(I) precursors to obtain early-late heterometallic complexes as well as Lewis acid-base adducts with BH3. The compounds were in-depth investigated by spectroscopic techniques, single-crystal X-ray diffraction, and femtosecond laser spectroscopy. The coordination of different metal fragments to the dimolybdenum metalloligand leads to a fine-tuning of the system's optical properties, which correlates well with fluorescence quantum yield measurements. Nevertheless, triplet dynamics still remain the dominating channel in these systems with an intersystem crossing time constant below 1 ps.

When the Ostrich-Algorithm Fails: Blanking Method Affects Spike Train Statistics.

Modern electroceuticals are bound to employ the usage of electrical high frequency (130-180 Hz) stimulation carried out under closed loop control, most prominent in the case of movement disorders. However, particular challenges are faced when electrical recordings of neuronal tissue are carried out during high frequency electrical stimulation, both in-vivo and in-vitro. This stimulation produces undesired artifacts and can render the recorded signal only partially useful. The extent of these artifacts is often reduced by temporarily grounding the recording input during stimulation pulses. In the following study, we quantify the effects of this method, "blanking," on the spike count and spike train statistics. Starting from a theoretical standpoint, we calculate a loss in the absolute number of action potentials, depending on: width of the blanking window, frequency of stimulation, and intrinsic neuronal activity. These calculations were then corroborated by actual high signal to noise ratio (SNR) single cell recordings. We state that, for clinically relevant frequencies of 130 Hz (used for movement disorders) and realistic blanking windows of 2 ms, up to 27% of actual existing spikes are lost. We strongly advice cautioned use of the blanking method when spike rate quantification is attempted. IMPACT STATEMENT: Blanking (artifact removal by temporarily grounding input), depending on recording parameters, can lead to significant spike loss. Very careful use of blanking circuits is advised.

A highly luminescent octanuclear gold(i) carbide cluster.

The ligand [{Me3SiC[triple bond, length as m-dash]CC(NDipp)2}Li(thf)3] (Dipp = 2,6-diisopropylphenyl) was used for salt metathesis reactions with [AuCl(tht)] (tht = tetrahydrothiophene) to obtain the dinuclear alkyne functionalized bisamidinate [{Me3SiC[triple bond, length as m-dash]CC(NDipp)2}2Au2]. This compound serves as a building block for the polynuclear carbide bridged gold(i) amidinate complex [Au8{µ3-(η1:η2-C[triple bond, length as m-dash]C)}2(Me3SiC[triple bond, length as m-dash]CC(NDipp)2)4(tht)2], which is the first gold(i) complex with a µ3-η1:η2 carbide coordination. Both gold(i) compounds show distinct aurophilic interactions and are remarkably stable at ambient conditions. Photophysical investigations revealed intense luminescence with notable high quantum yields both in the solid state and in solution.