14-Membered Macrocyclic ß-Diiminato Gold(II) - A New Member for the Gold(II) Complex Family?

The chemistry of molecular gold compounds is dominated by the oxidation states +I and +III. For the intermediate oxidation state +II with 5d9 electron configuration, dimerization or disproportionation of the gold(II) radicals is favored, so that only a few mononuclear gold(II) complexes have been isolated to date. The present study addresses the one-electron reduction of the macrocyclic gold(III) complex [AuIIIL]+ of the innocent ß-diiminato ligand L2- with a 14-membered macrocycle (L2-=5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradeca-5,7,12,14-tetraenato). Electrochemistry, spectroelectrochemistry and chemical reduction of [AuIIIL]+ monitored by UV/Vis, NMR and EPR spectroscopy together with density functional theory calculations reveal disproportionation of the initially generated but elusive gold(II) complex AuIIL and provide guidelines for prospective stable mononuclear tetraazamacrocyclic gold(II) complexes.

Oxidative two-state photoreactivity of a manganese(IV) complex using near-infrared light.

Highly reducing or oxidizing photocatalysts are a fundamental challenge in photochemistry. Only a few transition metal complexes with Earth-abundant metal ions have so far advanced to excited state oxidants. All these photocatalysts require high-energy light for excitation, and their oxidizing power has not been fully exploited due to energy dissipation before reaching the photoactive state. Here we demonstrate that the complex [Mn(dgpy)2]4+, based on Earth-abundant manganese and the tridentate 2,6-diguanidylpyridine ligand (dgpy), evolves to a luminescent doublet ligand-to-metal charge transfer (2LMCT) excited state (1,435 nm, 0.86 eV) with a lifetime of 1.6 ns after excitation with low-energy near-infrared light. This 2LMCT state oxidizes naphthalene to its radical cation. Substrates with extremely high oxidation potentials up to 2.4 V enable the [Mn(dgpy)2]4+ photoreduction via a high-energy quartet 4LMCT excited state with a lifetime of 0.78 ps, proceeding via static quenching by the solvent. This process minimizes free energy losses and harnesses the full photooxidizing power, and thus allows oxidation of nitriles and benzene using Earth-abundant elements and low-energy light.

Electronic Structure and Excited-State Dynamics of the NIR-II Emissive Molybdenum(III) Analogue to the Molecular Ruby.

Photoactive chromium(III) complexes saw a conceptual breakthrough with the discovery of the prototypical molecular ruby mer-[Cr(ddpd)2]3+ (ddpd = N,N'-dimethyl-N,N'-dipyridin-2-ylpyridine-2,6-diamine), which shows intense long-lived near-infrared (NIR) phosphorescence from metal-centered spin-flip states. In contrast to the numerous studies on chromium(III) photophysics, only 10 luminescent molybdenum(III) complexes have been reported so far. Here, we present the synthesis and characterization of mer-MoX3(ddpd) (1, X = Cl; 2, X = Br) and cisfac-[Mo(ddpd)2]3+ (cisfac-[3]3+), an isomeric heavy homologue of the prototypical molecular ruby. For cisfac-[3]3+, we found strong zero-field splitting using magnetic susceptibility measurements and electron paramagnetic resonance spectroscopy. Electronic spectra covering the spin-forbidden transitions show that the spin-flip states in mer-1, mer-2, and cisfac-[3]3+ are much lower in energy than those in comparable chromium(III) compounds. While all three complexes show weak spin-flip phosphorescence in NIR-II, the emission of cisfac-[3]3+ peaking at 1550 nm is particularly low in energy. Femtosecond transient absorption spectroscopy reveals a short excited-state lifetime of 1.4 ns, 6 orders of magnitude shorter than that of mer-[Cr(ddpd)2]3+. Using density functional theory and ab initio multireference calculations, we break down the reasons for this disparity and derive principles for the design of future stable photoactive molybdenum(III) complexes.

Cluster Headache Genomewide Association Study and Meta-Analysis Identifies Eight Loci and Implicates Smoking as Causal Risk Factor.

OBJECTIVE: The objective of this study was to aggregate data for the first genomewide association study meta-analysis of cluster headache, to identify genetic risk variants, and gain biological insights. METHODS: A total of 4,777 cases (3,348 men and 1,429 women) with clinically diagnosed cluster headache were recruited from 10 European and 1 East Asian cohorts. We first performed an inverse-variance genomewide association meta-analysis of 4,043 cases and 21,729 controls of European ancestry. In a secondary trans-ancestry meta-analysis, we included 734 cases and 9,846 controls of East Asian ancestry. Candidate causal genes were prioritized by 5 complementary methods: expression quantitative trait loci, transcriptome-wide association, fine-mapping of causal gene sets, genetically driven DNA methylation, and effects on protein structure. Gene set and tissue enrichment analyses, genetic correlation, genetic risk score analysis, and Mendelian randomization were part of the downstream analyses. RESULTS: The estimated single nucleotide polymorphism (SNP)-based heritability of cluster headache was 14.5%. We identified 9 independent signals in 7 genomewide significant loci in the primary meta-analysis, and one additional locus in the trans-ethnic meta-analysis. Five of the loci were previously known. The 20 genes prioritized as potentially causal for cluster headache showed enrichment to artery and brain tissue. Cluster headache was genetically correlated with cigarette smoking, risk-taking behavior, attention deficit hyperactivity disorder (ADHD), depression, and musculoskeletal pain. Mendelian randomization analysis indicated a causal effect of cigarette smoking intensity on cluster headache. Three of the identified loci were shared with migraine. INTERPRETATION: This first genomewide association study meta-analysis gives clues to the biological basis of cluster headache and indicates that smoking is a causal risk factor. ANN NEUROL 2023;94:713-726.

Stable Molybdenum(0) Carbonyl Complex for Upconversion and Photoredox Catalysis.

Photoactive complexes with earth-abundant metals have attracted increasing interest in the recent years fueled by the promise of sustainable photochemistry. However, sophisticated ligands with complicated syntheses are oftentimes required to enable photoactivity with nonprecious metals. Here, we combine a cheap metal with simple ligands to easily access a photoactive complex. Specifically, we synthesize the molybdenum(0) carbonyl complex Mo(CO)3(tpe) featuring the tripodal ligand 1,1,1-tris(pyrid-2-yl)ethane (tpe) in two steps with a high overall yield. The complex shows intense deep-red phosphorescence with excited state lifetimes of several hundred nanoseconds. Time-resolved infrared spectroscopy and laser flash photolysis reveal a triplet metal-to-ligand charge-transfer (3MLCT) state as the lowest excited state. Temperature-dependent luminescence complemented by density functional theory (DFT) calculations suggest thermal deactivation of the 3MLCT state via higher lying metal-centered states in analogy to the well-known photophysics of [Ru(bpy)3]2+. Importantly, we found that the title compound is very photostable due to the lack of labilized Mo-CO bonds (as caused by trans-coordinated CO) in the facial configuration of the ligands. Finally, we show the versatility of the molybdenum(0) complex in two applications: (1) green-to-blue photon upconversion via a triplet-triplet annihilation mechanism and (2) photoredox catalysis for a green-light-driven dehalogenation reaction. Overall, our results establish tripodal carbonyl complexes as a promising design strategy to access stable photoactive complexes of nonprecious metals avoiding tedious multistep syntheses.

Coupled Potential Energy Surfaces Strongly Impact the Lowest-Energy Spin-Flip Transition in Six-Coordinate Nickel(II) Complexes.

Luminescent complexes of earth-abundant first-row transition metals are of renewed, broad interest due to their spectroscopic and photochemical properties as well as emerging applications. New strong-field polypyridine ligands have led to six-coordinate 3d3 chromium(III) complexes with intense spin-flip luminescence in solution at room temperature. The ground and emissive states both arise from the (t2)3 electron configuration involving the dπ levels (O point group symmetry labels). Pseudoctahedral 3d8 nickel(II) complexes with such strong ligands are a priori also promising candidates for spin-flip luminescence. In contrast, the relevant electron configurations involve the dσ orbitals and (e)2 configurations. We have prepared the known nickel(II) complexes [Ni(terpy)2]2+, [Ni(phen)3]2+, and [Ni(ddpd)2]2+ as well as the novel complexes [Ni(dgpy)2]2+ and [Ni(tpe)2]2+ forming a series with increasing ligand field strengths (terpy = 2,2':6',2″-terpyridine; phen = 1,10-phenanthroline; ddpd = N,N'-dimethyl-N,N'-dipyridine-2-ylpyridine-2,6-diamine; dgpy = 2,6-diguanidylpyridine; tpe = 1,1,1-tris(pyrid-2-yl)ethane). The lowest-energy singlet and triplet excited states of these nickel(II) complexes are analyzed based on absorption spectra using ligand field theory and CASSCF-NEVPT2 calculations for vertical transition energies and a model based on coupled potential energy surfaces, leading to calculated absorption spectra in good agreement with the experimental data. No photoluminescence signal was observed in the wavelength ranges identified through the analyses of the absorption spectra. The models provide insight into key differences between the nickel(II) complexes and their strongly luminescent chromium(III) analogues.

Substitution Effects on the Photophysical and Photoredox Properties of Tetraaza[7]helicenes.

A series of substituted derivatives of tetraaza[7]helicenes were synthesized and the influence of the substitution on their photophysical and photoredox-catalytic properties was studied. The combination of their high fluorescence quantum yields of up to 0.65 and their circularly polarized luminescence (CPL) activity results in CPL brightness values (BCPL ) that are among the highest recorded for [7]helicenes so far. A sulfonylation/hetarylation reaction using cyanopyridines as substrates for photoinduced electron transfer (PET) from the excited helicenes was conducted to test for viability in photoredox catalysis. DFT calculations predict the introduction of electron withdrawing substituents to yield more oxidizing catalysts.

Excited state energy landscape of phosphorescent group 14 complexes.

Great progress has been achieved on phosphorescent or photoactive complexes of the Earth-abundant transition metals, while examples for phosphorescent heavy main group element complexes are rare, in particular for group 14 complexes in the oxidation state +II. The known compounds often show only weak phosphorescence with fast non-radiative deactivation. The underlying photophysical processes and the nature of the phosphorescent electronic states have remained essentially unexplored. The present combined photophysical and theoretical study on tin(ii) and lead(ii) complexes E(bpep) with the dianionic tridentate ligand bpep2- (E = Sn, Pb; H2bpep = 2-[1,1-bis(1H-pyrrol-2-yl)ethyl]pyridine) provides unprecedented insight in the excited state energy landscape of tetrel(ii) complexes. The tin complex shows green intraligand charge transfer (ILCT) phosphorescence both in solution and in the solid state. In spite of its larger heavy-atom effect, the lead complex only shows very weak red phosphorescence from a strongly distorted ligand-to-metal charge transfer (LMCT) state at low temperatures in the solid state. Detailed (TD-)DFT calculations explain these observations and delineate the major path of non-radiative deactivation via distorted LMCT states. These novel insights provide rational design principles for tetrel(ii) complexes with long-lived phosphorescence.

Quantum Chemical Study of the Pressure-dependent Phosphorescence of [Cr(ddpd)2 ]3+ in the Solid State.

The chromium(III) complex [Cr(ddpd)2 ][BF4 ]3 shows two spin-flip emission bands in the near-infrared spectral region. These bands shift bathochromically by -14.1 and -7.7 cm-1 kbar-1 under hydrostatic pressure (Angew. Chem. Int. Ed. 2018, 57, 11069). The present study elucidates the structural changes of the chromium(III) cations under pressure using density functional theory with periodic boundary conditions and the resulting effects on the excited state energies using high-level CASSCF-NEVPT2 calculations. The differences of the bands in pressure sensitivity are traced back to a different orbital occupation of the intraconfigurational excited states.

Janus-type emission from a cyclometalated iron(III) complex.

Although iron is a dream candidate to substitute noble metals in photoactive complexes, realization of emissive and photoactive iron compounds is demanding due to the fast deactivation of their charge-transfer states. Emissive iron compounds are scarce and dual emission has not been observed before. Here we report the FeIII complex [Fe(ImP)2][PF6] (HImP = 1,1'-(1,3-phenylene)bis(3-methyl-1-imidazol-2-ylidene)), showing a Janus-type dual emission from ligand-to-metal charge transfer (LMCT)- and metal-to-ligand charge transfer (MLCT)-dominated states. This behaviour is achieved by a ligand design that combines four N-heterocyclic carbenes with two cyclometalating aryl units. The low-lying π* levels of the cyclometalating units lead to energetically accessible MLCT states that cannot evolve into LMCT states. With a lifetime of 4.6 ns, the strongly reducing and oxidizing MLCT-dominated state can initiate electron transfer reactions, which could constitute a basis for future applications of iron in photoredox catalysis.

Quantum Yield of DNA Strand Breaks under Photoexcitation of a Molecular Ruby.

Photodynamic therapy (PDT) used for treating cancer relies on the generation of highly reactive oxygen species, for example, singlet oxygen 1 O2 , by light-induced excitation of a photosensitizer (PS) in the presence of molecular oxygen, inducing DNA damage in close proximity of the PS. Although many precious metal complexes have been explored as PS for PDT and received clinical approval, only recently, the potential of photoactive complexes of non-noble metals as PS has been discovered. Using the DNA origami technology that can absolutely quantify DNA strand break cross sections, we assessed the potential of the luminescent transition metal complex [Cr(ddpd)2 ]3+ (ddpd=N,N'-dimethyl-N,N'-dipyridine-2-ylpyridine-2,6-diamine) to damage DNA in an air-saturated aqueous environment upon UV/Vis illumination. The quantum yield for strand breakage, that is, the ratio of DNA strand breaks to the number of absorbed photons, was determined to 1-4 %, indicating efficient transformation of photons into DNA strand breaks by [Cr(ddpd)2 ]3+ .

Correction: Distinct photodynamics of κ-N and κ-C pseudoisomeric iron(II) complexes.

Correction for 'Distinct photodynamics of κ-N and κ-C pseudoisomeric iron(II) complexes' by Philipp Dierks et al., Chem. Commun., 2021, 57, 6640-6643, https://doi.org/10.1039/D1CC01716K.

Towards Luminescent Vanadium(II) Complexes with Slow Magnetic Relaxation and Quantum Coherence.

Molecular entities with doublet or triplet ground states find increasing interest as potential molecular quantum bits (qubits). Complexes with higher multiplicity might even function as qudits and serve to encode further quantum bits. Vanadium(II) ions in octahedral ligand fields with quartet ground states and small zero-field splittings qualify as qubits with optical read out thanks to potentially luminescent spin-flip states. We identified two V2+ complexes [V(ddpd)2 ]2+ with the strong field ligand N,N'-dimethyl-N,N'-dipyridine-2-yl-pyridine-2,6-diamine (ddpd) in two isomeric forms (cis-fac and mer) as suitable candidates. The energy gaps between the two lowest Kramers doublets amount to 0.2 and 0.5 cm-1 allowing pulsed EPR experiments at conventional Q-band frequencies (35 GHz). Both isomers possess spin-lattice relaxation times T1 of around 300 µs and a phase memory time TM of around 1 µs at 5 K. Furthermore, the mer isomer displays slow magnetic relaxation in an applied field of 400 mT. While the vanadium(III) complexes [V(ddpd)2 ]3+ are emissive in the near-IR-II region, the [V(ddpd)2 ]2+ complexes are non-luminescent due to metal-to-ligand charge transfer admixture to the spin-flip states.

Charge-Transfer and Spin-Flip States: Thriving as Complements.

Transition metal complexes with photoactive charge-transfer excited states are pervasive throughout the literature. In particular, [Ru(bpy)3 ]2+ (bpy=2,2'-bipyridine), with its metal-to-ligand charge-transfer emission, has been established as a key complex. Meanwhile, interest in so-called spin-flip metal-centered states has risen dramatically after the molecular ruby [Cr(ddpd)2 ]3+ (ddpd=N,N'-dimethyl-N,N'-dipyridin-2-yl-pyridine-2,6-diamine) led to design principles to access strong, long-lived emission from photostable chromium(III) complexes. This Review contrasts the properties of emissive charge-transfer and spin-flip states by using [Ru(bpy)3 ]2+ and [Cr(ddpd)2 ]3+ as prototypical examples. We discuss the relevant excited states, the tunability of their energy and lifetimes, and their response to external stimuli. Finally, we identify strengths and weaknesses of charge-transfer and spin-flip states in applications such as photocatalysis and circularly polarized luminescence.

Bulky ligands protect molecular ruby from oxygen quenching.

Chromium(III) complexes can show phosphorescence from the spin-flip excited doublet states 2E/2T1 in the near-infrared with high photoluminescence quantum yields and extremely long lifetimes in the absence of dioxygen. The prototype molecular ruby, [Cr(ddpd)2]3+ (ddpd = N,N'-dimethyl-N,N'-dipyridine-2-ylpyridine-2,6-diamine), has a photoluminescence quantum yield and a luminescence lifetime of 13.7% and 1.1 ms in deaerated acetonitrile, respectively. However, its luminescence is strongly quenched by 3O2via an efficient Dexter-type energy transfer process. To enable luminescence applications of molecular rubies in solution under aerobic conditions, we explored the potential of sterically demanding ddpd ligands to shield the chromium(III) center from O2 using steady state and time-resolved photoluminescence spectroscopy. The structures of the novel complexes with sterically demanding ligands were investigated by single crystal X-ray diffraction and quantum chemically by density functional theory calculations. The O2 sensitivity of the photoluminescence was derived from absolutely measured photoluminescence quantum yields and excited state lifetimes under inert and aerobic conditions and by Stern-Volmer analyses of these data. Optimal sterically shielded chromium(III) complexes revealed photoluminescence quantum yields of up to 5.1% and excited state lifetimes of 518 µs in air-saturated acetonitrile, underlining the large potential of this ligand design approach to broaden the applicability of highly emissive chromium(III) complexes.

The Full d3-d5 Redox Series of Mononuclear Manganese Complexes: Geometries and Electronic Structures of [Mn(dgpy)2]n.

Although manganese ions exhibit a rich redox chemistry, redox processes are often accompanied by structural reorganization and a high propensity for ligand substitution, so that no complete structurally characterized manganese(II,III,IV) complex series without significant ligand sphere reorganization akin to the manganese(II,III,IV) oxides exists. We present here the series of pseudo-octahedral homoleptic manganese complexes [Mn(dgpy)2]n+ (n = 2-4) with the adaptable tridentate push-pull ligand 2,6-diguanidylpyridine (dgpy). Mn-N bond lengths and N-Mn-N bond angles change characteristically from n = 2 to n = 4, while the overall [MnN6] coordination sphere is preserved. The manganese(III) complex [Mn(dgpy)2]3+ exhibits a Jahn-Teller elongated octahedron and a negative D = -3.84 cm-1. Concomitantly with the consecutive oxidation of [Mn(dgpy)2]2+ to [Mn(dgpy)2]4+, the optical properties evolve with increasing ligand-to-metal charge transfer character of the absorption bands culminating in the panchromatic absorption of the purple-black manganese(IV) complex [Mn(dgpy)2]4+.

Pseudo-Octahedral Iron(II) Complexes with Near-Degenerate Charge Transfer and Ligand Field States at the Franck-Condon Geometry.

Increasing the metal-to-ligand charge transfer (MLCT) excited state lifetime of polypyridine iron(II) complexes can be achieved by lowering the ligand's π* orbital energy and by increasing the ligand field splitting. In the homo- and heteroleptic complexes [Fe(cpmp)2 ]2+ (12+ ) and [Fe(cpmp)(ddpd)]2+ (22+ ) with the tridentate ligands 6,2''-carboxypyridyl-2,2'-methylamine-pyridyl-pyridine (cpmp) and N,N'-dimethyl-N,N'-di-pyridin-2-ylpyridine-2,6-diamine (ddpd) two or one dipyridyl ketone moieties provide low energy π* acceptor orbitals. A good metal-ligand orbital overlap to increase the ligand field splitting is achieved by optimizing the octahedricity through CO and NMe units between the coordinating pyridines which enable the formation of six-membered chelate rings. The push-pull ligand cpmp provides intra-ligand and ligand-to-ligand charge transfer (ILCT, LL'CT) excited states in addition to MLCT excited states. Ground and excited state properties of 12+ and 22+ were accessed by X-ray diffraction analyses, resonance Raman spectroscopy, (spectro)electrochemistry, EPR spectroscopy, X-ray emission spectroscopy, static and time-resolved IR and UV/Vis/NIR absorption spectroscopy as well as quantum chemical calculations.

Molecular Rubies in Photoredox Catalysis.

The molecular ruby [Cr(tpe) 2 ] 3+ and the tris(bipyridine) chromium(III) complex [Cr(dmcbpy) 3 ] 3+ as well as the tris(bipyrazine)ruthenium(II) complex [Ru(bpz) 3 ] 2+ were employed in the visible light-induced radical cation [4+2] cycloaddition (tpe = 1,1,1-tris(pyrid-2-yl)ethane, dmcbpy = 4,4'-dimethoxycarbonyl-2,2'-bipyridine, bpz = 2,2'-bipyrazine), while [Cr(ddpd) 2 ] 3+ serves as a control system (ddpd = N,N'-dimethyl-N,N'-dipyridin-2-ylpyridine-2,6-diamine). Along with an updated mechanistic proposal for the CrIII driven catalytic cycle based on redox chemistry, Stern-Volmer analyses, UV/Vis/NIR spectroscopic and nanosecond laser flash photolysis studies, we demonstrate that the very weakly absorbing photocatalyst [Cr(tpe) 2 ] 3+ outcompetes [Cr(dmcbpy) 3 ] 3+ and even [Ru(bpz) 3 ] 2+ in particular at low catalyst loadings, which appears contradictory at first sight. The high photostability, the reversible redoxchemistry and the very long excited state lifetime account for the exceptional performance and even reusability of [Cr(tpe) 2 ] 3+ in this photoredox catalytic system.