Factorizing the Nephelauxetic Effect in Heteroleptic Molecular Rubies.

The interest in chromium(III) complexes has been renewed over the past decade for the design of efficient earth-abundant phosphorescent red-to-near-infrared spin-flip emitters and photocatalysts with long excited state lifetimes. In this context, we report the energy tuning of spin-flip excited states based on heteroleptic bis(tridentate) polypyridine chromium(III) complexes , namely, , and with the tridentate ligands L and L [X/Y = NMe, ,'-dimethyl-,'-dipyridin-2-ylpyridine-2,6-diamine; X/Y = CH, 2,6-bis(2-pyridylmethyl)pyridine and X/Y = S, 2,6-bis(pyridine-2-ylthio)pyridine]. The heteroleptic complexes are obtained via a novel synthetic approach toward the required intermediate labile triflato complexes Cr(L)(OTf) () from the respective chlorido precursors CrCl(L) () using trimethylsilyl trifluoromethanesulfonate.

Bridge editing of spin-flip emitters gives insight into excited state energies and dynamics.

Six-coordinate chromium(iii) complexes with high spin-flip (SF) photoluminescence quantum yields and lifetimes (molecular rubies) have attracted huge interest in the past years due to their applicability in sensing, photocatalysis or circularly polarised emission. However, clearcut design rules for high quantum yields and lifetimes are still lacking due to the multidimensional problem of the non-radiative decay of the SF states. Based on an isostructural series of complexes differing in the ligand backbone, we disentangle decisive structural and electronic features for SF excited state energies and non-radiative decays promoted by spin-orbit coupling, Jahn-Teller distortions and (thermally activated) multiphonon relaxation.

Face-to-Face Gold Porphyrins.

The interaction of square-planar metal complexes through space is of fundamental interest and relevant for the potential cooperative catalysis of two metal complex sites. In order to elucidate gold/gold, gold/porphyrin, and porphyrin/porphyrin interactions in the formal oxidation states +III and +II (after reduction) and in the excited triplet state after light excitation, a Pacman bis(gold(III)) complex [Au(DPD)][PF] with square-planar face-to-face gold(porphyrin) moieties has been prepared and characterized. Absorption and luminescence spectroscopy, cyclic voltammetry, and EPR spectroscopy on [Au(DPD)] and a mononuclear reference are complemented by DFT and TDDFT calculations.

Triplet carbenes with transition-metal substituents.

The extraordinary advances in carbene (R-C-R) chemistry have been fuelled by strategies to stabilize the electronic singlet state via π interactions. In contrast, the lack of similarly efficient approaches to obtain authentic triplet carbenes with appreciable lifetimes beyond cryogenic temperatures hampers their exploitation in synthesis and catalysis. Transition-metal substitution represents a potential strategy, but metallocarbenes (M-C-R) usually represent high-lying excited electronic configurations of the well-established carbyne complexes (M≡C-R).

Gas-Phase Characterization of Redox-Active Manganese Complexes.

Manganese complexes exhibit a rich redox chemistry, usually accompanied by structural reorganization during the redox processes often followed by ligand dissociation or association. The push-pull ligand 2,6-diguanidylpyridine (dgpy) stabilizes manganese in the oxidation states +II, +III, and + IV in the complexes [Mn(dgpy)] ( = 2-4) without change in the coordination sphere in the condensed phase [Heinze et al., , 61, 14616].

A Tetracarbene Iron(II) Complex with a Long-lived Triplet Metal-to-Ligand Charge Transfer State due to a Triplet-Triplet Barrier.

Mixed N-heterocyclic carbene (NHC) / pyridyl iron(II) complexes have attracted a great deal of attention recently because of their potential as photocatalysts and light sensitizers made from Earth-abundant elements. The most decisive challenge for their successful implementation is the lifetime of the lowest triplet metal-to-ligand charge transfer state (MLCT), which typically decays via a triplet metal-centered (MC) state back to the ground state. We reveal by variable-temperature ultrafast transient absorption spectroscopy that the tripodal iron(II) bis(pyridine) complex isomers trans- and cis-[Fe(pdmi)] with four NHC donors show MLCT→MC population transfers with very different barriers and rationalize this by computational means.

14-Membered Macrocyclic β-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 5d 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 [AuL] of the innocent β-diiminato ligand L with a 14-membered macrocycle (L=5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradeca-5,7,12,14-tetraenato).

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.

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 -[Cr(ddpd)] (ddpd = ,'-dimethyl-,'-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 -MoX(ddpd) (, X = Cl; , X = Br) and -[Mo(ddpd)] (-), an isomeric heavy homologue of the prototypical molecular ruby.

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.

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.

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 3d chromium(III) complexes with intense spin-flip luminescence in solution at room temperature. The ground and emissive states both arise from the (t) electron configuration involving the d levels (O point group symmetry labels).

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 (B ) that are among the highest recorded for [7]helicenes so far.

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

The chromium(III) complex [Cr(ddpd) ][BF ] shows two spin-flip emission bands in the near-infrared spectral region. These bands shift bathochromically by -14.1 and -7.

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.

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 Fe complex [Fe(ImP)][PF] (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.

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 , , 2021, , 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.

Bulky ligands protect molecular ruby from oxygen quenching.

Chromium(III) complexes can show phosphorescence from the spin-flip excited doublet states E/T 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 = ,'-dimethyl-,'-dipyridine-2-ylpyridine-2,6-diamine), has a photoluminescence quantum yield and a luminescence lifetime of 13.7% and 1.

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) ] (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) ] (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.

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

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)] ( = 2-4) with the adaptable tridentate push-pull ligand 2,6-diguanidylpyridine (dgpy). Mn-N bond lengths and N-Mn-N bond angles change characteristically from = 2 to = 4, while the overall [MnN] coordination sphere is preserved.

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) ] (1 ) and [Fe(cpmp)(ddpd)] (2 ) 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.