Time-Resolved X-ray Emission Spectroscopy and Synthetic High-Spin Model Complexes Resolve Ambiguities in Excited-State Assignments of Transition-Metal Chromophores: A Case Study of Fe-Amido Complexes.

To fully harness the potential of abundant metal coordination complex photosensitizers, a detailed understanding of the molecular properties that dictate and control the electronic excited-state population dynamics initiated by light absorption is critical. In the absence of detectable luminescence, optical transient absorption (TA) spectroscopy is the most widely employed method for interpreting electron redistribution in such excited states, particularly for those with a charge-transfer character. The assignment of excited-state TA spectral features often relies on spectroelectrochemical measurements, where the transient absorption spectrum generated by a metal-to-ligand charge-transfer (MLCT) electronic excited state, for instance, can be approximated using steady-state spectra generated by electrochemical ligand reduction and metal oxidation and accounting for the loss of absorptions by the electronic ground state. However, the reliability of this approach can be clouded when multiple electronic configurations have similar optical signatures. Using a case study of Fe(II) complexes supported by benzannulated diarylamido ligands, we highlight an example of such an ambiguity and show how time-resolved X-ray emission spectroscopy (XES) measurements can reliably assign excited states from the perspective of the metal, particularly in conjunction with accurate synthetic models of ligand-field electronic excited states, leading to a reinterpretation of the long-lived excited state as a ligand-field metal-centered quintet state. A detailed analysis of the XES data on the long-lived excited state is presented, along with a discussion of the ultrafast dynamics following the photoexcitation of low-spin Fe(II)-Namido complexes using a high-spin ground-state analogue as a spectral model for the 5T2 excited state.

Use of Unprecedented Intramolecular 1, 3-Dipolar Cycloaddition Reaction in meso-Nitrile Oxide-Containing BODIPYs as a New Pathway for the Preparation of Fused NIR Platforms.

Meso-nitrile oxide group in 1,7-Diphenyl-containing BODIPYs can be involved in highly unusual [3+2] intramolecular cycloaddition reaction with the formation of the dihydrobenzo[d]isoxazole-containing BODIPYs. Oxidation of these compounds results in the formation of unprecedented either benzisoxazole- or benzo[b]azepine-fused fully conjugated NIR absorbing BODIPYs. The photophysical properties and electronic structures of the target compounds were studied by an array of experimental and theoretical methods.

Switching on emission in Zn(II) coordination complexes by tempering Namido character.

A series of four-coordinate zinc(II) complexes is presented in which the amido vs. imino character of a ligated nitrogen donor correlates to the luminescence intensity. DFT analysis points to a distinct mechanism for this trend wherein emission can be switched on by restricting non-radiative decay pathways through the resonance-induced delocalization of amido ligand lone-pairs.

A Titration Method for Standardization of Aqueous Sodium Chlorite Solutions Using Thiourea Dioxide.

Accurate and cost-effective methods for the analysis of oxychlorine compounds in water are critical to modern chlorine-based water treatment. With alternatives to elemental chlorine and hypochlorite bleaches growing in popularity, simple quantification methods for the disinfectant chlorine dioxide (ClO2) in water, as well as chlorite (ClO2-) and chlorate (ClO3-), which are commonly used precursors in ClO2 generation, are required. However, currently, regulated standard methods require specialized equipment and do not effectively discriminate between molecular and ionic species. In this contribution, we present a simple titration-based method for chlorite determination in water using commercially available and easy-to-handle reagents. Specifically, chlorite is reduced with a slight excess of thioureadioxide (TUD). The remaining reductant is then back-titrated against a known amount of potassium permanganate, affording calculatable chlorite concentrations through measured consumption of a reductant and a clear visual endpoint upon accumulation of excess KMnO4. Straightforward methods for chlorite standardization with reasonable error and accuracy for field and/or lab application have the potential to greatly enhance quality assurance and therefore assist in resource deployment in water treatment.

Photoactive monofunctional platinum(II) anticancer complexes of multidentate phenanthridine-containing ligands: photocytotoxicity and evidence for interaction with DNA.

Pt(II) complexes supported by chelating, multidentate ligands containing π-extended, planar phenanthridine (benzo[c]quinoline) donors (RLPtCl) exhibit a promising in vitro therapeutic index compared with phenanthriplatin, a leading preclinical anticancer complex containing a monodentate phenanthridine ligand. Here, we report evidence for non-specific interactions of CF3LPtCl with DNA through intercalation-mediated turn-on luminescence in O2-saturated aqueous buffer. Brief irradiation with visible light (490 nm) was also found to drastically increase the activity of CF3LPtCl, with photocytotoxicity increased up to 87% against a variety of human cancer cell lines. Mechanistic studies highlight significantly improved cellular uptake of CF3LPtCl compared with cisplatin, with localization in the nucleus and mitochondria triggering effective apoptosis. Photosensitization experiments with 1,3-diphenylisobenzofuran demonstrate that CF3LPtCl efficiently mediates the generation of singlet dioxygen (1O2), highlighting the potential of RLPtCl in photodynamic therapy.

Yellow-Emitting, Pseudo-Octahedral Zinc Complexes of Benzannulated N

A series of yellow-emitting, pseudo-octahedral Zn(II) complexes supported by monoanionic, tridentate acetylacetone-derived N^N-^O ligands incorporating phenanthridine (benzo[c]quinoline) units is presented. These species emit weakly in solution but exhibit extended millisecond luminescence lifetimes in the solid state at room temperature, and in a frozen glass at 77 K, indicative of phosphorescence from low-lying triplet excited states. Excitation spectra indicate a role for aggregation in enhancing emission in the solid state. In contrast to four-coordinate phenanthridinyl amide-supported tetradentate Zn(II) complexes which are nonemissive in fluid solution, solid-state X-ray crystallographic structures, solution IR spectroscopy, and computational analysis all indicate a delocalized character for the central deprotonated NH which tempers the amido character of the ligand. This design provides a mechanism for "turning on" long-lived luminescence from N-heterocycle/amido-supported Zn(II) coordination compounds.

Synthesis and Coordination Chemistry of a Benzannulated Bipyridine: 6,6'-Biphenanthridine.

The synthesis, characterization, and coordination chemistry of a doubly π-extended bipyridine analogue, 6,6'-biphenanthridine (biphe), is presented. The structure of the molecule has been determined in the solid state by X-ray diffraction, showing an angle of 72.6° between the phenanthridine planes. The free, uncoordinated organic molecule displays blue fluorescence in solution. It can be singly protonated with strong acids, and the protonated form displays more intense yellow emission. The effect of acid on the excited states is interpreted with the aid of TDDFT calculations. Two Ru(II) coordination complexes, tris(6,6'-biphenanthridine)ruthenium(II) dichloride, [Ru(biphe)3]Cl2, and bis(2,2'-bipyridine)(6,6'-biphenanthridine)ruthenium(II) tetraphenylborate, [Ru(bpy)2(biphe)](BPh4)2, are also reported and their structures determined in the solid state by X-ray diffraction. Both complexes display emission at 77 K that is strongly bathochromically shifted by almost 200 nm compared to that of the archetypal 3MLCT emitter [Ru(bpy)3]2+. Such a red shift is consistent with the more extended conjugation and lower-energy π* orbitals associated with the biphe ligand, lowering the energy of the 3MLCT excited state, as revealed by TDDFT calculations. The efficient non-radiative decay that is typical of such low-energy emitters renders the phosphorescence extremely weak and short-lived at ambient temperature, and rapid ligand photodissociation also competes with radiative decay, especially in the heteroleptic complex. Electrochemical analysis illustrates the effect of biphe's stabilized vacant π* manifold, with multiple reversible reductions evident at much less negative potentials than those observed for [Ru(bpy)3]2+.

Radical Complexes of Nickel(II)/Copper(II) and Redox Non-innocent MB-DIPY Ligands: Unusual Stability and Strong Near-Infrared Absorption at λmax ∼1300†nm.

The preparation of radicals with intense and redox-switchable absorption beyond 1000 nm is a long-standing challenge in the chemistry of functional dyes. Here we report the preparation of a series of unprecedented stable neutral nickel(II) and copper(II) complexes of "Manitoba dipyrromethenes" (MB-DIPYs) in which the organic chromophore is present in the radical-anion state. The new stable radicals have an intense absorption at λmax ∼1300 nm and can be either oxidized to regular [MII (MB-DIPY)]+ (M=Cu or Ni) or reduced to [MII (MB-DIPY)]- compounds. The radical nature of the stable [MII (MB-DIPY)] complexes was confirmed by EPR spectroscopy with additional insight into their electronic structure obtained by UV-Vis spectroscopy, electro- and spectroelectrochemistry, magnetic measurements, and X-ray crystallography. The electronic structures and spectroscopic properties of the radical-based chromophores were also probed by density functional theory (DFT) and time-dependent DFT (TDDFT) calculations. These nickel(II) and copper(II) complexes represent the first stable radical compounds with a MB-DIPY ligand.

Donor-Acceptor Boron-Ketoiminate Complexes with Pendent N-Heterocyclic Arms: Switched-on Luminescence through N-Heterocycle Methylation.

A series of intramolecular, donor-stabilized BF2 complexes supported by phenanthridinyl-decorated, ß-ketoiminate chelating ligand scaffolds is described, along with their characterization by spectroscopy and X-ray diffraction. In solution, the relative orientation of the pendent phenanthridinyl arm is fixed despite not coordinating to the boron center, and a well-resolved through-space interaction between a phenanthridinyl C-H and a single fluorine atom can be observed by 19F-1H NOE NMR spectroscopy. The neutral compounds are nonetheless only weakly luminescent in fluid solution, ascribed to nonradiative decay pathways enabled by rotation of the N-heterocyclic unit. Methylation of the phenanthridinyl nitrogen restricts this rotation, "switching on" comparably strong emission in solution. Modeling by density functional theory (DFT) and time-dependent DFT (TDDFT) indicates that the character of the lowest energy excitation changes upon methylation, with shallow calculated potential energy surfaces of the neutral complexes consistent with their lack of significant radiative decay.

Reduction of Electron Repulsion in Highly Covalent Fe-Amido Complexes Counteracts the Impact of a Weak Ligand Field on Excited-State Ordering.

The ability to access panchromatic absorption and long-lived charge-transfer (CT) excited states is critical to the pursuit of abundant-metal molecular photosensitizers. Fe(II) complexes supported by benzannulated diarylamido ligands have been reported to broadly absorb visible light with nanosecond CT excited state lifetimes, but as amido donors exert a weak ligand field, this defies conventional photosensitizer design principles. Here, we report an aerobically stable Fe(II) complex of a phenanthridine/quinoline diarylamido ligand, Fe(ClL)2, with panchromatic absorption and a 3 ns excited-state lifetime. Using X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) at the Fe L-edge and N K-edge, we experimentally validate the strong Fe-Namido orbital mixing in Fe(ClL)2 responsible for the panchromatic absorption and demonstrate a previously unreported competition between ligand-field strength and metal-ligand (Fe-Namido) covalency that stabilizes the 3CT state over the lowest energy triplet metal-centered (3MC) state in the ground-state geometry. Single-crystal X-ray diffraction (XRD) and density functional theory (DFT) suggest that formation of this CT state depopulates an orbital with Fe-Namido antibonding character, causing metal-ligand bonds to contract and accentuating the geometric differences between CT and MC excited states. These effects diminish the driving force for electron transfer to metal-centered excited states and increase the intramolecular reorganization energy, critical properties for extending the lifetime of CT excited states. These findings highlight metal-ligand covalency as a novel design principle for elongating excited state lifetimes in abundant metal photosensitizers.

Brightly Luminescent Platinum Complexes of N∧C-∧N Ligands Forming Six-Membered Chelate Rings: Offsetting Deleterious Ring Size Effects Using Site-Selective Benzannulation.

Brightly emissive platinum(II) complexes (λemission,max = 607-612 nm) of the type RLPtCl are reported, where RL is a cyclometalated N∧C-∧N-coordinating ligand derived from 1,3-di(2-trifluoromethyl-4-phenanthridinyl)benzene (CF3LH) or 1,3-di(2-tert-butyl-4-phenanthridinyl)benzene (tBuLH). Metathesis of the chlorido ligand can be achieved under mild conditions, enabling isolation of ionic compounds with the formula [CF3LPtL']PF6 where L' = pyridine or (4-dimethylamino)pyridine (DMAP), as well as the charge-neutral species tBuLPt(C≡C─C6H4─tBu) (C≡C─C6H4─tBu = 4-tert-butylphenylacetylido). Compared with N∧N∧N-ligated Pt(II) complexes that form 5-membered chelates, these compounds all contain 6-membered rings. Expanding the chelate ring size from 5 to 6 has been previously demonstrated to enhance emission in some N∧N∧N-coordinated Pt(II) species─for example, in complexes of 2,6-di(8-quinolinyl)pyridine vs those of 2,2':6',2″-terpyridine─but in related N∧C-∧N-coordinated species, luminescence quantum yields are significantly lower for the 6-membered chelate ring complexes. Here, we demonstrate that site-selective benzannulation of the quinolinyl side-arms can offset the deleterious effect of changing the chelate ring-size and boost photophysical properties such as the quantum yield. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations suggest that benzannulation counterintuitively destabilizes the emissive triplet states compared to the smaller π-system, with the "imine-bridged biphenyl" form of the phenanthridinyl arm helping to buffer against larger molecular distortions, enhancing photoluminescence quantum yields up to 0.09 ± 0.02. The spontaneous formation under aerated conditions of a Pt(IV) derivative (CF3LPtCl3) is also reported, together with its molecular structure in the solid state.

The isolation, purification and complete characterization of the diterpene forskolin from nutritional supplements.

Forskolin (1) is a diterpene found in the Coleus forskohlii plant that has been examined for its medical properties resulting from adenylyl cyclase activation. This article describes a straightforward purification method of 1 from commercially available weight loss capsules. In addition, there has been some ambiguity with respect to the use of the name 'forskolin' to describe 1 and related diterpenes, which this report serves to eliminate. Herein we detail the complete spectroscopic characterization of purified 1 as well as its single crystal X-ray structure.

Accurate Prediction of Mössbauer Hyperfine Parameters in Bis-Axially Coordinated Iron(II) Phthalocyanines Using Density Functional Theory Calculations: A Story of a Single Orbital Revealed by Natural Bond Orbital Analysis.

Density Functional Theory (DFT) calculations coupled with several exchange-correlation functionals were used for the prediction of Mössbauer hyperfine parameters of 36 bis-axially coordinated iron(II) phthalocyanine complexes with the general formulas PcFeL2, PcFeL'L″, and [PcFeX2]2-, including four new compounds. Both gas-phase and PCM calculations using BPW91 and MN12L exchange-correlation functionals were found to accurately predict both Mössbauer quadrupole splittings and the correct trends in experimentally observed isomer shifts. In comparison, hybrid exchange-correlation functionals underestimated quadrupole splittings, while still accurately predicted isomer shifts. Out of ∼40 exchange-correlation functionals tested, only MN12L was found to correctly reproduce quadrupole splitting trends in the PcFeL2 complexes coordinated with phosphorus-donor axial ligands (i.e., P(OnBu)3 ≈ P(OEt)3 < PMe3 < P[(CH2O)2CH2]-p-C6H4NO2 < PEt3 ≈ PnBu3). Natural Bond Orbital (NBO) analysis was successfully used to explain the general trends in the observed quadrupole splitting for all compounds of interest. In particular, the general trends in the quadrupole splitting correlate well with the axial ligand dependent, NBO-predicted population of the 3dz2 orbital of the Fe ion and are reflective of the hypothesis proposed by Ohya and co-workers ( Inorg. Chem., 1984, 23, 1303) on the adaptability of the phthalocyanine's π-system toward Fe-Lax interactions. The first X-ray crystal structure of a PcFeL2 complex with axial phosphine ligands is also reported.

ß-Isoindigo-azaDIPYs: Fully Conjugated Hybrid Systems with Broad Absorption in the Visible Region.

A one-step synthetic pathway for the preparation of fully conjugated ß-isoindigo-azaDIPY hybrid chromophores comprised of ß-isoindigo and azadipyrromethene moieties is reported. The target compounds were characterized by spectroscopic, crystallographic, and theoretical methods and show unprecedented broad absorption across the visible region of the electromagnetic spectrum. The X-ray crystal structure of the octa(n-butyl)-ß-isoindigo-azaDIPY derivative revealed that a trans-configuration of the ß-isoindigo fragment accompanies a planar conjugated core.

Pseudo-octahedral nickel(ii) complexes of strongly absorbing benzannulated pincer-type amido ligands: ligand-based redox and non-Aufbau electronic behaviour.

The synthesis, structures and electronic characterization of three strongly coloured, pseudo-octahedral Ni(ii) complexes supported by redox-active diarylamido ligands featuring benzannulated N-heterocyclic donor arms are reported. The S = 1 paramagnets each present two singly occupied molecular orbitals (SOMOs) identified as metal-based by density functional theory (DFT), consistent with solid-state and solution magnetism measurements. Upon applying oxidative potentials, non-Aufbau behaviour leads to the appearance of intense and well-defined absorption features extending into the near IR (NIR). The attribution of these features to the onset of aminyl radical character through ligand-based redox is corroborated by exceptionally strong intervalence charge-transfer (IVCT) transitions ascribed to electronic communication between two Namido moieties across a Ni(ii) bridge.

In Pursuit of Panchromatic Absorption in Metal Coordination Complexes: Experimental Delineation of the HOMO Inversion Model Using Pseudo-Octahedral Complexes of Diarylamido Ligands.

The ability of a compound to broadly absorb light across the incident solar spectrum is an important design target in the development of molecular photosensitizers. The 'HOMO inversion' model predicts that for [(tpy)2Fe]2+ (tpy = 2,2':6',2″-terpyridine) compounds, adjusting the character of the highest occupied molecular orbital (HOMO) from metal-centered to ligand-centered can drastically improve photophysical properties by broadening absorption in the visible and increasing molar extinction coefficients. In an effort to experimentally realize strong, panchromatic absorption, a tridentate N^N-^N diarylamido ligand bearing flanking benzannulated N-heterocyclic donors (tBuL) was used to prepare deeply colored, pseudo-octahedral coordination complexes of a range of first-row transition and main-group metals [(tBuL)2M0/+; M = Fe, Co, Ni, Zn, Ga]. While the Fe(II) congener exhibits the sought-after broad absorption, isostructural and isoelectronic complexes of other first-row transition and main-group metals show vastly different absorption and redox properties. Density functional theory (DFT) calculations point toward the relative energies of the metal d orbitals and ligand orbitals as the source of major changes in electronic structure, confirming aspects and limitations of the predictive 'HOMO inversion' model in experimentally realized systems with implications for the design of abundant transition-metal sensitizers with broad, panchromatic absorptive properties.

Catalytic Synthesis of Luminescent Pyrimidines via Acceptor-less Dehydrogenative Coupling.

A simple catalytic synthesis of luminescent pyrimidines from benzamidines and alcohols is reported. These one-pot, acceptor-less dehydrogenative coupling reactions are catalyzed by a ruthenium hydrido chloride complex (1), supported by a chelating P^N ligand (L1) bearing a benzannulated phenanthridine donor arm. The pyrimidines thus produced are emissive in solution, with photoluminescence quantum yields reaching 72%. Details of the catalytic synthesis and characterization of the pyrimidines in both solution and the solid state are reported, along with computational modeling of the emissive excited states of representative examples.

Deep-Red Luminescence from Platinum(II) Complexes of N

A synthetic methodology for accessing narrow-band, deep-red phosphorescence from mononuclear Pt(II) complexes is presented. These charge-neutral complexes have the general structure (N^N-^N)PtCl, in which the Pt(II) centers are supported by benzannulated diarylamido ligand scaffolds bearing substituted quinolinyl and/or phenanthridinyl arms. Emission maxima ranging from 683 to 745 nm are observed, with lifetimes spanning from 850 to 4500 ns. In contrast to the corresponding proligands, benzannulation is found to counterintuitively but markedly blue-shift emission from metal complexes with differing degrees of ligand benzannulation but similar substitution patterns. This effect can be further tuned by incorporation of electron-releasing (Me, tBu) or electron-withdrawing (CF3) substituents in either the phenanthridine 2-position or quinoline 6-position. Compared with symmetric bis(quinoline) and bis(phenanthridine) architectures, "mixed" ligands incorporating one quinoline and one phenanthridine unit present a degree of charge transfer between the N-heterocyclic arms that is more pronounced in the proligands than in the Pt(II) complexes. The impact of benzannulation and ring-substitution on the structure and photophysical properties of both the proligands and their deep-red emitting Pt(II) complexes is discussed.

(8-Amino)quinoline and (4-Amino)phenanthridine Complexes of Re(CO)3 Halides.

In this report, we present a study on the synthesis, structure, and electronics of a series of (8-amino)quinoline and (4-amino)phenanthridine complexes of Re(CO)3X, where X = Cl and Br. In all cases, the (amino)heterocycles bind as bidentate ligands, with surprisingly symmetric modes of binding based on Re-N bond lengths. Between the complexes of (8-amino)quinolines and (4-amino)phenanthridines studied in this report, we do not observe much structural variation, and remarkably similar UV-visible absorption spectra. Expansion of the π-system in the (4-amino)phenanthridine complexes does result in an increase in the intensity of the lowest energy transitions (λmax), which computational modeling suggests are more purely MLCT in character compared with the mixed π-π*/MLCT character of these transitions in the smaller (8-amino)quinoline-supported complexes. DFT and TDDFT modeling further showed that consideration of spin-orbit coupling (SOC) is essential; omitting SOC misses the π-π* contributions to λmax and is unable to accurately model the observed electronic absorption spectra.