A comparative study of the spectroscopy and oxidative spectroelectrochemistry of a series of homo- and heterobimetallic Ru(II) and Os(II) polypyridine complexes

A spectroscopic and spectroelectrochemical comparison is made among homo- and heterobimetallic complexes of the form [(bpy)₂Ru(BL)Os(byp)₂]⁴⁺, [(bpy)₂Ru(BL)Ru(bpy)₂]⁴⁺ and [(bpy)₂Os(BL)Os(bpy)₂]⁴⁺ (BL = 2,3,-bis(2′-pyridyl)pyrazzine(dpp),2,3-bis(2′-pyridyl)quinoxaline(dpq) or 2,3-bis(2′-pyridyl)benzoquinoxaline(dpb); bpy = 2,2′-bipyridine). It has been postulated that the spectroscopy of the mixed-metal bimetallic complexes bridged by polyazine bridging ligands can be assigned by comparison to those of the homobimetallic analogs. We have in hand a unique series of complexes where such a postulate can be tested. Utilizing the visible spectra of the homobimetallic Os,Os and Ru,Ru systems, we have been able to generate the spectra of the mixed-metal complexes. Some differences have been seen, particularly in the energy of the Os → dpp ³MLCT. Oxidative spectroelectrochemistry studies on the homobimetallic ruthenium or osmium based systems indicate that upon complete oxidation of both metal centers, transitions in the visible are lost. Hence, partial oxidation of the ruthenium based homobimetallics and Os, Ru mixed-metal bimetallics allows for the direct comparison of the spectroscopic character of the one remaining ruthenium chromophore within these mixed-valence systems. Oxidation to form the Os(III)/Ru(II) species and the Ru(III)/Ru(II) species resulted in similar spectra. This establishes further that the visible spectroscopy of mixed-metal systems of this nature can be accurately interpreted by comparison to the homobimetallic analogs.     

Comparing the spectroscopic and electrochemical properties of ruthenium and osmium complexes of the tridentate polyazine ligands 2,2′:6′,2″-terpyridine and 2,3,5,6-tetrakis(2-pyridyl)pyrazine

A number of osmium and ruthenium complexes of the tridentate ligands 2,2′:6′,2″-terpyridine (tpy) and 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tpp) have been prepared and characterized by our laboratory. All these complexes possess metal based oxidations and ligand based reductions localized on each polyazine ligand. Polymetallic complexes bridged by the tpp ligand exhibit two sequential tpp based reductions prior to the reduction of other polyazine ligands in these complexes. The spectroscopy of these complexes is dominated by ligand based π-π^* transitions in the ultraviolet and MLCT (metal-to-ligand charge transfer) bands terminating on each polyzine ligand in the visible. For the complexes reported herein the lowest lying optical transitionis a M → BL CT band. For most of the complexes reported, occupation of this excited state gives rise to an observable emission at room temperature. For ruthenium complexes of these tridentate ligands, the presence of a low-lying LF state shortens the excited state lifetimes of these chromophores. This gives rise to ruthenium complexes that display shorter excited state lifetimes than the analogous osmium based systems. Incorporation of tpp based chromophores into polymetallic frameworks leads to the production of bimetallic species with long-lived excited states, 100 ns at room temperature. This makes these chromophores good candidates for the development of stereochemically defined supramolecular complexes. It is possible to measure an electrochemical HOMO-LUMO energy gap and a correlation between this electrochemically measured energy gap and the spectroscopic energy associated with this HOMO→LUMO transition are reported herein (HOMO== highest occupied molecular orbital, LUMO = lowest unoccupied molecular orbital).     

Synthesis and characterization of 1:2 metal complexes of the biheteroaromatic ligand 2-(2′-pyridyl)quinoxaline (L) and the X-ray structure of [CuL2](PF6)

The first 1:2 metal complexes of 2-(2′-pyridyl)quinoxaline (L) have been isolated. The physical and spectroscopic characteristics of the compounds [MCl₂L₂] (M = Ni, Cu, Cd) and [Cu^IL₂](PF₆) are described. The structure of the copper(I) complex has been determined by X-ray diffraction methods. Crystals are orthorhombic, space group P_cnb with A = 11.014(2), B = 12.886(2), C = 17.806(4) Å, V = 2527.1(9) ų and Z = 4. Refinement of the structure gave a final R factor of 0.046 (R_w = 0.041) for 814 unique reflections having I > 2.0σ(I). The ligand L acts as a bidentate chelate, the ligated atoms being the pyridine nitrogen and the nearest quinoxaline nitrogen. The structure of [CuL₂]⁺ consists of a distorted tetrahedral arrangement around the copper(I) atom with Cu---N bond lengths of 2.023(6) and 2.059(5) Å and the N---Cu---N angle of the chelating ligand equal to 80.6(2)°. A monomeric trans pseudo-octahedral stereochemistry is assigned for the [MCl₂L₂] complexes.     

Mononuclear copper(II) complexes with quinolones and nitrogen-donor heterocyclic ligands: Synthesis, characterization, biological activity and interaction with DNA

The neutral mononuclear copper(II) complexes with the quinolone antibacterial drugs, pipemidic acid and N-propyl-norfloxacin, in the presence or absence of nitrogen-donor heterocyclic ligands, 2,2′-bipyridine, 1,10-phenanthroline or 2,2′-dipyridylamine, have been prepared and characterized spectroscopically. The interaction of copper(II) with the deprotonated quinolone ligand leads to the formation of the neutral mononuclear complexes of the type [Cu(quinolone)₂(H₂O)] (1)–(2) while the presence of the N-donor ligand leads to the formation of the neutral mononuclear complexes of the type [Cu(quinolone)(N-donor)Cl] (3)–(8). In all the complexes, copper(II) is pentacoordinate having a distorted square pyramidal geometry. The electron paramagnetic resonance spectra of 1 and 2 are typical of mononuclear Cu(II) complexes, while for the mixed-ligands complexes 3–8 a mixture of dimeric and monomeric species is indicated. The interaction of the complexes with calf-thymus DNA has been investigated with diverse spectroscopic techniques and has shown that the complexes can be bound to calf-thymus DNA by the intercalative mode. The antimicrobial activity of the complexes has been tested on three different microorganisms. All the complexes show an increased biological activity in comparison to the corresponding free quinolone ligand.     

Multinucleating ligands from multiple palladium(0)-catalysed cross-coupling reactions — synthesis and characterisation of a trinuclear cyclometallated ruthenium(II) complex and a hexanuclear EPR-active molybdenum complex

Two multinucleating ligands have been prepared from 1,3,5-tris(3,5-dibromophenyl)benzene by multiple Pd(0)-catalysed cross-coupling reactions. 1,3,5-Tris[3,5-bis(4-pyridylethenyl)phenyl]benzene (L¹) has six remote pyridyl moieties, each of which can coordinate a 17 valence-electron Mo(tp^*)(NO)Cl fragment (tp^* = hydrotris(3,5-dimethylpyrazolyl)borate), affording the hexanuclear complex [Cl(NO)(tp^*)Mo₆(L¹) (1). 1,3,5-Tris[3,5-bis(2-pyridyl)phenyl]benzene (L²) incorporates three potentially terdentate, cyclometallating N,C,N-donor sets, and can coordinate three Ru(tpy)²⁺ fragments (tpy = 2,2′:6′,2″-terpyridine) giving the trinuclear complex [(tpy)Ru₃(L²)][PF₆]₃ (2). Complex 1 is EPR active, with nearest-neighbour pairs of molybdenum centres displaying magnetic exchange interactions. Electrochemical studies of the two complexes suggest that there is little ground-state interaction between the metal centres in either case.     

Isolation and X-ray structure determination of a neolignan from Clerodendron inerme seeds

A new neolignan, 5,8-epoxy-6,7-dimethyl 2′,3′,2″,3″-dimethylene dioxy-4′,1″-dimethoxy-1,2:3,4-dibenzo-1,3-cyclooctadiene, from the petrol extract of Clerodendron inerme seeds, was characterized by spectroscopic and X-ray crystallographic methods. This compound makes up ca 5% by wt of the seeds.     

Variation of DNA photocleavage efficiency for [(TL)2Ru(dpp)]Cl2 complexes where TL=2,2'-bipyridine, 1,10-phenanthroline, or 4,7-diphenyl-1,10-phenanthroline

The complexes [(bpy)₂Ru(dpp)]Cl₂, [(phen)₂Ru(dpp)]Cl₂, and [(Ph₂phen)₂Ru(dpp)]Cl₂ (where dpp = 2,3-bis(2-pyridyl)pyrazine, bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline, Ph₂phen = 4,7-diphenyl-1,10-phenanthroline) have been investigated and found to photocleave DNA via an oxygen-mediated pathway. These light absorbing complexes possess intense metal-to-ligand charge transfer (MLCT) transitions in the visible region of the spectrum. The [(TL)₂Ru(dpp)]²⁺ systems populate ³MLCT states after visible light excitation, giving rise to emissions in aqueous solution centered at 692, 690, and 698 nm for TL = bpy, phen, and Ph₂phen respectively. The ³MLCT states and emissions are quenched by O₂, producing a reactive oxygen species. These complexes photocleave DNA with varying efficiencies, [(Ph₂phen)₂Ru(dpp)]²⁺ > [(phen)₂Ru(dpp)]²⁺ > [(bpy)₂Ru(dpp)]²⁺. The presence of the polyazine bridging ligand will allow these chromophores to be incorporated into larger supramolecular assemblies.     

Synthesis of some ruthenium complexes with mixed diimine ligands

The use of Ru(DMSO)₄Cl₂ and Ru(PY)₄Cl₂ (DMSO=dimethyl sulphoxide; Py=pyridine) in synthesizing mixed ligand complexes is reported. The bidentate ligands used are of the diimine type, namely, 2,2′-bipyrimidine (bpm); 3,6-di-(2-pyridyl)-1,2,4, 5-tetrazine (dpt); 2,3-bis(2-pyridyl)-5,6-dihydropyrazine (dhp); 2,3-bis(2-pyridyl)-pyrazine (dpp); 2,3-bis-(2-pyridyl)-quinoxaline (dpq); 2,3,5,6-tetrakis(2-pyridyl)-pyrazine (tpp). Characterization of the complexes has been accomplished using elemental analysis, conductivity, IR and UV-Vis spectroscopy.     

Synthesis, structure and reactivity of the homoleptic iron(II) complex of the novel 4′-(4?-pyridyl-N-oxide)-2,2′:6′,2″-terpyridine ligand

The new ligand 4′-(4?-pyridyl-N-oxide)-2,2′:6′,2″-terpyridine (pyNoxterpy) and its homoleptic iron(II) complex have been synthesised, and structural and spectroscopic studies have been carried out. The obtained results have been compared with the reported data for the parent ligand 4′-(4?-pyridyl)-2,2′:6′,2″-terpyridine (pyterpy) and its homoleptic iron(II) complex. Significant differences between the spectral and electrochemical properties of the metal complexes have been found, derived from the changes in the electronic properties of the coordinated ligands.     

Deuterium labeling of diethylstilbestrol and analogues

E-2,2,3',3″,5,5,5',5″-octadeuteriodiethylstilbestrol (DES-d8) and Z-2,3',3″,4,5,5,5',5″-octadeuterio-3,4-bis(p-hydroxyphenyl)-2-hexene (ψ-DES-d8) were synthesized from E-diethylstilbestrol (DES) by hydrogen/ deuterium exchange in a mixture of methanol-d and deuterium chloride in deuterium oxide. The structures, isotopic purity, and positions of up-take of deuterium were determined by nuclear magnetic resonance (NMR) and mass spectrometry (MS). Additional confirmation of the positions of deuterium exchange in stilbestrols was obtained from an analysis of the oxidation of DES-d8 to Z,Z-2,3',3″,5,5',5″-hexadeuteriodienestrol (β-DIES-d6) and of the hydrogen/deuterium exchange reaction of hexestrol (HEX) to 3',3″,5',5″-hexestrol (HEX-d4). Structural analysis and the determination of isotopic purity of the latter two compounds were also carried out by NMR and MS. The uptake of eight deuterium atoms by DES is postulated to proceed via two different reactions occurring simultaneously: 1. acid catalyzed deuteration of all four phenolic ortho-positions (3',3″,5',5″); 2. acid catalyzed deuteration of the olefin bridge with subsequent formation of deuterated ψ-DES (3 or 4). Due to the equilibration between DES, ψ-DES, and Z-diethylstilbestrol (cis-DES) in the acidic reaction mixture at 85°C, the deuterated ψ-DES is thought to rapidly rearrange to deuterated DES. Repeated deuteration will eventually form DES-d8 fully labeled in the 2,2,5,5 methylene positions.     

Stereochemistry of quinoxaline antagonist binding to a glutamate receptor investigated by Fourier transform infrared spectroscopy

The stereochemistry of the interactions between quinoxaline antagonists and the ligand-binding domain of the glutamate receptor 4 (GluR4) have been investigated by probing their vibrational modes using Fourier transform infrared spectroscopy. In solution, the electron-withdrawing nitro groups of both compounds establish a resonance equilibrium that appears to stabilize the keto form of one of the cyclic amide carbonyl bonds. Changes in the 6,7-dinitro-2,3-dihydroxyquinoxaline vibrational spectra on binding to the glutamate receptor, interpreted within the framework of a published crystal structure, illuminate the stereochemistry of the interaction and suggest that the binding site imposes a more polarized electronic bonding configuration on this antagonist. Similar spectral changes are observed for 6-cyano-7-dinitro-2,3-dihydroxyquinoxaline, confirming that its interactions with the binding site are highly similar to those of 6,7-dinitro-2,3-dihydroxyquinoxaline and leading to a model of the 6-cyano-7-dinitro-2,3-dihydroxyquinoxaline-S1S2 complex, for which no crystal structure is available. Conformational changes within the GluR ligand binding domain were also monitored. Compared with the previously reported spectral changes seen on binding of the agonist glutamate, only a relatively small change is detected on antagonist binding. This correlation between the functional effects of different classes of ligand and the magnitude of the spectroscopic changes they induce suggests that the spectral data reflect physiologically relevant conformational processes.     

SERRS study of the DNA binding by Ru(II) tris-(Bipyridyl) complexes bearing one carboxylic group

Surface enhanced resonance Raman scattering (SERRS) is shown to be a satisfying method to study the interaction between DNA and ruthenium complexes [Ru(bpy)(2)(Hcmbpy)][PF(6)](2), where Hcmbpy = 4-carboxy-4'-methyl-2,2'-bipyridine. Such metallic complexes are known for their fluorescence properties. To validate this spectroscopic approach we have checked that i) at a given lambda(ex), silver colloidal SERRS spectra of Ru complexes closely resemble resonance Raman spectra in aqueous solutions, intensity excepted, and ii) the DNA fragments are not altered when they are adsorbed on the Ag nanoparticles surface. This investigation shows that the intensity of the Ru complexes SERRS spectra is reduced in the presence of DNA, in particular for the specific bands assigned to the Hcmbpy ligand. This collapse demonstrates that the Ru complexes bind DNA through the Hcmbpy moiety, and intercalation is suggested as the binding mode. The DNA binding by the enantiopure Ru complexes (Delta or Lambda) is more efficient than by the racemic complexes.     

Five lignan derivatives from in vitro cultures of the liverwort Jamesoniella autumnalis

Five new lignan derivatives, 2,3,6′-tricarboxy-6,7-dihydroxy-1(3′)-2′-pyranonyl-1,2-dihydronaphthalene, its two monomethyl esters, 2,6′-dicarboxy-6,7-dihydroxy-1(3′)-2′-pyranonyl-1,2-dihydronaphthalene and 2,3-dicarboxy-6,7-dihydroxy-1-(3′,4′-dihydroxy)-phenylnaphthalene, were isolated from the methanolic extract of aseptic cultures of the liverwort Jamesoniella autumnalis. Their structures were determined by spectroscopic analysis.     

A new family of lanthanide terpyridine nitrate complexes: Solvothermal syntheses, crystal structures and luminescent properties of [Ln(pytpy)(NO3)2(μ-OCH3)]2

The complexes [Ln(pytpy)(NO₃)₂(μ-OCH₃)]₂ (Ln = Eu(III), Tb(III), Dy(III), pytpy=4′-(n-pyridyl)-2,2′:6′,2″-terpyridine, n = 2, 3) were synthesized and characterized by IR, elemental analyses, UV–Vis and luminescent spectroscopy. Three complexes crystallized in monoclinic system, P2₁/n space group. Lanthanide ions are nine-coordinated by three nitrogen atoms from tridentate pytpy ligands, four oxygen atoms from two bidentate nitrate groups and two oxygen atoms from two methoxo groups, forming distorted tricapped trigonal prismatic geometries. The dimethoxo-bridges connect two metal ions in asymmetric fashion into dimeric structures with short LnLn distances of 3.767(1), 3.740(1) and 3.720(1) Å for Eu(III), Tb(III) and Dy(III) complexes, respectively. Photoluminescence measurement indicates that 1 and 3 emit the characteristic luminescence of Tb(III) and Eu(III) ions in the solid state, respectively. The luminescent spectrum of Eu(III) complex in solvents was also investigated.     

Quantification of raltegravir (MK0518) in human plasma by high-performance liquid chromatography with photodiode array detection

A precise and accurate high-performance liquid chromatography (HPLC) method with photodiode array detection has been developed and validated for raltegravir, a human immunodeficiency virus integrase strand transfer inhibitor (HIV-1 INSTI). Plasma (300 μL) was extracted with dichloromethane/hexane 50:50 (v/v) after addition of the internal standard, 6,7-dimethyl-2,3-di(2-pyridyl) quinoxaline. The compounds were separated using a dC18 column and detected with ultraviolet detection at 320 nm. The limit of quantification was 10 ng/mL for raltegravir. The method was linear and validated over a concentration range of 0–10,000 ng/mL. The intra-day precision ranged from 3.1 to 12.3%, while the intra-day accuracy ranged from ?15.0 to ?0.5%, the inter-day precision and accuracy were less than 7%. The mean recovery was 76.8%. Application to clinical samples taken from patients treated with raltegravir indicated that the method is suitable for measuring plasma concentrations of raltegravir in pharmacokinetic studies of clinical trials.     

Ternary complexes in solution with hydrogen phosphate and methyl phosphate as ligands

The stability constants of the 1:1 complexes formed between Cu(Arm)²⁺, where Arm = 2,2′-bipyridyl or 1,10-phenanthroline, and methyl phosphate, CH₃OPO₃²⁻, or hydrogen phosphate, HOPO₃²⁻, were determined by potentiometric pH titration in aqueous solution (25°C; l = 0.1 M, NaNO₃). On the basis of previously established log K versus pK_a straight-line plots (D. Chen et al., J. Chem. Soc., Dalton Trans. (1993) 1537–1546) for the complexes of simple phosphate monoesters and phosphonate derivatives, R-PO₃²⁻, where R is a non-coordinating residue, it is shown that the stabilities of the Cu(Arm) (CH₃OPO₃) complexes are solely determined by the basicity of the -PO₃²⁻ residue. In contrast, the Cu(Arm) (HOPO₃) complexes are slightly more stable (on average by 0.15 log unit) than expected on the basicity of HPO₄²⁻; this is possibly due to a more effective solvation including hydrogen bonding, an interaction not possible with coordinated CH₃OPO₃²⁻ species. Regarding biological systems the observation that HOPO₃²⁻ is somewhat favored over R-PO₃²⁻ species in metal ion interactions is meaningful.     

Zinc(II)-phenoxyl radical complexes: Dependence on complexation properties of Zn-phenolate species

Zinc(II) complexes of N₃O-donor tripodal ligands, 2,4-di(tert-butyl)-6-{[bis(2-pyridyl)methyl]aminomethyl}phenol (HtbuL), 2,4-di(tert-butyl)-6-{[(6-methyl-2-pyridyl)methyl]-(2-pyridyl)methylaminomethyl}phenol (HtbuLMepy), and 2,4-di(tert-butyl)-6-{[bis(6-methyl-2-pyridyl)methyl]aminomethyl}phenol (HtbuL(Mepy)₂), [Zn(tbuL)Cl] · CH₃OH (1), [Zn(tbuLMepy)Cl] (2), and [Zn(tbuL(Mepy)₂)Cl] (3), respectively, were prepared and structurally characterized by the X-ray diffraction method. All the complexes were found to have a mononuclear structure with a coordinated phenolate moiety, the geometry of the Zn(II) center being 5-coordinate trigonal-bipyramidal. The Zn(II) binding ability of the ligands with and without 6-methyl-2-pyridylmethyl moieties was evaluated for similar ligands, which lacked the t-butyl groups at the 2- and 4-positions of the phenol moiety, by the stability constants determined by potentiometric titration at 25 °C (I = 0.1 M (KNO₃)). The stability of the complexes was found to be in the order L > LMepy > L(Mepy)₂, reflecting the steric hindrance of the 6-methyl group of the pyridine ring. Complexes 1, 2, and 3 were converted to the phenoxyl radicals upon oxidation with Ce(IV), giving a phenoxyl radical π-π∗ transition band at 394-407 nm. ESR and resonance Raman spectra established that the radical species had a Zn(II)-phenoxyl radical bond. The cyclic voltammograms showed similar quasi-reversible redox waves with E_1/2 = 0.68, 0.67, and 0.63 V (versus Ag/AgCl) for 1, 2, and 3, respectively, corresponding to the formation of the phenoxyl radical, which displayed a first-order decay. The half-lives, 58.6, 25.8, and 15.6 min at −40 °C for 1, 2, and 3, respectively, follow the order of the stability constants of the complexes, indicating that the metal(II)-phenoxyl radical stability is in close relationship with the complexation properties of the present series of N₃O-donor ligands.     

Prenylated flavonoids of Erythrina lysistemon grown in Egypt

Three prenylated flavonoid derivatives; 5,7,4′-trihydroxy-8-(3-methylbut-2-enyl)-6-(2″-hydroxy-3″-methylbut-3″enyl) isoflavone (isoerysenegalensein E), 5,7,2′-trihydroxy-4′-methoxy-5′-(3″-methylbut-2″-enyl) isoflavanone (lysisteisoflavanone), 5, 4′-dihydroxy-6-(3-methylbut-2-enyl)-2″-hydroxyisopropyl dihydrofurano [4″,5″:8,7] isoflavone (isosenegalensin), together with the four known flavonoids abyssinone V-4′-methylether, alpinumisoflavone, wighteone and burttinone were isolated from the stem bark of Erythrina lysistemon Hutch. (Leguminosae). Structures were elucidated by spectroscopic methods.     

A comparison of the gas, solution, and solid state coordination environments for the Ni(II) complexes of a series of linear penta- and hexadentate aminopyridine ligands with accessible Ni(III) oxidation states

The synthesis and characterization of the nickel(II) complexes of a series of pentadentate and hexadentate aminopyridine ligands that contain ethylenediamine and/or propylenediamine groups are described. The ligands include: 1,12-bis(2-pyridyl)-2,5,8,11-tetraazadodecane, TRIEN-pyr; 1,13-bis(2-pyridyl)-2,5,9,12-tetraazatridecane, DIEN-PN-pyr; 1,14-bis(2-pyridyl)-2,6,9,13-tetraazatetradecane, DIPN-EN-pyr; 1,15-bis(2-pyridyl)-2,6,10,14-tetraazapentadecane, TRIPN-pyr; 1,9-bis(2-pyridyl)-2,5,8-triazanonane, DIEN-pyr; and 1,11-bis(2-pyridyl)-2,6,10-triazaundecane, DIPN-pyr. The following methods were used to determine the binding geometries of the nickel(II) complexes in the solid, solution, and gas phases: magnetic susceptibility measurements, absorption spectroscopy, EPR spectroscopy, electrochemistry, and electrospray ionization mass spectrometry. All of the ligands form 6-coordinate compounds in the solid, liquid, and gas states, with the exception of the TRIEN-pyr, DIEN-PN-pyr(partially), DIPN-pyr, and DIEN-pyr ligands which form 5-coordinate species in the gas state. All of the complexes could be oxidized to Ni(III) species electrochemically, although the Ni(III) complexes of TRIPN-pyr and DIPN-pyr were much less stable than the other four ligands. EPR spectra of the frozen solutions showed the low spin d⁷ Ni(III) complexes of TRIEN-pyr and DIPN-EN-pyr to be similar to those that have been found for poly-aza macrocyclic compounds.     

Eryvarins F and G,two 3-phenoxychromones from the roots of Erythrina variegata

Two 3-phenoxychromones, eryvarins F and G, were isolated from the roots of Erythrina variegata. Their structures were established to be 3-(2,4-dihydroxyphenoxy)-7-hydroxy-6,8-di(3,3-dimethylallyl)chromen-4-one and 3-(2,4-dihydroxyphenoxy)-8-(3,3-dimethylallyl)-2,2-dimethylpyrano[5,6:6,7]chromen-4-one on the basis of spectroscopic and chemical evidence. Eryvarins F and G are unusual 3-phenoxychromone derivatives with two isoprenoid groups.