Electronic Structure of Metallophlorins: Lessons from Iridium and Gold Phlorin Derivatives.

Phlorins have long remained underexplored relative to their fully conjugated counterparts, such as porphyrins, hydroporphyrins, and corroles. Herein, we have attempted to bridge that knowledge gap with a scalar-relativistic density functional theory (DFT) study of unsubstituted iridium and gold phlorin derivatives and a multitechnique experimental study of iridium-bispyridine and gold complexes of 5,5-dimethyl-10,15,20-tris(pentafluorophenyl)phlorin. Theory and experiments concur that the phlorin derivatives exhibit substantially smaller HOMO-LUMO gaps, as reflected in a variety of observable properties. Thus, the experimentally studied Ir and Au complexes absorb strongly in the near-infrared (NIR), with absorption maxima at 806 and 770 nm, respectively. The two complexes are also weakly phosphorescent with emission maxima at 950 and 967 nm, respectively. They were also found to photosensitize singlet oxygen formation, with quantum yields of 40 and 28%, respectively. The near-infrared (NIR) absorption and emission are consonants with smaller electrochemical HOMO-LUMO gaps of ∼1.6 V, compared to values of ∼2.1 V, for electronically innocent porphyrins and corroles. Interestingly, both the first oxidation and reduction potentials of the Ir complex are some 600 mV shifted to more negative potentials relative to those of the Au complex, indicating an exceptionally electron-rich macrocycle in the case of the Ir complex.

Longitudinal changes in device-measured physical activity from childhood to young adulthood: the PANCS follow-up study.

BACKGROUND: There is a lack of longitudinal studies examining changes in device-measured physical activity and sedentary time from childhood to young adulthood. We aimed to assess changes in device-measured physical activity and sedentary time from childhood, through adolescence, into young adulthood in a Norwegian sample of ostensibly healthy men and women. METHODS: A longitudinal cohort of 731 Norwegian boys and girls (49% girls) participated at age 9 years (2005-2006) and 15 years (2011-2012), and 258 of these participated again at age 24 years (2019-2021; including the COVID-19 pandemic period). Physical activity and sedentary time were measured using ActiGraph accelerometers. Linear mixed models were used to analyse changes in physical activity and sedentary time and whether low levels of childhood physical activity track, i.e., persist into young adulthood (nchange=721; ntracking=640). RESULTS: The most prominent change occurred between the ages of 9 to 15 years, with an increase in sedentary time (150 min/day) and less time spent in light (125 min/day), moderate (16 min/day), and vigorous physical activity (8 min/day). Only smaller changes were observed between the ages of 15 and 24 years. Changes in moderate-to-vigorous physical activity from childhood to young adulthood differed between subgroups of sex, tertiles of body mass index at baseline and tertiles of peak oxygen uptake at baseline. While the tracking models indicated low absolute stability of physical activity from childhood to young adulthood, children in the lowest quartiles of moderate-to-vigorous (OR:1.88; 95%CI: 1.23, 2.86) and total physical activity (OR: 1.87; 95%CI: 1.21, 2.87) at age 9 years were almost 90% more likely to be in these quartiles at age 24 years compared to those belonging to the upper three quartiles at baseline. CONCLUSIONS: We found a substantial reduction in physical activity and increase in time spent sedentary between age 9 and 15 years. Contrary to previous studies, using mainly self-reported physical activity, little change was observed between adolescence and young adulthood. The least active children were more likely to remain the least active adults and could be targeted for early intervention.

Structure-sensitive marker bands of metallocorroles: A resonance Raman study of manganese and gold corrole derivatives.

Soret-excited resonance Raman spectra (λex 413.1 nm) were acquired for manganese(III) and gold(III) tris(pentafluorophenyl)corrole, each as four different isotopomeric samples: natural abundance, fully pyrrole-15N-substituted, fully meso-13C-substituted, and fully pyrrole-15N-meso-13C-substituted. The spectra were modeled with density functional theory-based vibrational analyses, which in general did an excellent job of reproducing both the absolute frequencies and isotope shifts. The results led to the assignment and visualization of approximately 10 prominent Raman bands. A key finding was that the bands could be categorized into two broad classes: Class A, exhibiting large 15N isotope shifts, assignable to vibrations with predominant Cα-N character, and Class B, exhibiting large meso-13C isotope shifts, assignable to vibrations with predominant Cα-Cmeso character. Preliminary evidence suggests that the class A bands may serve as core size markers, while class B bands may correlate with the innocence or otherwise of the corrole macrocycle.

The Story of 5d Metallocorroles: From Metal-Ligand Misfits to New Building Blocks for Cancer Phototherapeutics.

Porphyrin chemistry is Shakespearean: over a century of study has not withered the field's apparently infinite variety. Heme proteins continually astonish us with novel molecular mechanisms, while new porphyrin analogues bowl us over with unprecedented optical, electronic, and metal-binding properties. Within the latter domain, corroles occupy a special place, exhibiting a unique and rich coordination chemistry. The 5d metallocorroles are arguably the icing on that cake.New Zealand chemist Penny Brothers has used the word "misfit" to describe the interactions of boron, a small atom with a predilection for tetrahedral coordination, and porphyrins, classic square-planar ligands. Steve Jobs lionized misfits as those who see things differently and push humanity forward. Both perspectives have inspired us. The 5d metallocorroles are misfits in that they encapsulate a large 5d transition metal ion within the tight cavity of a contracted porphyrin ligand.Given the steric mismatch inherent in their structures, the syntheses of some 5d metallocorroles are understandably capricious, proceeding under highly specific conditions and affording poor yields. Three broad approaches may be distinguished.(a) In the metal-alkyl approach, a free-base corrole is exposed to an alkyllithium and the resulting lithio-corrole is treated with an early transition metal chloride; a variant of the method eschews alkyllithium and deploys a transition metal-alkyl instead, resulting in elimination of the alkyl group as an alkane and insertion of the metal into the corrole. This approach is useful for inserting transition metals from groups 4, 5, and, to some extent, 6, as well as lanthanides and actinides.(b) In our laboratory, we have often deployed a low-valent organometallic approach for the middle transition elements (groups 6, 7, 8, and 9). The reagents are low-valent metal-carbonyl or -olefin complexes, which lose one or more carbon ligands at high temperature, affording coordinatively unsaturated, sticky metal fragments that are trapped by the corrole nitrogens.(c) Finally, a metal acetate approach provides the method of choice for gold and platinum insertion (groups 10 and 11).This Account provides a first-hand perspective of the three approaches, focusing on the last two, which were largely developed in our laboratory. In general, the products were characterized with X-ray crystallography, electrochemistry, and a variety of spectroscopic methods. The physicochemical data, supplemented by relativistic DFT calculations, have provided fascinating insights into periodic trends and relativistic effects.An unexpected feature of many 5d metallocorroles, given their misfit character, is their remarkable stability under thermal, chemical, and photochemical stimulation. Many of them also exhibit long triplet lifetimes on the order of 100 µs and effectively sensitize singlet oxygen formation. Many exhibit phosphorescence in the near-infrared under ambient conditions. Furthermore, water-soluble ReO and Au corroles exhibit impressive photocytotoxicity against multiple cancer cell lines, promising potential applications as cancer phototherapeutics. We thus envision a bright future for the compounds as rugged building blocks for new generations of therapeutic and diagnostic (theranostic) agents.

X-ray absorption spectroscopy of exemplary platinum porphyrin and corrole derivatives: metal- versus ligand-centered oxidation.

A combination of Pt L3-edge X-ray absorption spectroscopy (EXAFS and XANES) and DFT (TPSS) calculations have been performed on powder samples of the archetypal platinum porphyrinoid complexes PtII[TpCF3PP], PtIV[TpCF3PP]Cl2, and PtIV[TpCF3PC](Ar)(py), where TpCF3PP2- = meso-tetrakis(p-trifluoromethylphenyl)porphyrinato and TpCF3PC3- = meso-tris(p-trifluoromethylphenyl)corrolato. The three complexes yielded Pt L3-edge energies of 11 566.0 eV, 11 567.2 eV, and 11 567.6 eV, respectively. The 1.2 eV blueshift from the Pt(ii) to the Pt(iv) porphyrin derivative is smaller than expected for a formal two-electron oxidation of the metal center. A rationale was provided by DFT-based Hirshfeld which showed that the porphyrin ligand in the Pt(iv) complex is actually substantially oxidized relative to that in the Pt(ii) complex. The much smaller blueshift of 0.4 eV, going from PtIV[TpCF3PP]Cl2, and PtIV[TpCF3PC](Ar)(py), is ascribable to the significantly stronger ligand field in the latter compound.

Correction: X-ray absorption spectroscopy of exemplary platinum porphyrin and corrole derivatives: metal- versus ligand-centered oxidation.

[This corrects the article DOI: 10.1039/D1RA06151H.].

Molecular Structure of Copper and µ-Oxodiiron Octafluorocorrole Derivatives: Insights into Ligand Noninnocence.

Single-crystal X-ray structures were obtained for the copper and µ-oxodiiron complexes of 2,3,7,8,12,13,17,18-octafluoro-5,10,15-triphenylcorrole, hereafter denoted as Cu[F8TPC] and {Fe[F8TPC]}2O. A comparison with the crystal structures of other undecasubstituted Cu corroles, including those with H, Ar, Br, I, and CF3 as ß-substituents, showed that the degree of saddling increases in the order: H ≲ F < Ar ≲ Br ≲ I < CF3. In other words, Cu[F8TPC] is marginally more saddled than ß-unsubstituted Cu triarylcorroles, but substantially less saddled than Cu undecaarylcorroles, ß-octabromo-meso-triarylcorroles, and ß-octaiodo-meso-triarylcorroles, and far less saddled than Cu ß-octakis(trifluoromethyl)-meso-triarylcorroles. As for {Fe[F8TPC]}2O, the moderate quality of the structure did not allow us to draw firm conclusions in regard to bond length alternations in the corrole skeleton and hence also the question of ligand noninnocence. The Fe-O bond distances, 1.712(8) and 1.724(8), however, are essentially identical to those observed for {Fe[TPFPC]}2O, where TPFPC3- is the trianion of 5,10,15-tris(pentafluorophenyl)corrole, suggesting that a partially noninnocent electronic structural description may be applicable for both compounds.

Facile Supramolecular Engineering of Porphyrin cis Tautomers: The Case of ß-Octabromo-meso-tetraarylporphyrins.

A porphyrin cis tautomer, where the two central NH protons are on adjacent pyrrole rings, has long been invoked as an intermediate in porphyrin tautomerism. Only recently, however, has such a species been isolated and structurally characterized. Thus, single-crystal X-ray structure determinations of two highly saddled free-base porphyrins, ß-heptakis(trifluoromethyl)-meso-tetrakis(p-fluorophenyl)porphyrin, H2[(CF3)7TFPP], and ß-octaiodo-5,10,15,20-tetrakis(4'-trifluoromethylphenyl)porphyrin, H2[I8TCF3PP], unambiguously revealed cis tautomeric structures, each stabilized as a termolecular complex with a pair of ROH (R = CH3 or H) molecules that form hydrogen-bonded N-H···O-H···N straps connecting the central NH groups with the antipodal unprotonated nitrogens. The unusual substitution patterns of these two porphyrins, however, have left open the question how readily such supramolecular assemblies might be engineered, which prompted us to examine the much more synthetically accessible ß-octabromo-meso-tetraphenylporphyrins. Herein, single-crystal X-ray structures were obtained for two such compounds, 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis(4'-trifluoromethylphenyl)porphyrin, H2[Br8TCF3PP], and 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis(4'-fluorophenyl)porphyrin, H2[Br8TFPP], and although the central hydrogens could not all be located unambiguously, the electron density could be convincingly modeled as porphyrin cis tautomers, existing in each case as a bis-methanol adduct. In addition, a perusal of the Cambridge Structural Database suggests that there may well be additional examples of porphyrin cis tautomers that have not been recognized as such. We are therefore increasingly confident that porphyrin cis tautomers are readily accessible via supramolecular engineering, involving the simple stratagem of crystallizing a strongly saddled porphyrin from a solvent system containing an amphiprotic species such as water or an alcohol.

Free-base porphyrins with localized NH protons. Can substituents alone stabilize the elusive cis tautomer?

The elusive cis tautomer of free-base porphyrins has recently been isolated and structurally characterized in the form of a supramolecular complex. The question as to whether a suitable set of peripheral substituents might lead to a stable cis tautomer in the absence of supramolecular interactions, however, remains unanswered and is one we have attempted to address here by means of density functional theory calculations. The fact that many antipodally ß-tetrasubstituted tetraphenylporphyrin derivatives exhibit localized central protons attached to the ß-unsubstituted pyrrole rings led us to surmise that ß-tetrasubstitution of adjacent pyrrole rings might lead to a porphyrin cis tautomer, an idea that proved fruitful. Indeed, for the "adjacently" substituted tetraphenylporphyrin derivative H2[adj-(CF3)4(CH3)4TPP], the global energy minimum proved to be a highly saddled cis tautomer, with the trans tautomer about 0.07 eV higher in energy. It is important to underscore, however, that the asymmetric ß-substitution pattern is far from the only factor contributing to the stability of the cis tautomer for this porphyrin. A strongly saddled conformation resulting from meso-ß steric interactions also helps alleviate the repulsion between the two central NH protons, thereby stabilizing the cis tautomer relative to the trans.

Advanced Paramagnetic Resonance Studies on Manganese and Iron Corroles with a Formal d4 Electron Count.

Metallocorroles wherein the metal ion is MnIII and formally FeIV are studied here using field- and frequency-domain electron paramagnetic resonance techniques. The MnIII corrole, Mn(tpfc) (tpfc = 5,10,15-tris(pentafluorophenyl)corrole trianion), exhibits the following S = 2 zero-field splitting (zfs) parameters: D = -2.67(1) cm-1, |E| = 0.023(5) cm-1. This result and those for other MnIII tetrapyrroles indicate that when D ≈ - 2.5 ± 0.5 cm-1 for 4- or 5-coordinate and D ≈ - 3.5 ± 0.5 cm-1 for 6-coordinate complexes, the ground state description is [MnIII(Cor3-)]0 or [MnIII(P2-)]+ (Cor = corrole, P = porphyrin). The situation for formally FeIV corroles is more complicated, and it has been shown that for Fe(Cor)X, when X = Ph (phenyl), the ground state is a spin triplet best described by [FeIV(Cor3-)]+, but when X = halide, the ground state corresponds to [FeIII(Cor•2-)]+, wherein an intermediate spin (S = 3/2) FeIII is antiferromagnetically coupled to a corrole radical dianion (S = 1/2) to also give an S = 1 ground state. These two valence isomers can be distinguished by their zfs parameters, as determined here for Fe(tpc)X, X = Ph, Cl (tpc = 5,10,15-triphenylcorrole trianion). The complex with axial phenyl gives D = 21.1(2) cm-1, while that with axial chloride gives D = 14.6(1) cm-1. The D value for Fe(tpc)Ph is in rough agreement with the range of values reported for other FeIV complexes. In contrast, the D value for Fe(tpc)Cl is inconsistent with an FeIV description and represents a different type of iron center. Computational studies corroborate the zfs for the two types of iron corrole complexes. Thus, the zfs of metallocorroles can be diagnostic as to the electronic structure of a formally high oxidation state metallocorrole, and by extension to metalloporphyrins, although such studies have yet to be performed.

X-ray absorption spectroscopy of archetypal chromium porphyrin and corrole derivatives.

A combination of Cr K-edge XAS and DFT calculations have been performed on archetypal chromium porphyrinoid complexes CrIV[TMP]O (2) and CrV[TPC]O (3), and the results have been compared to the reference compound CrIII[TPP]Cl (1), where TPP2-, TMP2-, and TPC3- are the anions of meso-tetraphenylporphyrin, meso-tetramesitylporphyrin, and meso-triphenylcorrole, respectively. The intensity-weighted average energy position in 1 (5990.9 eV), 2 (5992.0 eV) and 3 (5992.6 eV) are consistent with increasing the metal oxidation state along the series. EXAFS and theoretical analysis of 2 and 3 reveal that the Cr-O bond is longer and weaker in 3 relative to 2, despite the structural similarity and increase in oxidation state in 3. This is also reflected in a comparison of the Cr K-pre-edge transitions. The roughly twenty-fold increase in intensity in the two oxo complexes is unsurprising and well-precedented for other first-row transition metals. However, although 3 had greater overall intensity, the intensity of transitions along the Cr-O bond is greater. EXAFS, DFT and TDDFT analyses show that the more contracted N4 core of the corrole results in a greater out-of-plane displacement of the Cr in 3 relative to 2, which in turn accentuates the lower local symmetry of the Cr in 3 relative to 2. This difference helps us to appreciate the TDDFT result that whereas two 1s→ 3d z 2 transitions make up the majority of the intensity in the pre-edge of 2, the pre-edge of 3 also includes fairly intense transitions to molecular orbitals with 3d xz , 3d yz and 3d z 2 character, thus accounting for the somewhat higher overall intensity for 3.

X-ray Absorption Spectroscopy as a Probe of Ligand Noninnocence in Metallocorroles: The Case of Copper Corroles.

The question of ligand noninnocence in Cu corroles has long been a topic of discussion. Presented herein is a Cu K-edge X-ray absorption spectroscopy (XAS) study, which provides a direct probe of the metal oxidation state, of three Cu corroles, Cu[TPC], Cu[Br8TPC], and Cu[(CF3)8TPC] (TPC = meso-triphenylcorrole), and the analogous Cu(II) porphyrins, Cu[TPP], Cu[Br8TPP], and Cu[(CF3)8TPP] (TPP = meso-tetraphenylporphyrin). The Cu K rising-edges of the Cu corroles were found to be about 0-1 eV upshifted relative to the analogous porphyrins, which is substantially lower than the 1-2 eV shifts typically exhibited by authentic Cu(II)/Cu(III) model complex pairs. In an unusual twist, the Cu K pre-edge regions of both the Cu corroles and the Cu porphyrins exhibit two peaks split by 0.8-1.3 eV. Based on time-dependent density functional theory calculations, the lower- and higher-energy peaks were assigned to a Cu 1s → 3d x2- y2 transition and a Cu 1s → corrole/porphyrin π* transition, respectively. From the Cu(II) porphyrins to the corresponding Cu corroles, the energy of the Cu 1s → 3d x2- y2 transition peak was found to upshift by 0.6-0.8 eV. This shift is approximately half that observed between Cu(II) to Cu(III) states for well-defined complexes. The Cu K-edge XAS spectra thus show that although the metal sites in the Cu corroles are more oxidized relative to those in their Cu(II) porphyrin analogues, they are not oxidized to the Cu(III) level, consistent with the notion of a noninnocent corrole. The relative importance of σ-donation versus corrole π-radical character is discussed.

Gold dipyrrin-bisphenolates: a combined experimental and DFT study of metal-ligand interactions.

Given that noninnocent and metalloradical-type electronic structures are ubiquitous among dipyrrin-bisphenolate (DPP) complexes, we synthesized the gold(iii) derivatives as potentially innocent paradigms against which the properties of other metallo-DPP derivatives can be evaluated. Electronic absorption spectra, electrochemical studies, a single-crystal X-ray structure, and DFT calculations all suggest that the ground states of the new complexes indeed correspond to an innocent AuIII-DPP3-, paralleling a similar description noted for Au corroles. Interestingly, while DFT calculations indicate purely ligand-centered oxidations, reduction of AuDPP is predicted to occur across both the metal and the ligand.

Halterman Corroles and Their Use as a Probe of the Conformational Dynamics of the Inherently Chiral Copper Corrole Chromophore.

Halterman corroles have been synthesized for the first time from pyrrole and Halterman's aldehyde via Gryko's "water-methanol method". These were derivatized to the corresponding copper complexes and subsequently to the ß-octabromo complexes. Electronic circular dichroism spectra were recorded for the enantiopure copper complexes, affording the first such measurements for the inherently chiral Cu corrole chromophore. Interestingly, for a given configuration of the Halterman substituents, X-ray crystallographic studies revealed both P and M conformations of the Cu-corrole core, proving that the substituents, even in conjunction with ß-octabromination, are unable to lock the Cu-corrole core into a given chirality. The overall body of evidence strongly indicates a dynamic equilibrium between the P and M conformations. Such an interconversion, which presumably proceeds via saddling inversion, provides a rationale for our failure so far to resolve sterically hindered Cu corroles into their constituent enantiomers by means of chiral HPLC.

Secular and longitudinal physical activity changes in population-based samples of children and adolescents.

The aims of this study were to investigate whether physical activity (PA) and sedentary time (ST) in 9- and 15-year-olds differed between 2005-2006 and 2011-2012 (secular change), and to investigate changes in PA and ST from age 9 to 15 (longitudinal change). In 2005-2006, we invited nationally representative samples of Norwegian 9- (n=1470) and 15-year-olds (n=1348) to participate. In 2011-2012, we invited a new nationally representative sample of 9-year-olds (n=1945), whereas 15-year-olds (n=1759) were invited to participate either based on previous participation in 2005-2006 or from a random sample of schools. We assessed PA and ST objectively using accelerometers. In 2011-2012, both 9- and 15-year-olds spent more time sedentary (≥35.7 min/d, P<.001) and less time in light PA (≥35.2 min/d, P<.001) compared to their peers in 2005-2006. Nine-year-old girls also spent less time in moderate-to-vigorous PA (MVPA) (4.2 min/d, P=.041). In both age groups, the proportion accumulating an average of 60 min/d of MVPA did not differ between the two cohorts. From age 9 to 15, girls and boys decreased their time spent in LPA (≥106.7 min/d, P<.001) and in MVPA (≥20.8 min/d, P<.001). During the same period, ST increased by a mean of >2 h/d (P<.011). We observed an adverse secular change in PA from 2005-2006 to 2011-2012 among 9- and 15-year-olds, and a large decline in PA in the participants followed longitudinally from age 9 to 15 years.

Cross-sectional and prospective associations between physical activity, body mass index and waist circumference in children and adolescents.

OBJECTIVE: To study the cross-sectional and prospective associations between physical activity (PA) of different intensities, body mass index (BMI) and waist circumference (WC) in children and adolescents using isotemporal substitution modelling. METHODS: Physical activity (accelerometry), BMI and WC were assessed in 6- (n = 970), 9- (n = 2,423) and 15-year-olds (n = 1,544) in 2005/2006 and 2011/2012. Participants aged 9 years in 2005/2006 were followed prospectively to 2011/12 (age 15). Associations between PA of different intensities (light, moderate and vigorous), BMI and WC were examined using isotemporal substitution models. RESULTS: Substituting 10 min per day of sedentary time with light PA was associated with higher WC (0.17 to 0.29 cm, p ≤ 0.003)) in all age groups. Substituting 10 min per day of sedentary time with moderate PA was associated with lower WC in 6- and 9-year-olds (-0.32 to -0.47 cm, p ≤ 0.013)). Substituting 10 min per day of sedentary time with vigorous PA was associated with lower WC in 9- and 15-year-olds (-1.08 to -1.79 cm, p ≤ 0.015)). Associations were similar with BMI as the outcome. In prospective analyses, substituting sedentary time with light, moderate or vigorous PA at age 9 was not associated with BMI or WC at age 15. CONCLUSION: Substituting sedentary time with moderate PA appears favourably associated with adiposity in children, whereas vigorous PA may be required in adolescents. Cross-sectional associations were not replicated in prospective analyses.

Objectively measured sedentary time and physical activity and associations with body weight gain: does body weight determine a decline in moderate and vigorous intensity physical activity?

OBJECTIVES: High levels of physical activity (PA) may prevent the development of obesity. However, the magnitude and direction of the association between PA of various intensities, sedentary time and weight status remain unclear. Thus, we examined whether objectively measured sedentary time and PA independently predict gain in body weight, change in body weight and to examine the possibility of reverse causation. METHODS: We examined the prospective associations between sedentary time, PA and body weight (BW). Baseline measurements were conducted in 2008/2009 and follow-up measurements in 2014/2015 in a random sample of the adult Norwegian population (N=1710, 45.1% men). Moderate and vigorous intensity PA (MVPA) and sedentary time were measured by accelerometry and BW and height self-reported. We first modelled the associations between baseline sedentary time and PA with BW at follow-up. We then modelled the reverse associations (BW as the exposure) and sedentary time and PA (as outcomes) in separate models. All models were adjusted for age, sex, baseline value of the outcome, socio-economic status, alcohol consumption, smoking, monitor wear time and follow-up time. RESULTS: Body mass index (BMI) increased by 0.2 units (P=0.003) between baseline and follow-up, and 46.5% of participants were either overweight (36.4%) or obese (10.1%) at baseline increasing to 49.6% (11.7% obese) at follow-up. Baseline sedentary time, MVPA and vigorous PA were not associated with BW at follow-up after adjustment for covariates. In contrast, baseline BW was inversely associated with MVPA (ß=-0.11; 95% confidence interval (CI); -0.21, -0.009) and VPA (ß=-0.035; 95% CI; -0.059, -0.011) in adjusted models. These associations were unchanged when BW was substituted by BMI. CONCLUSIONS: Baseline BW seems to determine a decrease in MVPA in healthy adult Norwegian men and women, more so than the reverse.

Ligand Noninnocence in Iron Corroles: Insights from Optical and X-ray Absorption Spectroscopies and Electrochemical Redox Potentials.

Two new series of iron meso-tris(para-X-phenyl)corrole (TpXPC) complexes, Fe[TpXPC]Ph and Fe[TpXPC]Tol, in which X=CF3 , H, Me, and OMe, and Tol=p-methylphenyl (p-tolyl), have been synthesized, allowing a multitechnique electronic-structural comparison with the corresponding FeCl, FeNO, and Fe2 (µ-O) TpXPC derivatives. Optical spectroscopy revealed that the Soret maxima of the FePh and FeTol series are insensitive to the phenyl para substituent, consistent with the presumed innocence of the corrole ligand in these compounds. Accordingly, we may be increasingly confident in the ability of the substituent effect criterion to serve as a probe of corrole noninnocence. Furthermore, four complexes-Fe[TPC]Cl, Fe[TPC](NO), {Fe[TPC]}2 O, and Fe[TPC]Ph-were selected for a detailed XANES investigation of the question of ligand noninnocence. The intensity-weighted average energy (IWAE) positions were found to exhibit rather modest variations (0.8 eV over the series of corroles). The integrated Fe-K pre-edge intensities, on the other hand, vary considerably, with a 2.5 fold increase for Fe[TPC]Ph relative to Fe[TPC]Cl and Fe[TPC](NO). Given the approximately C4v local symmetry of the Fe in all the complexes, the large increase in intensity for Fe[TPC]Ph may be attributed to a higher number of 3d holes, consistent with an expected FeIV -like description, in contrast to Fe[TPC]Cl and Fe[TPC](NO), in which the Fe is thought to be FeIII -like. These results afford strong validation of XANES as a probe of ligand noninnocence in metallocorroles. Electrochemical redox potentials, on the other hand, were found not to afford a simple probe of ligand noninnocence in Fe corroles.

ß-Octabromo- and ß-Octakis(trifluoromethyl)isocorroles: New Sterically Constrained Macrocyclic Ligands.

Presented herein is a study of the acid-induced demetalation of two sterically hindered copper corroles, Cu ß-octabromo-meso-triphenylcorrole (Cu[Br8TPC]) and ß-octakis(trifluoromethyl)-meso-tris(p-methoxyphenyl)corrole (Cu[(CF3)8TpOMePC]). Unlike reductive demetalation, which affords the free-base ß-octabromocorrole, demetalation of Cu[Br8TPC] under non- reductive conditions (CHCl3/H2SO4) resulted in moderate yields of free-base 5- and 10-hydroxy isocorroles. The isomeric free bases could be complexed to CoII and NiII, affording stable complexes. Only reductive demetalation was found to work for Cu[(CF3)8TpOMePC], affording a highly saddled, hydrated corrole, H3[5-OH,10-H-(CF3)8TpOMePC], where the elements of water had added across C5 and C10. Interaction of this novel free base with CoII resulted in Co[iso-10-H-[CF3)8TpOMePC], a CoII 10-hydro isocorrole. The new metal complexes were all characterized by single-crystal X-ray diffraction analysis and, despite their sterically hindered nature, were found to exhibit almost perfectly planar isocorrole cores.

Metallocorroles as inherently chiral chromophores: resolution and electronic circular dichroism spectroscopy of a tungsten biscorrole.

An inherently chiral metallocorrole has been resolved for the first time by means of HPLC on a chiral stationary phase. For the compound in question, a homoleptic tungsten biscorrole, the absolute configurations of the enantiomers were assigned using online HPLC-ECD measurements in conjunction with time-dependent CAM-B3LYP calculations, which provided accurate simulations of the ECD spectra.