A perimidine-derived non-Kekulé triplet diradical

6,9-Di(tert-butyl)-1-methyltetrazolo[1,5-a]perimidine (1) has been synthesized from naphthalene in seven steps. The EPR spectra, recorded after irradiation of 1 in a butyronitrile matrix at 77 K (lambda = 351 nm) and in Ar and Xe matrixes at 4.6 K (lambda > or = 345 nm), showed a six-line, high-field signal (Delta m(S) = +/- 1), centered at 3350 G in butyronitrile, along with a half-field signal (Delta m(S) = +/- 2), which is characteristic for triplets. Simulation of the observed EPR spectra gave values for the zero-field splitting parameters of |D/hc|/cm(-1) = 0.0105, |E/hc|/cm(-1) = 0.0014 in butyronitrile and |D/hc|/cm(-1) = 0.0107, |E/hc|/cm(-1) = 0.0016 in Ar. These EPR parameters are consistent with the diradical 5,8-di(tert-butyl)-2-(N-methylimino)perimidine-1,3-diyl ((3)2) as source of the EPR spectra. Linearity of the Curie-Weiss plot and UB3LYP and (14/14)CASPT2 calculations of the singlet-triplet energy difference (DeltaE(ST) approximately 8-10 kcal/mol) indicate that the triplet is the ground state of 2, as predicted for such a nondisjoint diradical.     

Limits of delocalization in through-conjugated dinitrenes: aromatization or bond formation?

[reaction: see text] Dinitrenes 4 and 5 both can form quinonoidal structures by conjugative bond formation. However, ESR spectroscopy detects a thermally populated, excited-state, triplet quinonoidal structure only for 4, with a zero-field splitting of |D/hc| = 0.0822 cm(-)(1), |E/hc| congruent with 0.0 cm(-)(1). The tendency to maintain aromaticity in the additional ring of 5 favors a dinitrene structure (with one less formal pi-bond) over a quinonoidal structure. The thermally populated quintet state of 5 has a zero-field splitting of |D/hc| = 0.287 cm(-)(1), |E/hc| 相似文献   

Photolysis and oxidation of azidophenyl-substituted radicals: delocalization in heteroatom-based radicals

2-(4-Azidophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (14), 2-(4-azidophenyl)benzimidazole-1-oxide-3-oxyl (16), 2-(4-azidophenyl)-1,2,6-triphenylverdazyl (19), 2-(3-azidophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (21), and (3-azidophenyl)-N-tert-butyl-N-aminoxyl (25) were photolyzed in frozen solution to give S = 3/2 state ESR spectra of the corresponding nitrenophenyl radicals with the following zero-field splitting parameters: |D/hc| = 0.277 cm(-1), |E/hc| < or = 0.002 cm(-1) (7 from 14); |D/hc| = 0.256 cm(-1), |E/hc| < or = 0.002 cm(-1) (8 from 16); |D/hc| = 0.288 cm(-1), |E/hc| < or = 0.002 cm(-1) (9 from 19); |D/hc| = 0.352 cm(-1), |E/hc| = 0.006 cm(-1) (10 from 21); |D/hc| = 0.336 cm(-1), |E/hc| = 0.004 cm(-1) (11 from 25). UB3LYP/6-31G computations and ESR spectroscopic analyses suggest that these are nitreno radicals, even para-linked systems with possible quinonoidal resonance forms. Neat samples of azidophenyl radicals 14 and 21 showed bulk paramagnetic behavior, consistent with the lack of close contacts in their crystal structures. Efforts to make photolabile coordination complexes of 14 and 21 with paramagnetic transition metal ions were unsuccessful: Cu(ClO4)2 x 6H2O instead oxidized them to the corresponding diamagnetic nitrosonium perchlorate salts.     

Syntheses, optical and intramolecular magnetic properties of mono- and di-radicals based on nitronyl-nitroxide and oxoverdazyl groups appended to 2,6-bispyrazolylpyridine cores

This paper presents the synthesis of a series of nitronyl-nitroxide (NN), oxoverdazyl (OVZ) based mono-, and bi-radicals attached to 4-phenyl-2,6-bispyrazolylpyridine coupling unit, their optical, electron spin resonance (ESR) spectroscopic studies and computational analysis. The ESR studies revealed that the axial zero-field splitting (zfs) parameter of the NN biradical (|D/hc| = 0.00719 cm(-1)) is larger than the OVZ biradical (|D/hc| = 0.00601 cm(-1)). Additionally both biradicals displayed forbidden half-field transitions (ΔM(s) = ±2; g(av) ~ 4.01) at 170 K demonstrating their triplet nature. The cryogenic ESR measurements of the two biradicals showed a Curie magnetic behaviour of the ΔM(s) = ±2 signal intensities (χ(EPR)) down to 4.2 K. A detailed comparative analysis of the strength of hyperfine coupling, spin density distribution, zfs and the spin-spin exchange coupling (J) of both NN and OVZ based biradicals showed that the ground state spin multiplicity of both biradicals is probably triplet (S = 1) or it is nearly degenerate singlet-triplet states with J(NN)?J(OVZ).     

N-(2-methoxycarbonyl-2-yloethyl) (3-nitrenophenyl)aminyl: EPR observation of a quintet hetero-spin molecule

[reaction: see text]. The EPR observation of a ground-state quintet hetero-spin molecule, N-(2-methoxycarbonyl-2-yloethyl) (3-nitreno-phenyl)aminyl 3, in a MTHF matrix at cryogenic temperatures is reported. The molecule has two different kinds of triplet sites, and the ZFS parameters of the quintet are /D/hc/ = 0.170 cm(-1) and /E/hc/ = 0.004 cm(-1). As a result of the nature of the 1,3-localized biradical, the quintet 3 was thermally labile over 5 K.     

Parity and heteroatom effects on open-shell exchange interactions: nitrenophenyl iminoylnitroxides

Photolysis of pN3PhIN and mN3PhIN in frozen matrix yields pNPhIN and mNPhIN, respectively. pNPhIN gives a quartet state with nonlinear ESR intensity behavior (|D/hc| = 0.300 cm(-1), |E/hc| congruent with 0.0 cm(-1)); mNPhIN gives a thermally excited quartet state (|D/hc| = 0.336 cm(-1), |E/hc| = 0.006 cm(-1)) with inverse Curie behavior. Computations show little nitrene delocalization onto the radicals even for the para system. The NPhIN systems behave differently from analogous nitronylnitroxides due to asymmetric radical spin distribution. [reaction: see text]     

Reactive carbon-chain molecules: synthesis of 1-diazo-2,4-pentadiyne and spectroscopic characterization of triplet pentadiynylidene (H-C[triple bond]C-:C-C[triple bond]C-H)

1-Diazo-2,4-pentadiyne (6a), along with both monodeuterio isotopomers 6b and 6c, has been synthesized via a route that proceeds through diacetylene, 2,4-pentadiynal, and 2,4-pentadiynal tosylhydrazone. Photolysis of diazo compounds 6a-c (lambda > 444 nm; Ar or N2, 10 K) generates triplet carbenes HC5H (1) and HC5D (1-d), which have been characterized by IR, EPR, and UV/vis spectroscopy. Although many resonance structures contribute to the resonance hybrid for this highly unsaturated carbon-chain molecule, experiment and theory reveal that the structure is best depicted in terms of the dominant resonance contributor of penta-1,4-diyn-3-ylidene (diethynylcarbene, H-C[triple bond]C-:C-C[triple bond]C-H). Theory predicts an axially symmetric (D(infinity h)) structure and a triplet electronic ground state for 1 (CCSD(T)/ANO). Experimental IR frequencies and isotope shifts are in good agreement with computed values. The triplet EPR spectrum of 1 (absolute value(D/hc) = 0.6157 cm(-1), absolute value(E/hc) = 0.0006 cm(-1)) is consistent with an axially symmetric structure, and the Curie law behavior confirms that the triplet state is the ground state. The electronic absorption spectrum of 1 exhibits a weak transition near 400 nm with extensive vibronic coupling. Chemical trapping of triplet HC5H (1) in an O2-doped matrix affords the carbonyl oxide 16 derived exclusively from attack at the central carbon.     

Low-tempereture photolysis of diazoketones: the conformational isomerism of benzoylphenylmethylene and the IR spectrum of anthronylidene

Low-temperature photolysis of benzoylphenyldiazomethane, 1, and diazoanthrone, 2, in the polycrystal phase resulted in the high-intensity ESR spectra of benxoylphenymethylene 1a and anthronylidene 2a, respectively. Photolyses of argon matrix-isolated 1 and 2, coupled with IR spectroscopy, have now been carried out. Photolysis of 1 yielded the IR spectrum of diphenylketene as the only IR-observable product and indicated the presence in the matrix of the two s-E, s-Z, isomers of 1. On the other hand, photolysis of 2 yielded the IR spectrum of carbene 2a as the only observable product.     

Selective formation of triplet alkyl nitrenes from photolysis of beta-azido-propiophenone and their reactivity

Photolysis of beta-azido propiophenone derivatives, 1, with built-in sensitizer units, leads to selective formation of triplet alkyl nitrenes 2 that were detected directly with laser flash photolysis (lambdamax = 325 nm, tau = 27 ms) and ESR spectroscopy (|D/hc| = 1.64 cm-1, |E/hc| = 0.004 cm-1). Nitrenes 2 were further characterized with argon matrix isolation, isotope labeling, and molecular modeling. The triplet alkyl nitrenes are persistent intermediates that do not abstract H-atoms from the solvent but do decay by dimerizing with another triplet nitrene to form azo products, rather than reacting with an azide precursor. The azo dimer tautomerizes and rearranges to form heterocyclic compound 3. Nitrene 2a, with an n,pi* configuration as the lowest triplet excited state of the its ketone sensitizer moiety, undergoes intramolecular 1,4-H-atom abstraction to form biradical 6, which was identified by argon matrix isolation, isotope labeling, and molecular modeling. beta-Azido-p-methoxy-propiophenone, with a pi,pi* lowest excited state of its triplet sensitizer moiety, does not undergo any secondary photoreactions but selectively yields only triplet alkyl nitrene intermediates that dimerize to form 3b.     

Donor stabilized borylnitrene: a highly reactive BN analogue of vinylidene

A donor atom stabilized borylnitrene, 2-nitreno-1,3,2-benzodioxaborole 4c, is characterized by matrix isolation IR, UV, and ESR spectroscopy as well as multiconfiguration SCF and CI computations. UV irradiation (lambda = 254 nm) of the corresponding azide 6c, isolated in solid argon at 10 K, produces 4c in high yield. The oxygen donor atoms in 4c result in a triplet ground state (|D/hc| = 1.492 cm(-)(1), |E/hc| = 0.004 cm(-)(1)) for the borylnitrene. The lowest energy singlet state ((1)A(1)) is 33 kcal mol(-)(1) higher in energy and closely related to the ground state of vinylidene. Under the conditions of matrix isolation, triplet 4c is photochemically and thermally stable toward rearrangement to the corresponding cyclic iminoborane. Photochemical irradiation (lambda > 550 nm) of 4c rather causes an efficient reaction with molecular nitrogen, lying in matrix sites nearby, to give 6c. Similarly, photochemical, but not thermal, trapping of 4c with CO is possible and results in the corresponding isocycanate 9c. Thermal reaction of 4c with O(2) in doped argon matrixes at 35 K could be observed by IR spectroscopy to result in borylnitroso-O-oxide 17c as shown by (18)O(2) labeling experiments and DFT computations. The diradical 17c is very photolabile and quickly rearranges to the nitritoborane 16c upon irradiation.     

Triplet 1,3-diphenylpropynylidene (Ph-C-C-C-Ph)

Photolysis (lambda>571 nm) of 1,3-diphenyldiazopropyne (9) affords triplet 1,3-diphenylpropynylidene (3), as characterized by IR, UV/vis, and EPR spectroscopy in low-temperature matrices. Two conformational isomers of triplet 3 are spectroscopically distinguishable. The initially formed, non-relaxed conformer is believed to reflect the geometry of the diazo precursor, as enforced by the rigid matrix. Annealing the matrix permits the structure to relax to the equilibrium D2d geometry. The highly symmetric equilibrium structure of 3 is best envisioned as a 1,3-allenic diradical. Density functional theory calculations suggest that the equilibrium structure does not exhibit a bond-localized structure that would be characteristic of an acetylenic carbene. Chemical trapping with O2, however, affords products that are familiar as carbene trapping products: carbonyl oxide 10, ketone 11, and dioxirane 12. Irradiation (lambda>261 nm) of triplet 1,3-diphenylpropynylidene (3) results in cyclization to singlet diphenylcyclopropenylidene (6), a process that is photochemically reversible at lambda=232 nm. Diphenyl-1,2-propadienylidene (7) was not observed under any irradiation conditions.     

NC-(CF2)4-CNSSN radical containing 1,2,3,5-dithiadiazolyl radical dimer exhibiting triplet excited states at low temperature and thermal hysteresis on melting-solidification: structural, spectroscopic, and magnetic characterization

A high yield, one-pot synthesis of the 1,2,3,5-dithiadiazolyl radical NC-(CF2)4-CNSSN radical by reduction of the corresponding 1,3,2,4-dithiadiazolium salt is reported. In the solid state, the title compound is dimerized in trans-cofacial fashion with intra-dimeric Sdelta+...N(delta-) interactions of ca. 3.2 angstroms, and the dimeric units are linked by electrostatic -C triple bond N(delta-)...Sdelta+ interactions forming an infinite chain. Magnetic susceptibility measurements performed on the solid state sample indicate a magnetic moment of 1.8 microB per dimer (1.3 microB per monomer) at 300 K and a good fit to the Bleaney-Bowers model in the temperature range 2-300 K with 2J = -1500 +/- 50 cm(-1), g = 2.02(5), rho = 0.90(3)%, and TIP = 1.25(4) x 10(-3) emu mol(-1). The [NC-(CF2)4-CNSSN radical]2 dimer is the second example of a 1,2,3,5-dithiadiazolyl radical dimer with an experimentally detected triplet excited state as probed by solid-state EPR [2J = -1730 +/- 100 cm(-1), |D| = 0.0278(5) cm(-1), |E| = 0.0047(5) cm(-1)]. The value of the singlet-triplet gap has enabled us to estimate the "in situ" dimerization energy of the radical dimer as ca. -10 kJ mol(-1). The diradical character of the dimer was calculated [CASSCF(6,6)/6-31G*] as 35%. The title radical shows magnetic bistability in the temperature range of 305-335 K as probed by the solid-state EPR presumably arising from the presence of a metastable paramagnetic supercooled phase. Bistability is accompanied by thermochromic behavior with a color change from dark green (dimeric solid) to dark brown (paramagnetic liquid).     

Electron spin-spin exchange coupling mediated by the porphyrin pi system

The syntheses and electron paramagnetic resonance (EPR) spectral characterizations of porphyrins (1-3) substituted with two radical groups bound to trans-meso positions are described. One of these compounds, 3, has been studied by variable-temperature magnetic susceptibility and has been structurally characterized. Biradical porphyrin 3 is monoclinic, space group P2(1)/n, with a = 12.239(2) A, b = 17.819(3) A, c = 34.445(7) A, alpha = 90 degrees , beta = 97.466(3) degrees , gamma = 90 degrees , and Z = 2. The bis(nitroxide) porphyrins 1 and 2 exhibit fluid solution EPR spectra consistent with |J| > |a|. No evidence was observed for conformational modulation of J by rotation about single bonds as shown by the lack of change of the EPR spectra as a function of temperature. The bis(semiquinone) porphyrin 3 exhibits frozen-solution EPR spectra with zero-field splitting and a Deltam(s) = 2 transition characteristic of a triplet state. The intensity of the Deltam(s) = 2 transition of 3 was measured as a function of temperature, and the data fit according to a singlet-triplet model to yield J(3,solution) = -75 cm(-1) (H = - 2J?1.?2). Polycrystalline samples of porphryin 3 were examined by variable-temperature magnetometry. The paramagnetic susceptibility data were fit using a modified Bleaney-Bowers equation to give J(3,solid) = -29 cm(-1) (H = - 2J?(1).?(2)). The antiferromagnetic J values are consistent with the pi topology of the porphyrin ring.     

Cu(II)-mediated intramolecular carbene cation radical formation: relevance to unimolecular metal-ligand radical intermediates.

We report the syntheses of the photochemically labile 9-diazo-4,5-diazafluorene (1) framework and the corresponding Cu(9-diazo-4,5-diazafluorene)(2)(NO(3))(2) compound (2). The X-ray structure of 2 reveals a 6-coordinate, tetragonal geometry with one nitrogen donor of an asymmetrically chelated diazafluorene in the equatorial position and the other defining the weak Jahn-Teller axis. The nitrate counterions bind in a monodentate fashion in the equatorial plane to complete the coordination sphere. Extended Hückel calculations reveal that the unusual solid-state structure derives from the enlarged bite angle of the fluorene skeleton and steric interactions between the adjacent hydrogen atoms in the higher energy (0.45 eV) symmetrically coordinated state. This is in contrast to Cu(py)(4)(NO(3))(2) which is 1.3 eV more stable with the nitrate counterions bound along the Jahn-Teller axis. Electron paramagnetic resonance (EPR) studies in solution reveal that the nitrates dissociate to yield 6-coordinate CuN(2)X(2)N(2)' structures with either a bound chloride ion (g(x) = 2.10, g(y) = 2.04, g(z) = 2.23, A(z) = 177 x 10(-4) cm(-1)) or a mixture of counterion and solvent (g(x)(a) = 2.05, g(y)(a) = 2.06, g(z)(a) = 2.29, A(z)(a) = 170 x 10(-4) cm(-1); g(x)(b) = 2.07, g(y)(b) = 2.08, g(z)(b) = 2.34, A(z)(b) = 155 x 10(-4) cm(-1)). Photolyses of 1 and 2 indicate loss of N(2) and formation of either carbene ([D/hc] = 0.408 cm(-1), [E/hc] = 0.0292 cm(-1)) or Cu(I)-L(*)(+) (S = (1)/(2), g = 2.0019) intermediates, which are identified by EPR, UV-vis, and time-dependent density functional theory methods. The results illustrate the important role redox active transition metals play in determining the nature of fundamental metal-ligand radical intermediates.     

Spectroscopy and photophysics of self-organized zinc porphyrin nanolayers. 3. Fluorescence detected magnetic resonance of triplet States

Fluorescence detected magnetic resonance (FDMR) has been applied to approximately 25-nm-thick porphyrin films, containing ordered domains of zinc tetra-(p-octylphenyl)-porphyrin (ZnTOPP) spin-coated onto quartz slides. Illuminating the films at 1.4 K with 457.9-nm light from a continuous wave Ar(+) laser produces at least two different, Jahn-Teller-distorted, ZnTOPP triplet species, labeled i and ii. Microwave-induced magnetic resonance of i and ii in the absence or presence of an externally applied magnetic field affects the fluorescence intensity of ZnTOPP, thus allowing FDMR. For triplet species i, formed in films spin-coated from toluene solution, the zero-field splitting (ZFS) parameters were determined as |D| = (316.9 +/- 0.1) x 10(-4) cm(-1) and |E| = (32.0 +/- 0.5) x 10(-4) cm(-1). By exposure of the spin-coated films to chloroform vapor at room temperature, triplet i is converted into species ii, with |D| = (295 +/- 3) x 10(-4) cm(-1) and |E| = (121 +/- 3) x 10(-4) cm(-1). For the excited triplet state of ZnTOPP in a toluene glass, ZFS parameters with values of |D| = (295 +/- 1) x 10(-4) cm(-1) and |E| = (91 +/- 1) x 10(-4) cm(-1) are found. From a combined study of the FDMR- and microwave-induced fluorescence spectra, i and ii are identified as unligated and ligated ZnTOPP triplet species, respectively. From the asymmetrically shaped zero-field FDMR signals of i, we conclude that the local crystal field perturbations of the stacked molecules are anisotropic. The FDMR results of the ZnTOPP films are compared with those for a film of zinc tetraphenylporphyrin (ZnTPP), which lacks the octyl substituents, and therefore is nonordered. Upon illumination, the ZnTPP films contain only a single, ligated, triplet species with ZFS parameters very similar to those of ligated ZnTOPP. At approximately 5 K, the lifetime of triplet i is considerably shortened compared to that of ZnTOPP in a glass at the same temperature.     

Carbene stabilization by aryl substituents. Is bigger better?

The geometries and relative stabilities of the singlet and triplet states of phenyl- (Cs), diphenyl- (C2), 1-naphthyl- (Cs), di(1-naphthyl)- (C2), and 9-anthryl-substituted (Cs) carbenes were investigated at the B3LYP/6-311+G(d,p) + ZPVE level of density functional theory. The singlet-triplet energy separations (DeltaEST), 2.7, 2.9, 3.4, 3.7, and 5.7 kcal/mol, respectively, after including an empirical correction (2.8 kcal/mol) based on the error in the computed singlet-triplet gap for methylene versus experiment, are in good agreement with available experimental values. Consistent with literature reports, triplet di(9-anthryl)carbene has a linear, D2d symmetrical, allene structure with 1.336 A C=C bond lengths and considerable biradical character. B3LYP favors such cumulene biradical structures and triplet spin states and predicts a large (>15 kcal/mol) "di(9-anthryl)carbene" singlet-triplet (biradical) energy gap. The resonance stabilization of both singlet and triplet carbenes increases modestly with the size of the arene substituent and overall, (di)arylcarbenes, both singlet and triplet, are better stabilized by bigger substituents. For example, methylene is stabilized more by a naphthyl than a phenyl group (singlets, 26.6 versus 24.4; and triplets, 20.9 versus 18.1 kcal/mol, respectively). The carbene geometries are affected by both steric effects and arene-carbene orbital interactions (sigma-p and p-pi). For instance, the central angles at the carbene are widened by a second arene group, which leads to increased s-character and shorter carbene bond lengths (i.e., C-C, C-H). In general, the aromaticity of the substituted rings in triplet carbenes is most affected by the presence of the unpaired electrons.     

Prototypical triplet alkyl phosphonatocarbenes

The current case study focuses on the generation, identification, and characterization of two representative mono- and disubstituted alkyl phosphonatocarbenes by means of matrix isolation techniques in conjunction with density functional theory [B3LYP/6-311++G(d,p)] and coupled cluster [CCSD(T)/cc-pVXZ, X = D, T] computations. The EPR measurements identify both carbenes as triplet ground-state species with D values of 0.660 and 0.623 cm(-1), respectively, exhibiting persistency toward intramolecular reactions (the EPR signal observable in perfluoromethylcyclohexane up to around 70 K for the disubstituted molecule). While the reaction of the carbene center of the conformationally rich tetramethyl bisphosphonatocarbene with the CH bonds of the methyl groups leads to phosphaoxetane at room temperature, its fragmentation via a Wittig-type reaction during high vacuum flash pyrolysis (HVFP) results in dimethyl vinylphosphonate and methyl metaphosphate. The latter has been observed for the first time as an isolated entity.     

Tuning anisotropy barriers in a family of tetrairon(III) single-molecule magnets with an S = 5 ground state

Tetrairon(III) Single-Molecule Magnets (SMMs) with a propeller-like structure exhibit tuneable magnetic anisotropy barriers in both height and shape. The clusters [Fe4(L1)2(dpm)6] (1), [Fe4(L2)2(dpm)6] (2), [Fe4(L3)2(dpm)6].Et2O (3.Et2O), and [Fe4(OEt)3(L4)(dpm)6] (4) have been prepared by reaction of [Fe4(OMe)6(dpm)6] (5) with tripodal ligands R-C(CH2OH)3 (H3L1, R = Me; H3L2, R = CH2Br; H3L3, R = Ph; H3L4, R = tBu; Hdpm = dipivaloylmethane). The iron(III) ions exhibit a centered-triangular topology and are linked by six alkoxo bridges, which propagate antiferromagnetic interactions resulting in an S = 5 ground spin state. Single crystals of 4 reproducibly contain at least two geometric isomers. From high-frequency EPR studies, the axial zero-field splitting parameter (D) is invariably negative, as found in 5 (D = -0.21 cm(-1)) and amounts to -0.445 cm(-1) in 1, -0.432 cm(-1) in 2, -0.42 cm(-1) in 3.Et2O, and -0.27 cm(-1) in 4 (dominant isomer). The anisotropy barrier Ueff determined by AC magnetic susceptibility measurements is Ueff/kB = 17.0 K in 1, 16.6 K in 2, 15.6 K in 3.Et2O, 5.95 K in 4, and 3.5 K in 5. Both |D| and U(eff) are found to increase with increasing helical pitch of the Fe(O2Fe)3 core. The fourth-order longitudinal anisotropy parameter B4(0), which affects the shape of the anisotropy barrier, concomitantly changes from positive in 1 ("compressed parabola") to negative in 5 ("stretched parabola"). With the aid of spin Hamiltonian calculations the observed trends have been attributed to fine modulation of single-ion anisotropies induced by a change of helical pitch.     

Spectroscopic and magnetic properties of an iodo Co(I) tripodal phosphine complex

Reaction of the tripodal phosphine ligand 1,1,1-tris((diphenylphosphino)phenyl)ethane (PhP3) with CoI(2) spontaneously generates a one-electron reduced complex, [(PhP3)Co(I)(I)] (1). The crystal structure of 1 reveals a distorted tetrahedral environment, with an apical Co-I bond distance of ～2.52 ?. Co(II/I) redox occurs at an unusually high potential (+0.38 V vs. SCE). The electronic absorption spectrum of 1 exhibits an MLCT peak at 320 nm (ε = 8790 M(-1) cm(-1)) and a d-d feature at 850 nm (ε = 840 M(-1) cm(-1)). Two more d-d bands are observed in the NIR region, 8650 (ε = 450) and 7950 cm(-1) (ε = 430 M(-1) cm(-1)). Temperature dependent magnetic measurements (SQUID) on 1 (solid state, 20-300 K) give μ(eff) = 2.99(6) μ(B), consistent with an S = 1 ground state. Magnetic susceptibilities below 20 K are consistent with a zero field splitting (zfs) |D| = 8 cm(-1). DFT calculations also support a spin-triplet ground state for 1, as optimized (6-31G*/PW91) geometries (S = 1) closely match the X-ray structure. EPR measurements performed in parallel mode (X-band; 0-15?000 G, 15 K) on polycrystalline 1 or frozen solutions of 1 (THF/toluene) exhibit a feature at g≈ 4 that arises from a (Δm = 2) transition within the M(S) = <+1,-1> manifold. Below 10 K, the EPR signal decreases significantly, consistent with a solution zfs parameter (|D|≈ 8 cm(-1)) similar to that obtained from SQUID measurements. Our work provides an EPR signature for high-spin Co(I) in trigonal ligation.     

An "S"-shaped pentanuclear CuII cluster derived from the metal-assisted hydrolysis of pyCOpyCOpy: structural, magnetic and spectroscopic studies

Reaction of [Cu2(O2CMe)4(H2O)2] with 2,6-di-(2-pyridylcarbonyl)-pyridine (pyCOpyCOpy or dpcp) in MeCN-H2O 10:1, led to the pentanuclear copper(II) complex [Cu5(O2CMe)6{pyC(O)(OH)pyC(O)(OH)py}2] () which crystallizes in the triclinic P1 space group. The copper(II) atoms are arranged in an "S"-shaped configuration, and are bridged by the doubly deprotonated bis(gem-diol) form of the ligand, pyC(O)(OH)pyC(O)(OH)py2-. Magnetic susceptibility data indicate the interplay of both ferro- and antiferromagnetic intramolecular interactions stabilizing an S=3/2 ground state. Fitting of the data according to a next-nearest-neighbour model {H=-[J1(S1S2+S1'S2')+J2(S2S3+S3'S2')+J3(S1S3+S3'S1')+J4(S2S2')]} yields exchange coupling constants J1=+39.7 cm(-1), J2=-15.9 cm(-1), J3=-8.3 cm(-1) and J4=+4.3 cm(-1), leading to an S=3/2 ground state. X-Band EPR spectroscopy indicates a zero-field splitting of the ground state with |D3/2|=0.38 cm(-1).