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]     

Photochemistry of furyl- and thienyldiazomethanes: spectroscopic characterization of triplet 3-thienylcarbene

Photolysis (λ > 543 nm) of 3-thienyldiazomethane (1), matrix isolated in Ar or N(2) at 10 K, yields triplet 3-thienylcarbene (13) and α-thial-methylenecyclopropene (9). Carbene 13 was characterized by IR, UV/vis, and EPR spectroscopy. The conformational isomers of 3-thienylcarbene (s-E and s-Z) exhibit an unusually large difference in zero-field splitting parameters in the triplet EPR spectrum (|D/hc| = 0.508 cm(-1), |E/hc| = 0.0554 cm(-1); |D/hc| = 0.579 cm(-1), |E/hc| = 0.0315 cm(-1)). Natural Bond Orbital (NBO) calculations reveal substantially differing spin densities in the 3-thienyl ring at the positions adjacent to the carbene center, which is one factor contributing to the large difference in D values. NBO calculations also reveal a stabilizing interaction between the sp orbital of the carbene carbon in the s-Z rotamer of 13 and the antibonding σ orbital between sulfur and the neighboring carbon-an interaction that is not observed in the s-E rotamer of 13. In contrast to the EPR spectra, the electronic absorption spectra of the rotamers of triplet 3-thienylcarbene (13) are indistinguishable under our experimental conditions. The carbene exhibits a weak electronic absorption in the visible spectrum (λ(max) = 467 nm) that is characteristic of triplet arylcarbenes. Although studies of 2-thienyldiazomethane (2), 3-furyldiazomethane (3), or 2-furyldiazomethane (4) provided further insight into the photochemical interconversions among C(5)H(4)S or C(5)H(4)O isomers, these studies did not lead to the spectroscopic detection of the corresponding triplet carbenes (2-thienylcarbene (11), 3-furylcarbene (23), or 2-furylcarbene (22), respectively).     

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.     

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   

Synthese und EPR-spektroskopie dicyclopentadienylanaloger der schlenkschen und tschitschibabinschen kohlenwasserstoffe

The synthesis of several hydrocarbon biradicals consisting of two tetraphenylcyclopentadienyl moieties with different bridge fragments is described. The ESR powder spectra show that there is an intramolecular coupling of two unpaired electron spins to a triplet spin state. The magnitude of the zero field splitting (zfs) is used to discriminate between different molecular conformations. More detailed structural informations are obtained from the observed zfs by quantummechanical calculations of the zfs-parameter D as a function of various torsional angles and cis- or trans-orientations of molecular fragments. The behaviour of the four highest occupied MO's with respect to structural changes in the biradicals is discussed.     

Pulsed electron spin nutation spectroscopy of weakly exchange-coupled biradicals: a general theoretical approach and determination of the spin dipolar interaction

Weakly exchange-coupled biradicals have attracted much attention in terms of their DNP application in NMR spectroscopy for biological systems or the use of synthetic electron-spin qubits. Pulse-ESR based electron spin nutation (ESN) spectroscopy applied to biradicals is generally treated as transition moment spectroscopy from the theoretical side, illustrating that it is a powerful and facile tool to determine relatively short distances between weakly exchange-coupled electron spins. The nutation frequency as a function of the microwave irradiation strength ω(1) (angular frequency) for any cases of weakly exchange-coupled systems can be classified into three categories; D(12) (spin dipolar interaction)-driven, Δg-driven and ω(1)-driven nutation behaviour with the increasing strength of ω(1). For hetero-spin biradicals, Δg effects can be a dominating characteristic in the biradical nutation spectroscopy. Two-dimensional pulse-based electron spin nutation (2D-ESN) spectroscopy operating at the X-band can afford to determine small values of D(12) in weakly exchange-coupled biradicals in rigid glasses. The analytical expressions derived here for ω(1)-dependent nutation frequencies are based on only four electronic spin states relevant to the biradicals, while real biradical systems often have sizable hyperfine interactions. Thus, we have evaluated nuclear hyperfine effects on the nutation frequencies to check the validity of the present theoretical treatment. The experimental spin dipolar coupling of a typical TEMPO-based biradical 1, (2,2,6,6-tetra[((2)H(3))methyl]-[3,3-(2)H(2),4-(2)H(1),5,5-(2)H(2)]piperidin-N-oxyl-4-yl)(2,2,6,6-tetra[((2)H(3))methyl]-[3,3-(2)H(2),4-(2)H(1),5,5-(2)H(2),(15)N]piperidin-(15)N-oxyl-4-yl) terephthalate in a toluene glass, with a distance of 1.69 nm between the two spin sites is D(12) = -32 MHz (the effect of the exchange coupling J(12) is vanishing due to the homo-spin sites of 1, i.e.Δg = 0), while 0 < |J(12)|≦ 1.0 MHz as determined by simulating the random-orientation CW ESR spectra of 1. In addition, we have carried out Q-band pulsed ELDOR (ELectron-electron DOuble Resonance) experiments to confirm whether the obtained values for D(12) and J(12) are accurate. The distance is in a fuzzy region for the distance-measurements capability of the conventional, powerful ELDOR spectroscopy. The strong and weak points of the ESN spectroscopy with a single microwave frequency applicable to weakly exchange-coupled multi-electron systems are discussed in comparison with conventional ELDOR spectroscopy. The theoretical spin dipolar tensor and exchange interaction of the TEMPO biradical, as obtained by sophisticated quantum chemical calculations, agree with the experimental ones.     

Matrix isolation ESR spectroscopy and quantum chemical calculations on 5-methylhexa-1,2,4-triene-1,3-diyl, a highly delocalized triplet "hybrid" carbene

The ESR spectrum of 5-methylhexa-1,2,4-triene-1,3-diyl (1) was recorded in an argon matrix at 15 K. The derived zero-field splitting (ZFS) parameters (D = 0.5054 ± 0.0006 cm(-1) and E = 0.0045 ± 0.0002 cm(-1)) fall between those determined previously for propargylene (2) and vinylcarbene (3). DFT and ab initio (CAS and MRCI) quantum-chemical calculations of the ZFS parameters of 1, 2, and 3 were performed. These calculations indicate that multireference methods are needed to successfully predict ZFS parameters of delocalized carbenes/biradicals such as 1-3. The calculated singly occupied MOs and spin density distributions show that the spin is more delocalized in 1 than in 2 and 3, indicating that 1 is a "hybrid" of the constituent ethynyl- and vinylcarbenes, 2 and 3, respectively. The dominant contribution to the D-value in 1 and 2 is found to result from spin-spin interactions on the C atoms of the propylidene moiety, which is strongly affected by spin polarization. Accurate values for the D-parameter are also predicted for other types of delocalized triplet carbenes such as HC(5)H and HCCN.     

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.     

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.     

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.     

Peculiarity in the electronic structure of Cu(II) complex ferromagnetically coupled with bisimino nitroxides

By means of the electron spin resonance (ESR) technique, we have investigated the electronic structures of the tridentate imino nitroxyl diradical complex with copper(II) (Cu-bisimpy), which has a square planar structure and a ground quartet state with an extremely strong ferromagnetic exchange interaction, and its related compounds (bisimpy = 2,6-bis(1'-oxyl-4',4',5',5'-tetramethyl-4',5'-dihydro-1' H-imidazol-2'-yl)pyridine). It was clarified that Cu-bisimpy had unique magnetic orbitals, compared with the biradical ligand (bisimpy), a zinc(II) biradical complex (Zn-bisimpy) and a copper(II) terpyridine complex (Cu-tpy) (tpy = 2,2';6',2'-terpyridine). Multifrequency ESR spectroscopy provided a reliable set of magnetic parameters of Cu-bisimpy, which has a small g anisotropy ( g x = 2.02, g y = 2.01, g z = 2.08) and small hyperfine coupling with Cu (|A x| = 42.0 MHz, |A y|相似文献   

Study on the heteroatom influence in pyridine-based nitronyl nitroxide biradicals with phenylethynyl spacers on the molecular ground state

Novel pyridine-based nitronyl nitroxide (NIT) biradicals, 3,5-bis[4-(1-oxyl-3-oxo-4,4,5,5-tetramethylimidazolin-2-yl)phenylethynyl)]pyridine (1) and 2,6-bis[4-(1-oxyl-3-oxo-4,4,5,5-tetramethylimidazolin-2-yl)phenylethynyl)]pyridine (2), and monoradicals, 4-(5-bromopyridine-3-ylethynyl)-1-(1-oxyl-3-oxo-4,4,5,5-tetramethylimidazolin-2-yl)benzene (3), 4-trimethylsilylethynyl-1-(1-oxyl-3-oxo-4,4,5,5-tetramethylimidazolin-2-yl)benzene (4), and 4-trimethylsilylethynyl-1-(1-oxyl-3-oxo-4,4,5,5-tetramethylimidazolin-2-yl)pyridine (5), were synthesized and investigated by ESR and UV-vis spectroscopy. The solution EPR measurements of the biradicals gave well-resolved, nine-line spectra with exact half line spacing as compared to monoradicals (giso = 2.0067) with isotropic line spacing /aN/= 7.36 G. This indicates strong, intramolecular exchange coupling (J > 7 x 10(-4) cm(-1); J/aN > 1) of the biradicals with in the limit of EPR. The temperature dependence on the Deltams = +/-2 signal intensity of biradicals follow Curie behavior down to 4 K ascertaining the triplet ground state or its near-degeneracy with the singlet state. UV-vis studies of 1-5 show characteristic differences in the extinctions of n-pi transitions around 600 nm. Both biradicals 1 and 2 were crystallized in monoclinic space groups C2/c and P2(1)/a with the intraradical distances 1.54 and 1.47 nm, respectively. Computational studies of the biradicals 1, 2, and 1,3-bis[4-(1-oxyl-3-oxo-4,4,5,5-tetramethylimidazolin-2-yl)phenylethynyl)]benzene (T) were performed by the AM1/CAS(8,8) method to calculate the singlet-triplet (DeltaEST) energy difference and the spin density distribution. Results show that the position of the pyridyl nitrogen in 1 and 2 in comparison with T does not alter the triplet ground-state spin multiplicities supporting the obtained experimental results.     

Preparation, spectral behaviour and oxidation of some new zinc(II) salicylaldimines containing sterically hindered phenol.

A series of new bis[N-(2,6-di-tert-butyl-1-hyxyphenyl)salicylideneminato]zinc(II) complexes bearing one or two HO- and CH3O-substituents on the salicylaldehyde moiety were prepared, and their spectroscopic properties (IR, electronic, 1H NMR) as well as the ESR spectra of the one-electron oxidation products were examined. The 1H NMR examination of Zn(Lx)2 indicates that, contrary to expectations, the proton resonances of the complexes are shifted to the high-field side compared with those of the free ligands. Oxidation of these compounds with PbO2 results in the formation of mono- and biradical types Zn(II)-stabilized phenoxyls in which there are both anisotropic and alternating line-width trends. Some spectral patterns are typical for weak interacting (J < A) or the case of J approximately A biradicals, in which ESR signal appeared as superimposition of two non-interacting monoradical centers with S = 1/2. ESR studies on biradicals type of Zn(L*x)2 at 300 and 77 K did not show any evidence of strong exchange coupling in these systems. All radical species were characterized by the ESR parameters.     

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.     

Donor-acceptor biradicals as ground state analogues of photoinduced charge separated states

A Valence Bond Configuration Interaction (VBCI) model is used to relate the intraligand magnetic exchange interaction (J) to the electronic coupling matrix element (HAB) in Tp(Cum,MeZn)(SQNN), a compound that possesses a Donor-Acceptor (D-A) SemiQuinone-NitronylNitroxide (SQNN) biradical ligand. Within this framework, an SQ --> NN charge transfer state mixes with the ground state and stabilizes the spin triplet (S = 1). This charge-transfer transition is observed spectroscopically and probed using resonance Raman spectroscopy. In addition, the temperature-dependent electronic absorption spectrum of the Ni(II) complex, Tp(Cum,MeNi)(SQNN), has been studied. Exchange coupling between the S = 1 Ni(II) ion and S = 1 SQNN provides a mechanism for observing the formally spin-forbidden, ligand-based 3GC --> 1CTC transition. This provides a means of determining U, the mean GC --> CTC energy, and a one-center exchange integral, K(0). The experimental determination of J, U, and K(0) permits facile calculation of HAB, and we show that this methodology can be extended to determine the electronic coupling matrix element in related SQ-Bridge-NN molecules. As magnetic susceptibility measurements are easily acquired in the solid state, H(AB) may be effectively determined for single molecules in a known geometry, provided a crystal structure exists for the biradical complex. Thus, SQ-Bridge-NN molecules possess considerable potential for probing both geometric and electronic structure contributions to the magnitude of the electronic coupling matrix element associated with a given bridge fragment.     

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.     

Some observations of various 1,8 naphthoquino-dimethane biradicals by electron spin resonance spectroscopy

Photolysis of 8-methyl-1-naphthyldiazomethane at 4 K gives the triplet ESR spectrum of 1,8-naphthoquinodimethane but not that of 8-methyl-1-naphthylcarbene. Photolysis of either 8-methyl-1-azido-naphthalene or 8-amino-1-azidonaththalene does produce the triplet biradical spectra of 8-imino-1-naphthoquinomethane and 1,8-diiminonaphthoquinodimethane, in addition to the triplet nitrene spectra of 8-methyl-1-nitreno-naphthalene and 8-amino-1-nitreno-naphthalene. Curie Law analyses demonstrate that these biradicals are all ground state triplets. Hückel and INDO calculations pertaining to the biradicals are reported. Large charge transfer interactions were observed in the ESR spectra of 8 substituted-1-naphthyl nitrenes.     

A new family of pi-conjugated delocalized biradicals: Electronic structures of 1,4-bis(2,5-diphenylimidazol-4-ylidene)cyclohexa-2,5-diene

A new family of pi-conjugated delocalized biradical compound is developed. The solution of 1,4-bis(2,5-diphenylimidazol-4-ylidene)cyclohexa-2,5-diene shows the ESR signal consisting of a moderately broad unresolved line, Delta H(pp) approximately 1 mT, at room temperature. The presence of the thermal equilibrium between a triplet biradical state and a singlet state is confirmed by the ESR measurements, and the spin concentration is determined as 7.90 x 10(21) spin/mol at 300 K. The spin concentration can also be controlled by modifying the molecular planarity. Moreover, the unrestricted DFT/B3LYP calculations suggest the biradical character of the singlet ground state, and the modulation of the energy gap between the singlet state and the triplet state is investigated from the theoretical point of view. Controlling the equilibrium between a diamagnetic state and a paramagnetic state will provide significant progress in the field of biradical chemistry, and the materials with the biradical character in a ground state will lead to a novel development of molecular-based organic magnets.     

Pi topology and spin alignment in unique photoexcited triplet and quintet states arising from four unpaired electrons of an organic spin system

Syntheses, electronic structures in the ground state, unique photoexcited states, and spin alignment are reported for novel biradical 1, which was designed as an ideal model compound to investigate photoinduced spin alignment in the excited state. Electron spin resonance (ESR), time-resolved ESR (TRESR), and laser-excitation pulsed ESR experiments were carried out. The magnetic properties were examined with a SQUID magnetometer. In the electronic ground state, two radical moieties interact very weakly (almost no interaction) with each other through the closed-shell diphenylanthracene spin coupler. On photoirradiation, a novel lowest photoexcited state with the intermediate spin (S = 1) arising from four unpaired electrons with low-lying quintet (S = 2) photoexcited state was detected. The unique triplet state has an interesting electronic structure, the D value of which is reduced by antiferromagnetic spin alignment between two radical spins through the excited triplet spin coupler. The general theoretical predictions of the spin alignment and the reduction of the fine-structure splitting of the triplet bis(radical) systems are presented. The fine-structure splitting of the unique photoexcited triplet state of 1, as well as the existence of the low-lying quintet state, is interpreted well on the basis of theoretical predictions. Details of the spin alignment in the photoexcited states are discussed.