Biradical Complexes Research Articles

Origin of Ferromagnetic Exchange Coupling in Donor–Acceptor Biradical Analogues of Charge-Separated Excited States

A new donor-acceptor biradical complex, TpCum,MeZn(SQ-VD) (TpCum,MeZn+ = zinc(II) hydro-tris(3-cumenyl-5-methylpyrazolyl)borate complex cation; SQ = orthosemiquinone; VD = oxoverdazyl), which is a ground-state analogue of a charge-separated excited state, has been synthesized and structurally characterized. The magnetic exchange interaction between the S = 1/2 SQ and the S = 1/2 VD within the SQ-VD biradical ligand is observed to be ferromagnetic, with JSQ-VD = +77 cm-1 (H = -2JSQ-VDŜSQ·ŜVD) determined from an analysis of the variable-temperature magnetic susceptibility data. The pairwise biradical exchange interaction in TpCum,MeZn(SQ-VD) can be compared with that of the related donor-acceptor biradical complex TpCum,MeZn(SQ-NN) (NN = nitronyl nitroxide, S = 1/2), where JSQ-NN ≅ +550 cm-1. This represents a dramatic reduction in the biradical exchange by a factor of ∼7, despite the isolobal nature of the VD and NN acceptor radical SOMOs. Computations assessing the magnitude of the exchange were performed using a broken-symmetry density functional theory (DFT) approach. These computations are in good agreement with those computed at the CASSCF NEVPT2 level, which also reveals an S = 1 triplet ground state as observed in the magnetic susceptibility measurements. A combination of electronic absorption spectroscopy and CASSCF computations has been used to elucidate the electronic origin of the large difference in the magnitude of the biradical exchange coupling between TpCum,MeZn(SQ-VD) and TpCum,MeZn(SQ-NN). A Valence Bond Configuration Interaction (VBCI) model was previously employed to highlight the importance of mixing an SQSOMO → NNLUMO charge transfer configuration into the electronic ground state to facilitate the stabilization of the high-spin triplet (S = 1) ground state in TpCum,MeZn(SQ-NN). Here, CASSCF computations confirm the importance of mixing the pendant radical (e.g., VD, NN) LUMO (VDLUMO and NNLUMO) with the SOMO of the SQ radical (SQSOMO) for stabilizing the triplet, in addition to spin polarization and charge transfer contributions to the exchange. An important electronic structure difference between TpCum,MeZn(SQ-VD) and TpCum,MeZn(SQ-NN), which leads to their different exchange couplings, is the reduced admixture of excited states that promote ferromagnetic exchange into the TpCum,MeZn(SQ-VD) ground state, and the intrinsically weaker mixing between the VDLUMO and the SQSOMO compared to that observed for TpCum,MeZn(SQ-NN), where this orbital mixing is significant. The results of this comparative study contribute to a greater understanding of biradical exchange interactions, which are important to our understanding of excited-state singlet-triplet energy gaps, electron delocalization, and the generation of electron spin polarization in both the ground and excited states of (bpy)Pt(CAT-radical) complexes.

Radiationless deactivation pathways versus H-atom elimination from the N-H bond photodissociation in PhNH2-(Py)n (n = 1,2) complexes.

Minimum energy structures of the ground and lowest excited states of aniline (PhNH2) solvated by pyridine (Py) show that the clusters formed are stabilized by hydrogen bonds in which only one or both hydrogen atoms of the NH2 group take part. Two different N-H bonds photodissociation in PhNH2-(Py)n (n = 1,2) complexes, free and hydrogen bonded have been studied by analyzing excited state potential energy surfaces. In the first one, only N-H bonds engaged in hydrogen bonding in these complexes are considered. RICC2 calculations of potential energy (PE) profiles indicate that all photochemical reaction paths along N-H stretching occur mainly via the proton-coupled electron transfer (PCET) mechanism. The repulsive charge transfer 1ππ*(CT) state dominates the PE profiles, leading to low-lying 1ππ*(CT)/S0 conical intersections and thus provide channels for ultrafast radiationless deactivation of the electronic excitation or stabilization to biradical complexes. The second photoreaction consists of a direct dissociation along the free N-H bond of the NH2 group. It has been shown that this process is played by excited singlet states of 1πσ* character having repulsive potential energy profiles with respect to the stretching of N-H bond, which dissociates over an exit barrier about 0.5eV giving rise to the formation of a 1πσ*/S0 conical intersection. This may cause an internal conversion to the ground state or may lead to H-atom elimination. This photophysical process is the same in both planar and T-shaped conformers of the PhNH2-Py monomer complex. Our findings reveal that there is no single dominating path in the photodissociation of N-H bonds in PhNH2-(Py)n complexes, but rather a variety of paths involving H-atom elimination and several quenching mechanisms.

Diffusion process in photoreaction of ketoprofen probed by transient grating method

Translational diffusion dynamics in photoreaction of ketoprofen (KP), one of the most popular nonsteroidal anti−inflammatory drugs, with and without triethylamine (TEA) in methanol was studied by transient grating method coupled with transient absorption spectroscopy. We successfully determined diffusion coefficients of neutral, carboxylate anion, ketyl radical of KP as well as ketyl biradical complex with TEA in methanol for the first time. The diffusion coefficients for the ketyl radical (6.9 × 10−10 m2 s−1), the carboxylate anion (8.1 × 10−10 m2 s−1), and the complex (5.6 × 10−10 m2 s−1) were found to be smaller than that for neutral KP (9.8 × 10−10 m2 s−1). The molecular volume, the viscosity of the solvent, and/or a specific attractive interaction with solvent molecules would contribute to the diffusion process of these species. These new findings on the diffusion property and the interaction of each species with surrounding molecules are essential for understanding the photoreaction of KP with various biomolecules in vivo.

Slow relaxation of magnetization in lanthanide-biradical complexes based on a functionalized nitronyl nitroxide biradical.

Three novel lanthanide-biradical complexes {[Ln(hfac)3]2(mbisNITPyPh)(H2O)}{[Ln(hfac)3](mbisNITPyPh)}·CHCl3 (1-Gd; 2-Tb; 3-Dy) were successfully achieved by reacting the biradical mbisNITPyPh (5-(3-pyridyl)-1,3-bis(1-oxyl-3'-oxido-4',4',5',5'-tetramethyl-4,5-hydro-1H-imidazol-2-yl)benzene) with Ln(hfac)3·2H2O (hfac = hexafluoroacetylacetonate). These Ln-biradical complexes consist of two kinds of spin moieties, namely, dinuclear {[Ln(hfac)3]2(mbisNITPyPh)(H2O)} and mononuclear {[Ln(hfac)3](mbisNITPyPh)}, in which two adjacent dinuclear units are linked by intermolecular hydrogen bonds involving the uncoordinated nitroxide units and the coordinated water molecules of Ln ions, forming a cyclic tetranuclear structure unit. The magnetization study reveals that intramolecular Ln(iii)-coordinated NO ferromagnetic interactions are dominant in the present system. Moreover, the clear frequency dependence of ac magnetic susceptibilities of complex 3-Dy is indicative of slow relaxation of magnetization behavior, indicating its single-molecule magnet nature.

Correction to “Superexchange Contributions to Distance Dependence of Electron Transfer/Transport: Exchange and Electronic Coupling in Oligo(para-Phenylene)- and Oligo(2,5-Thiophene)-Bridged Donor–Bridge–Acceptor Biradical Complexes”

Correction to “Superexchange Contributions to Distance Dependence of Electron Transfer/Transport: Exchange and Electronic Coupling in Oligo(<i>para-</i>Phenylene)- and Oligo(2,5-Thiophene)-Bridged Donor–Bridge–Acceptor Biradical Complexes”

Superexchange Contributions to Distance Dependence of Electron Transfer/Transport: Exchange and Electronic Coupling in Oligo(para-Phenylene)- and Oligo(2,5-Thiophene)-Bridged Donor–Bridge–Acceptor Biradical Complexes

The preparation and characterization of three new donor-bridge-acceptor biradical complexes are described. Using variable-temperature magnetic susceptibility, EPR hyperfine coupling constants, and the results of X-ray crystal structures, we evaluate both exchange and electronic couplings as a function of bridge length for two quintessential molecular bridges: oligo(para-phenylene), β = 0.39 Å(-1) and oligo(2,5-thiophene), β = 0.22 Å(-1). This report represents the first direct comparison of exchange/electronic couplings and distance attenuation parameters (β) for these bridges. The work provides a direct measurement of superexchange contributions to β, with no contribution from incoherent hopping. The different β values determined for oligo(para-phenylene) and oligo(2,5-thiophene) are due primarily to the D-B energy gap, Δ, rather than bridge-bridge electronic couplings, H(BB). This is supported by the fact that the H(BB) values extracted from the experimental data for oligo(para-phenylene) (H(BB) = 11,400 cm(-1)) and oligo(2,5-thiophene) (12,300 cm(-1)) differ by <10%. The results presented here offer unique insight into the intrinsic molecular factors that govern H(DA) and β, which are important for understanding the electronic origin of electron transfer and electron transport mediated by molecular bridges.

Redox‐Induced Carbon–Carbon Bond Formation by Using Noninnocent Ligands

AbstractThe control of radical reactions to afford selective carbon–carbon bond formation is a significant synthetic challenge with applications ranging from small‐molecule activation to natural product synthesis. Oxidation of (IP–)2Al(CH3) (1, IP = iminopyridine) with TrBPh4 (Tr = trityl) afforded the C–C coupled product [(IP)(Tr‐IP)Al(CH3)][BPh4] (2) in which the trityl radical and the IP– radical have undergone C–C bond formation. In contrast, oxidation of 1 with TrBArF24 {BArF24 = tetrakis[(3,5‐trifluoromethyl)phenyl]borate} or TrB(C6F5)4 affords cationic [(IP)(IP–)Al(CH3)][BArF24] (3a) or [(IP)(IP–)Al(CH3)][B(C6F5)4] (3b), respectively . The different reaction outcomes provided by the different counteranions of Tr+ imply that a difference in stability of the products or of the intermediate mixed‐valent [(IP)(IP‐)Al(CH3)]+ state exists. We speculate that the most likely factor is the difference in solubility afforded by the different anions of the products that are formed. We also show that the formation of stable, cationic biradical complexes is possible and that these complexes do not undergo C–C radical coupling at the IP ligand. Cationic [(IP–)2Al(OEt2)][BArF24] (4) was obtained by protonolysis of 1 with H(OEt2)2BArF24, and two‐electron oxidation of [(IP2–)2Al]– (5) afforded [(IP–)2Al(thf)][BArF24] (6).

Paramagnetic calcium melanins

Treatment of catechol, pyrogallol, DOPA, dopamine, norepinephrine, and natural polyhydroxy-1,4-naphthoquinone echinochrome by aqueous solution of potassium superoxide (KO2) in the presence of CaCl2 leads to the formation of water-insoluble dark pigments with stable paramagnetic properties ("calcium melanins"). In control experiments in the same procedure without Ca2+, the pigments were not formed. EPR spectra of the calcium melanins had little difference from each other and from known melanins in shape, line width, and the g factor about 2,004. Addition of EDTA water solution to dried paramagnetic pigments leads to their fast dissolving and disappearing of EPR signal. Formation of similar polymers is also observed during autoxidation of o-diphenols in Ca(2+)-containing alkaline buffer solution, however, this process takes a few days instead of few seconds in the presence of KO2. Thus, calcium (and other divalent cation M2+) can consider as a key structural element in formation of M(2+)-catecholate paramagnetic Polymer. We assume the existence of two types of paramagnetic centers in melanin-like polymer: M(2+)-stabilized o-semiquinone radical or bi-radical complex containing o-semiquinone and superoxide anion radicals, stabilized by M2+.

Magnetic properties of a new N-TEMPO-tert-butyl substituted salicylaldimines and their biradical palladium(II) complexes

A new TEMPO bearing tert-butylated salicylaldimines 1 and 2, as well as early reported 3, and their bis(N-TEMPO-tert-butylated salicylaldiminato)palladium(II) biradical complexes 4–6 have been synthesized and characterized by elemental analyses, IR, UV/vis, ESR and an SQUID magnetometer. The solid state g-factors (2.0116–2.0168) for 4–6 suggest the existence of the significant metal-orbital contribution to the SOMO of nitroxyl radicals. The χmT vs. T plots for 1 and 2 indicate that the χmT decreases as T is lowered from 300 to 20 K, suggesting the existence of weak antiferromagnetic interactions in these radicals. Variable-temperature dependence (10–300 K) magnetic susceptibility data for biradical complexes 4–6 revealed the existence of ferromagnetic and antiferromagnetic behavior around at 10–220 K range for 4. The 1/χm data for 1–6 follow the Curie–Weiss law with negative θ throughout the above temperature range.

Spectroscopic studies of bridge contributions to electronic coupling in a donor-bridge-acceptor biradical system.

Variable-temperature electronic absorption and resonance Raman spectroscopies are used to probe the excited state electronic structure of Tp(Cum,Me)Zn(SQ-Ph-NN) (1), a donor-bridge-acceptor (D-B-A) biradical complex and a ground state analogue of the charge-separated excited state formed in photoinduced electron transfer reactions. Strong electronic coupling mediated by the p-phenylene bridge stabilizes the triplet ground state of this molecule. Detailed spectroscopic and bonding calculations elucidate key bridge distortions that are involved in the SQ(π)(SOMO) → NN-Ph (π*)(LUMO) D → A charge transfer (CT) transition. We show that the primary excited state distortion that accompanies this CT is along a vibrational coordinate best described as a symmetric Ph(8a) + SQ(in-plane) linear combination and underscores the dominant role of the phenylene bridge fragment acting as an electron acceptor in the D-B-A charge transfer state. Our results show the importance of the phenylene bridge in promoting (1) electron transfer in D-Ph-A systems and (2) electron transport in biased electrode devices that employ a 1,4-phenylene linkage. We have also developed a relationship between the spin density on the acceptor, as measured via the isotropic NN nitrogen hyperfine interaction, and the strength of the D → A interaction given by the magnitude of the electronic coupling matrix element, H(ab).

Synthesis, reactions with DNA, and antitumor activity of platinum complexes with aminonitroxyl radicals

The work is a review of the data on the synthesis of mono- and biradical PtII complexes with mono- and diaminonitroxyl radicals, as well as of a binuclear complex with diaminonitroxyl radical. A “mild” method is considered for the synthesis of a number of PtIV nitroxyl complexes (9–11), whose lipophilicity varies within a wide range due to the trans-ligands, i.e., the linear aliphatic acid moieties. Correlations between the structures of the complexes, efficiency of their binding to DNA, and the effect of this binding on the DNA stability were established. Cytotoxic properties of the complexes against the HeLa, H1299, and MCF7 tumor cells, the effect of the complexes on the cell cycle, and the p53 protein expression were studied. The data on the antitumor activity of the complexes in the animal tumor model, P388 leukemia, are given. The rate of the development of resistance to complex 10a for P388 leukemia is 2.5 times lower than the corresponding value for cisplatin. It was found that a synergistic enhancement of antitumor activity is observed when low doses of cisplatin and complexes 9b or 10b are simultaneously administered. The specificities of biological activity of the platinum nitroxyl complexes are presumably due to the antioxidant properties of the nitroxyl pharmacophore and the ability of these complexes to cause the p53-independent tumor cell death.

Exploiting Non-Innocent Ligands to Prepare Masked Palladium(0) Complexes

Is it or isn't it: Reaction of [PdMe2(tmeda)] with pyridyl-N-di(tert-butyl)phosphinoimine spontaneously affords an unusual bimetallic palladium(I) ligand-based biradical complex, which behaves as a “masked” form of Pd0 in its reactions with neutral ligands and chlorobenzene.

Hyperfine Interaction, Spin Polarization, and Spin Delocalization as Probes of Donor−Bridge−Acceptor Interactions in Exchange-Coupled Biradicals

Computations and EPR spectroscopy are used to probe the spin distribution of donor-bridge-acceptor (D-B-A) biradical complexes: Tp(Cum,Me)Zn(SQ-NN) (1), Tp(Cum,Me)Zn(SQ-1,4-Ph-NN) (2), Tp(Cum,Me)Zn(SQ-2,5-TP-NN) (3), and Tp(Cum,Me)Zn(SQ-2,5-Xyl-NN) (4) (SQ = orthosemiquinone and NN = nitronylnitroxide). These complexes are ground-state analogs of the charge-separated excited states formed in photoinduced electron transfer reactions. The intraligand magnetic exchange interaction (J) in these complexes is mediated by the bridges and has been found to stabilize the triplet ground states of 1 and 2. Detailed spectroscopic and bonding calculations have been used to elucidate the role of the bridge fragment (B) and its conformation relative to donor (SQ) and acceptor (NN) on spin density distributions. The computed results correlate well with experimental nitrogen hyperfine coupling constants.

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|<or= 14 MHz, |A z| = 153 MHz) but huge zero-field splitting (D = +17.4 GHz, E = -1.0 GHz). The maximum principal axis of zero-field interaction ( z ZF) is perpendicular to the z axis for the g and A tensors, which is normal to the molecular plane. These characteristics of the magnetic properties prove that the substantial spin transfer from the d x (2) - y (2) orbital of copper to the n-orbitals of the ligand is caused by a sigma-type covalent bonding effect between the central metal and the ligand nitrogens. The covalent bonding effect produces carbene configurations on the nitrogen atoms of the imino nitroxyl radicals. The carbene configuration was concluded to be the main reason for the strong ferromagnetic coupling in Cu-bisimpy. Multifrequency electron spin resonance spectroscopy clarified the unique electronic structure of a square planar copper(II) complex with an imino nitroxyl diradical, which undergoes a strong ferromagnetic interaction caused by a covalent bonding effect.

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.

Analysis of the Primary Photocycle Reactions Occurring in the Light, Oxygen, and Voltage Blue-Light Receptor by Multiconfigurational Quantum-Chemical Methods.

The photocycle reactions occurring between the flavin mononucleotide cofactor and the reactive cysteine residue in the blue-light photoreceptor domain light, oxygen, and voltage (LOV) were modeled for a system consisting of lumiflavin and thiomethanol. The electronic structure and energies of the reactive species were estimated using the CASSCF and MCQDPT2 quantum-chemical methods. The reaction pathway for the S-C4a covalent adduct formation in the triplet state was determined. Concerted electron and proton transfer from the thiol to the flavin in the triplet electronic state results in a biradical complex that is, however, unstable because its structure corresponds to a triplet-singlet crossing. The covalent adduct dissociation in the ground electronic state is a reverse of the photoreaction proceeding via a single energy barrier for hydrogen transfer. Thus, both photo- and dark reactions were found to be single-step chemical transformations occurring without stable intermediates. The photoreaction yielding the S-C4a covalent adduct is an intrinsic property of the isoalloxazine-thiol complex in the specific geometry arranged by the protein in LOV. The S-C4a covalent adduct between lumiflavin and thiomethanol is rather stable implying that in LOV its dissociation is facilitated by the protein.

Trends in exchange coupling for trimethylenemethane-type Bis(semiquinone) biradicals and correlation of magnetic exchange with mixed valency for cross-conjugated systems.

A magnetostructural correlation (conformational electron spin exchange modulation) within an isostructural series of biradical complexes is presented. X-ray crystal structures, variable-temperature electron paramagnetic resonance spectroscopy, zero-field splitting parameters, and variable-temperature magnetic susceptibility measurements were used to evaluate molecular conformation and electron spin exchange coupling in this series of molecules. Our combined results indicate that the ferromagnetic portion of the exchange couplings occurs via the cross-conjugated pi-systems, while the antiferromagnetic portion occurs through space and is equivalent to incipient bond formation. Thus, molecular conformation controls the relative amounts of ferro- and antiferromagnetic contributions to exchange coupling. In fact, the exchange parameter correlates with average semiquinone ring torsion angles via a Karplus-Conroy-type relation. Because of the natural connection between electron spin exchange coupling and electronic coupling related to electron transfer, we also correlate the exchange parameters in the biradical complexes to mixed valency in the corresponding quinone-semiquinone radical anions. Our results suggest that delocalization in the cross-conjugated, mixed-valent radical anions is proportional to the ferromagnetic contribution to the exchange coupling in the biradical oxidation states.

Spectroscopy and kinetics of dithiophosphinate radicals coordinated with dithiophosphinate Ni(II) complex

The laser flash photolysis was used to study the mechanism of photochromic transformations for solutions of phosphinate disulfide ((S2P(i-Bu)2)2≡(S2PR2)2) and Ni(S2P(i-Bu)2)2(Ni(S2PR2)2) complex in acetonitrile. Under the excitation of an XeCl excimer laser (308 nm), this system manifests transient absorption in the visible and UV ranges which vanishes over a millisecond time domain. The cycle of phototransformations can be repeated without degradation of the optical spectrum of the solution. The process is initiated by photodissociation of a disulfide molecule into two S-radicals (S2P(i-Bu)2≡S2PR2). The radical with a constant of 2.5×109M−1s−1 enters the coordination sphere of Ni(S2PR2)2 complex to form the radical complex (R2PS2)Ni(S2PR2)2. When analyzing the kinetics of changes in the optical density of transient absorption, it is assumed that coordination of the second radical with a constant of 1.5×1010M−1s−1 results in the formation of the secondary or biradical complex (R2PS2)2Ni(S2PR2)2. The radical complexes dissociate with a radical escaping from the coordination sphere with rate constants equal to 7.5×103s−1 and 7×102s−1 for mono- and biradical particles, respectively. As a result, the system regains its initial state due to recombination of S2PR2 radicals into initial disulfide.

Singlet−Triplet Gap in Triplet Ground-State Biradicals Is Modulated by Substituent Effects

Three S = 1 bis(semiquinone) complexes have been prepared. To ensure ferromagnetic intramolecular exchange coupling, the two semiquinones are attached 1,3 to a 5-substituted phenylene ring. The biradical complexes differ in their meta-substituents: 1-NMe(2)(), X = N,N-dimethylamino; 1-t-Bu, X = tert-butyl; 1-NO(2)(), X = nitro. All three structures have been determined by X-ray crystallography. Results of structural studies indicate that the biradical ligands of all three complexes have nearly identical conformations with average semiquinone ring torsions of 32 degrees +/- 2 degrees relative to the 5-substituted phenylene ring. The exchange parameter, J (Eta = -2JS(1).S(2)), ranges from +31.0 +/- 0.6 cm(-)(1) for 1-NO(2)() to +59.3 +/- 1.2 cm(-)(1) for 1-t-Bu, with J = +34.9 +/- 0.7 cm(-)(1) for 1-NMe(2)(). Since the conformations are nearly identical, the differences in exchange coupling parameter J are due to substituent effects. The experimental results are supported by Hückel theory arguments and previous computational work.

Simulation of the molecular and electronic structure of C60 fullerene π-complex with twelve half-sandwich species FeC5H5

The problem of existence of η5-π-complexes of fullerenes and their derivatives is discussed. The stability of the η5-π-complex C60(FeCp)12 (viz., icosahedral C60 fullerene “coated” with twelve FeCp groups, each coordinated to its “own” pentagonal face of the fullerene cage) was first estimated in the framework of density functional approach (PBE approximation). The molecular and electronic structure of a biradical complex of C60 fullerene with ten FeCp groups, C60(FeCp)10 (D 5d symmetry), and a 2η5-π-complex of substituted fullerene H10C60, H10C60(FeCp)2 (D 5d symmetry) in which hydrogen atoms are attached to the C atoms in the α-positions relative to the atoms of the polar five-membered cycles, was simulated. According to calculations, the “coated” complex, I h-C60(FeCp)12, should be much more stable than the complex of “naked” fullerene with one or two polarly located FeCp groups and only slightly less stable than the ferrocene molecule FeCp2. The existence of C60(FeCp)12 and H10C60(FeCp)2 complexes was suggested.