Magnetic interactions in p-phenylene-bis(nitronyl nitroxide) biradicals with large torsion angles

We have designed and synthesized new biradicals of p-phenylene-bis(nitronyl nitroxide) substituted with two methoxy groups at 2,3- (2) and 2,5-positions (3). A parent biradical p-phenylene-bis(nitronyl nitroxide) (1) has intramolecular antiferromagnetic exchange interaction of 2J/k_B = −104 K ∼ −106 K with a torsion angle of 28.5° between the phenyl and the imidazole rings of nitronyl nitroxide. X-ray crystal structure analysis shows that the bulky substituents in 2 and 3 give large torsion angles of 65–70°. The larger torsion angles should weaken the magnitude of intramolecular exchange interactions, which is attributed to a decrease in π-conjugation over the p-phenylene and the radical groups. Magnetic susceptibility measurements indicate that the intramolecular exchange interactions in 2 and 3 are severely weakened to about 6% of that in 1, 2J/k_B = −6 K ∼ −8 K. The relation between the torsion angle and the intramolecular exchange interaction is consistent with DFT calculations. The ground-state singlet biradicals with suppressed intramolecular exchange interactions can be a building block for exotic exchange-coupled spin systems as predicted in our theoretical studies.     

2D and 3D Cu(hfac)2 complexes with nitronyl nitroxide biradicals

Reactions between Cu(hfac)2 and nitronyl nitroxide biradicals 1,4-bis[4-(4,4,5,5-tetramethyl-3-oxide-1-oxyl-4,5-dihydro-1H-imidazol-2-yl)pyrazol-1-yl]butane (L4) and 1,8-bis[4-(4,4,5,5-tetramethyl-3-oxide-1-oxyl-4,5-dihydro-1H-imidazol-2-yl)pyrazol-1-yl]octane (L8) gave respectively a framework compound [Cu(hfac)2]2L4 and a layered polymer compound [Cu(hfac)2]2L8. The framework of [Cu(hfac)2]2L4 consists of 66-membered condensed metallocycles. Inside the framework, the structure has macrohelixes (pitch approximately 25 A) extending along the [001] crystallographic direction. All the helixes have the same direction of winding; the crystals, therefore, are optically active, the structure corresponding either to P-isomer (P4(1)2(1)2) or to M-isomer (P4(3)2(1)2). The long distances between the Cu atoms and the O atoms of the coordinated >N-O groups (Cu-O 2.351-2.467 A) are responsible for ferromagnetic exchange interactions in Cu2+-O-N< and >N-O-Cu2+-O-N< exchange clusters.     

Crystals of the CuII complex with nitronyl nitroxide and imino nitroxide exhibiting mechanical activity

As part of continuing studies of multispin compounds capable of exhibiting chemomechanical activity, a series of heterospin solids of the composition [Cu(hfac)₂L _x L′_2?x ], [Cu(hfac)₂L′], [Cu₂(Piv)₄L′₂]·0.5C₆H₁₄, and [Cu₂(hfac)₂(Piv)₂L′2], where hfac is the hexafluoroacetylacetonate anion, L is 4,4,5,5-tetramethyl-2-(1-methyl-1H-imidazol-5-yl)-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl, L′ is the imino nitroxide analog of L, viz., 4,4,5,5-tetramethyl-2-(1-methyl-1H-imidazol-5-yl)-4,5-dihydro-1H-imidazole-1-oxyl, and Piv is the 2,2-dimethylpropionate anion, were synthesized and characterized. The packing of the synthesized crystals of the solid solutions [Cu(hfac)₂L _x L′_2-x ], where L predominates, is similar to that for [Cu(hfac)₂L₂], and these crystals are able to undergo chemomechanical motion. On the contrary, the crystals of [Cu(hfac)₂L _x L′_2?x ], where L′ predominates, have structural parameters similar to those of [Cu(hfac)₂L′₂] and do not exhibit thermally activated or photoactivated chemomechanical activity.     

含杂环并具有高自旋基态的双自由基体系的理论设计

以—·N—O—为自旋中心(SC),间苯为铁磁耦合单元(FC),苯、吡啶、哒嗪、嘧啶、吡嗪、三嗪为端基(EG),设计一系列新型稳定高自旋分子.另外以—·N—O—为SC,苯、吡啶、哒嗪、嘧啶、吡嗪、三嗪为FC,苯为EG,又设计另一系列新型稳定高自旋分子,并通过AM1—CI方法计算,研究了不同杂环作为端基或耦合单元对高自旋分子自旋多重度稳定性的影响.     

Analysis of the magnetic coupling in nitroxide organic biradicals

The magnetic coupling in organic biradicals has been analyzed by means of ab initio wave function-based methods. Attention is focused on the coupling between the spin moments localized on the NO-groups in meta and para phenylene-bridged nitroxides, and bis(nitronyl) nitroxide and bis(imino) nitroxide biradicals. The leading mechanisms governing the coupling have been isolated by means of class-partitioned CI calculations. It was found that the mechanisms of the coupling in the para and meta phenylene-bridged nitroxides are similar to that found in transition metal complexes, while for the other biradicals the dominance of other mechanisms (like the spin polarization) imposes restrictions on the computational strategy to be followed to best estimate the coupling.     

Synthesis and structure of a complex having a quartet ground state with three entirely different spin carriers: nitronyl nitroxide, o-semiquinone, and CuII

A "spin diverse" S = 3/2 ground-state complex, NN-SQCuTpCum,Me, has been prepared. The three S = 1/2 spin carriers are nitronyl nitroxide (NN), o-semiquinone (o-SQ), and cupric ion. The solid-state structure of the ZnII derivative, NN-SQZnTpCum,Me (C56H69BN8O4Zn), was determined: monoclinic, P2(1)/c, a = 12.5781(12) A, b = 17.7408(17) A, c = 24.440(2) A, alpha = 90.00 degrees, beta = 98.240(2) degrees, gamma = 90.00 degrees, Z = 4. The results of X-ray structural characterization of the ZnII derivative suggest substantial interaction between the two spin carriers NN and o-SQ. Indeed, strong intramolecular exchange coupling has been determined by variable-temperature magnetic susceptibility studies. Intraligand ferromagnetic exchange is considerably greater than kT, such that only the triplet state is populated at 300 K, and CuII-ligand exchange is ferromagnetic, with J = +75 cm-1.     

Synthesis and properties of the complexes of lanthanides with nitronyl nitroxide biradical

Five novel complexes of formula [Ln(hfac)3] · BNPhOM, where Ln = Gd, Ho, Dy, Y, Er; hfac = hexfluoracetylaceto-nate; BNPhOM = 1,3-[bis-2,2'-(4,4,5,5-tetramethyl-4,5-di-hydro-1H-imidazolyl-1-oxyl-3-oxide)phenoxy] propane, have been prepared and characterized by elemental analysis, molar conductances, IK and electronic spectra. The temperature dependence of the magnetic susceptibility for Gd( III) and radical was measured (2-300 K). The observed data were successfully simulated giving the exchange integral J = 0.28 cm-1, J' = - 0.33 cm-1. These results indicate a weak ferromagnetic spin exchange interaction between Gd(III) ion and the radical and a weak antiferromagnetic spin exchange interaction between the radical and radical.     

Electron donor-bridge-acceptor molecules with bridging nitronyl nitroxide radicals: influence of a third spin on charge- and spin-transfer dynamics

Appending a stable radical to the bridge molecule in a donor-bridge-acceptor system (D-B-A) is potentially an important way to control charge- and spin-transfer dynamics through D-B-A. We have attached a nitronyl nitroxide (NN*) stable radical to a D-B-A system having well-defined distances between the components: MeOAn-6ANI-Ph(NN*)-NI, where MeOAn = p-methoxyaniline, 6ANI = 4-(N-piperidinyl)naphthalene-1,8-dicarboximide, Ph = phenyl, and NI = naphthalene-1,8:4,5-bis(dicarboximide). MeOAn-6ANI, NN*, and NI are attached to the 1, 3, and 5 positions of the Ph bridge. Using both time-resolved optical and EPR spectroscopy, we show that NN* influences the spin dynamics of the photogenerated triradical states (2,4)(MeOAn(+)*-6ANI-Ph(NN*)-NI(-)*), resulting in slower charge recombination within the triradical compared to the corresponding biradical lacking NN*. The observed spin-spin exchange interaction between the photogenerated radicals MeOAn(+)(*) and NI(-)(*) is not altered by the presence of NN*, which only accelerates radical pair intersystem crossing. Charge recombination within the triradical results in the formation of (2,4)(MeOAn-6ANI-Ph(NN*)-(3)NI), in which NN* is strongly spin-polarized. Normally, the spin dynamics of correlated radical pairs do not produce a net spin polarization; however, net spin polarization appears on NN* with the same time constant as describes the photogenerated radical ion pair decay. This effect is attributed to antiferromagnetic coupling between NN* and the local triplet state (3)NI, which is populated following charge recombination. This requires an effective switch in the spin basis set between the triradical and the three-spin charge recombination product having both NN* and (3)NI present.     

Tandem arrays of TEMPO and nitronyl nitroxide radicals with designed arrangements on DNA

Herein we describe one-dimensional electron-spin arrays consisting of two different organic radicals with the designed arrangement based on the DNA sequence. Two mismatch-binding ligands carrying 2,2,6,6-tetramethylpiperidine N-oxide (TEMPO) and nitronyl nitroxide selectively bind to the predetermined sites on double stranded DNA. By using the two mismatch-binding ligands carrying the organic radicals as the glue for DNA, electron-spin assembly could be successfully synchronized with the hybridization. Periodically and tandemly arranged, two kinds of organic radical molecules at designed positions might be useful for an approach to build up scalable qubits of electron-spin-based quantum computing. The approach using DNA nanostructures as a scaffold to assembly functional small molecules can afford one of the promising ways for the future application of DNA nanostructures and nanotechnology.     

Millimetre-wave studies on single crystals of the organic radical 2-benzimidazolyl nitronyl nitroxide

We report temperature dependent millimetre-wave spectroscopic experiments on single crystals of the organic molecular magnet 2-benzimidazolyl nitronyl nitroxide, in the range 1.4–100 K. This organic radical shows quasi one-dimensional (1-d) ferromagnetic intermolecular interactions with the intrachain exchange coupling constant J/k_B = +22 K and interchain coupling constant J′/k_B = 0.24 K. The linewidth of the electron spin resonance at low temperatures was seen to be considerably broadened as compared to that at higher temperatures. This is consistent with the low dimensional behaviour of the linewidth predicted theoretically. We also see a shift in resonance field at low temperatures. We also present the results of angular dependence experiments carried out at temperatures of 1.4 and 50 K, and frequency dependence experiments at 1.4 and 50 K.     

Synthesis and crystal structures of the nickel(II) complex with nitronyl nitroxide

Two nickel(II) complexes [Ni(NIT-l′-MeBzlrn)₂(Dca)₂] (I, II) (NIT-l′-MeBzIm = 2-{2′-[(l′methyl)benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-l-oxyl-3-oxide) have been prepared and structurally characterized by single-crystal X-ray diffraction. They are structural epimers. The complexe crystallizes in monoclinic, space group P2₁/n, Z = 4. Crystal data: C₃₄H₃₈N₁₄NiO₄, M _r = 765.49, a = 15.019(3), b = 18.803(4), c = 15.756(3) Å, β = 109.399(3)°, γ = 90° (I); a = 13.934(3), b = 11.046(2), c = 24.570(5) Å, β = 90.024(2)° (II). The X-ray analysis reveals that Ni²⁺ ion resides in a distorted octahedral center. The complex was linked by intermolecular hydrogen bonds, resulting in a ID chain structure for I and a 2D network configuration for II.     

Magnetism in organic radical ion salts based on nitronyl nitroxide derivatives substituted with heterocyclic aromatic hydrocarbons

Radical cation and anion salts of the neutral organic radicals, 2-imidazolyl nitronyl nitroxide (2-IMNN) and 2-benzimidazolyl nitronyl nitroxide (2-BIMNN), have been prepared and their magnetic properties studied by SQUID magnetometry. The radical salts exhibit one-dimensional (1-d) antiferromagnetic (AFM) intermolecular interactions with the exchange coupling J/k between −0.8 and −6.3 K, which are significantly reduced from those observed in the two neutral radicals, while 2-IMNN shows an AFM interaction with J/k=−88 K within the molecular dimers and 2-BIMNN has quasi 1-d ferromagnetic (FM) intermolecular interactions with J/k=+22 K (intrachain) and zJ′/k=+0.24 K (interchain). The magnetic properties of the nitronyl nitroxide and iminonitroxide derivatives having molecular structure related to 2-IMNN have also been investigated. In 2-benzimidazolyl iminonitroxide (2-BIMIN), the FM interaction observed in 2-BIMNN is replaced by strong 1-d AFM interaction with J/k=−11.7 K.     

Two copper complexes based on nitronyl nitroxide with different halides: structures and magnetic properties

Complexes based on different halogen-substituted nitronyl nitroxide radicals and Cu(II), Cu₃(hfac)₆(NIT-Ph-F)₂ (1) and Cu₃(hfac)₆(NIT-Ph-Cl)₂ (2) (hfac = hexafluoroacetylacetonate; NIT-Ph-F = 2-(4′-fluorophenyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide; NIT-Ph-Cl = 2-(4′-chlorphenyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide), were synthesized and characterized structurally and magnetically. X-ray crystal structure analyses show that 1 and 2 have similar centrosymmetric five-spin structures consisting of three Cu(II) ions bridged by two nitroxide ligands. The Cu(II) is coordinated by six oxygens to form an octahedron, while the five coordination of the terminal Cu(II) ion is square pyramidal. Magnetic measurements reveal strong antiferromagnetic interactions between Cu(II) ions and radicals in 1 (J = ?38.9 cm^?1) and weak antiferromagnetic interactions between Cu(II) ions and radicals in 2 (J = ?1.23 cm^?1), which may be explained by the bond length of the Cu–O_rad (2.468(2) Å) in 1, which is shorter than that (2.514(2) Å) in 2, and the dihedral angle (73.17(1)°) of the plane O7–O8–Cu(2)–O7A–O8A with the moiety O5–N1–C11–N2–O6 in 1 is smaller than (77.82(1)°) in 2.     

Bis-radicals (nitronyl nitroxide and imino nitroxide) Substituted Benzene with Long Alkyl Chain: Synthesis, Magnetic Study and Formation of LB film

Sincethediscovery0fthefirstgenuineorganicferr0magnet,p-nitronylphenylnitronylnitroxide(P-NPN-N)in1991',greatprogresshasbeenachievedinthefieldof0rganicferromagnetism.Bynow,morethantwentypurelyorganicferromagnetshavebeenrep0rtedsuccessiveIy'.However,theferr0magnetictransiti0ntemperature(Tc)0fthesepurely0rganicferr0magnetsarestillveryl0wwiththehighestbeing0nlyl.48K3exceptforthecharge-transfercomplexesbasedontetracyanoquinodimethane(TCNQ)andC604.Atpresentstageofresearchinthisfield,0n0nehand,e…     

Phase transitions in the solvate of the heterospin complex Cu(hfac)2 with the nitronyl nitroxide radical

The temperature dependence of the heat capacity of a polycrystalline sample of the heterospin solvate [Cu(hfac)₂L]·0.5[1,4-(CF₃)₂C₆H₄] (L is 2-(1-butyl-1H-pyrazol-4-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide 1-oxyl) was studied in the range of 5–298 K. The results of the thermochemical study of this compound were shown to be in agreement with the data from magnetochemical and diffraction measurements providing evidence that, as the temperature changes, the complex undergoes phase transitions at 59 and 123 K.     

Partial orientation of nitroxide biradicals in the plastic phase of cyclohexane and in frozen toluene solution

Several nitroxide biradicals have been studied by electron spin resonance, in cyclohexane solution at ?10°C and in toluene solution at ?150°C. The ESR spectra change when the sample orientation in the spectrometer cavity is changed: under favourable circumstances oriented spectra are obtained.     

Effect of substituents on spin density in benzimidazole nitronyl nitroxide radicals studied by electron spin resonance

Several novel benzimidazole‐3‐oxide‐1‐oxyl radicals with substituents at 5 and/or 6 position were synthesized. The ESR analysis of nitrogen hyperfine coupling constants (hfccs) revealed that substituents at 5 and 6‐position affect the spin density to greater extent than substituents on the phenyl ring at 2‐position. Density functional theory calculations of nitrogen hfccs were performed using several different Pople type basis sets, as well as double and triple zeta quality individual gauge for localized orbital (IGLO‐II, IGLO‐III) and electron paramagnetic resonance (EPR‐II, EPR‐II) basis sets. Experimental and theoretical hfccs are compared. Copyright © 2009 John Wiley & Sons, Ltd.     

Shift of stereochemical nonrigidity from coordination units to polymethylene fragments in heterospin copper(<Emphasis Type="SmallCaps">II</Emphasis>) hexafluoroacetylacetonate complexes with nitronyl nitroxide biradicals

The reactions of bis(hexafluoroacetylacetonato)copper(II) [Cu(hfac)₂] with the nitronyl nitroxide biradicals bis[4-(4,4,5,5-tetramethyl-3-oxide-1-oxyl-4,5-dihydro-1H-imidazol-2-yl)pyrazol-1-yl]alkanes (L⁶, L¹⁰, and L¹²) produced the framework heterospin complex [Cu(hfac)₂]₂L⁶ and the layer-polymeric heterospin complexes [Cu(hfac)₂]₂L¹⁰ and {[Cu(hfac)₂]₂L¹²} [Cu(hfac)₂(PrⁱOH)₂], respectively. In the solid state of these compounds, the stereochemical nonrigidity is manifested as a deformation of the polymethylene fragments-(CH₂)_n-. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1732–1741, September, 2007.