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A mononuclear valence tautomeric (VT) complex, [Co(pycz)2(Sq)(Cat)] (1-trans), where pycz = 9-(pyridin-4-yl)-9H-carbazole, Sqâ - = 3,5-di-tert-butyl-semiquinonato, and Cat2- = 3,5-di-tert-butyl-catecholato, is synthesized in the trans configuration, which undergoes one-step valence tautomeric transition above room temperature. Remarkably, 1-trans can transform into its isomeric structure, [Co(pycz)2(Sq)(Sq)] (1-cis), at temperature above 350â K in a single-crystal-to-single-crystal way by in situ molecular twist, and the resulting 1-cis exhibits a pronounced two-step VT transition during magnetic measurements that is rare for mononuclear VT complexes. Such drastic solid-state structural transformation is reported in VT compounds for the first time, which is actuated by a crystal surface's melting-recrystallization induced phase transition process. DFT calculations offer an underlying mechanism suggesting a concerted bond rotation during the structural transformation. The results demonstrate an unconventional approach that realizes structural transformation of VT complexes and the control of VT performance.
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Valence tautomerism (VT) involves the stimulated reversible intramolecular electron transfer between a redox-active metal and ligand. Dinuclear cobalt complexes bridged by bis(dioxolene) ligands can undergo thermally-induced VT with access to {CoIII-cat-cat-CoIII}, {CoIII-cat-SQ-CoII} and {CoII-SQ-SQ-CoII} states (cat2- = catecholate, SQË- = semiquinonate, CoIII refers to low spin CoIII, CoII refers to high spin CoII). The resulting potential for two-step VT interconversions offers increased functionality over mononuclear examples. In this study, the bis(dioxolene) ligand 3,3',4,4'-tetrahydroxy-5,5'-dimethoxy-benzaldazine (thMH4) was paired with Mentpa (tpa = tris(2-pyridylmethyl)amine, n = 0-3 corresponds to methylation at 6-position of the pyridine rings) to afford [{Co(Mentpa)}2(thM)](PF6)2 (1a, n = 0; 2a, n = 2; 3a, n = 3). Structural, magnetic susceptibility and spectroscopic data show that 1a and 3a remain in the temperature invariant {CoIII-cat-cat-CoIII} and {CoII-SQ-SQ-CoII} forms in the solid state, respectively. In contrast, 2a exhibits incomplete thermally-induced VT between these two tautomeric forms via the mixed {CoIII-cat-SQ-CoII} tautomer. In solution, room temperature electronic absorption spectra are consistent with the assignments from the solid-state, with VT observed only for 2a. From electrochemistry, the proximity of the two 1e--processes for the thMn- ligand indicates weak electronic communication between the two dioxolene units, supporting the potential for a two-step VT interconversion in thMn- containing complexes. Comparison of the redox potentials of the Co and thMn- processes suggests that only 2a has these processes in sufficient proximity to afford the thermally-induced VT observed experimentally. Density functional theory calculations are consistent with the prerequisite energy ordering for a two-step transition for 2a, and temperature invariant {CoIII-cat-cat-CoIII} and {CoII-SQ-SQ-CoII} states for 1a and 3a, respectively. This work presents the third example, and the first formally conjugated example, of a bridging bis(dioxolene) ligand that can afford two-step VT in a Co complex, suggesting new possibilities towards applications based on multistep switching.
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Spin crossover (SCO) complexes can reversibly switch between low spin (LS) and high spin (HS) states, affording possible applications in sensing, displays, and molecular electronics. Dinuclear SCO complexes with access to [LS-LS], [LS-HS], and [HS-HS] states may offer increased levels of functionality. The nature of the SCO interconversion in dinuclear complexes is influenced by the local electronic environment. We report the synthesis and characterization of [{FeIII(tpa)}2spiro](PF6)2 (1), [{FeIII(tpa)}2Br4spiro](PF6)2 (2), and [{FeIII(tpa)}2thea](PF6)2 (3) (tpa = tris(2-pyridylmethyl)amine, spiroH4 = 3,3,3',3'-tetramethyl-1,1'-spirobi(indan)-5,5',6,6'-tetraol, Br4spiroH4 = 3,3,3',3'-tetramethyl-1,1'-spirobi(indan)-4,4',7,7'-tetrabromo-5,5',6,6'-tetraol, theaH4 = 2,3,6,7-tetrahydroxy-9,10-dimethyl-9,10-dihydro-9,10-ethanoanthracene), utilizing non-conjugated bis(catecholate) bridging ligands. In the solid state, magnetic and structural analysis shows that 1 remains in the [HS-HS] state, while 2 and 3 undergo a partial SCO interconversion upon cooling from room temperature involving the mixed [LS-HS] state. In solution, all complexes undergo SCO from [HS-HS] at room temperature, via [LS-HS] to mixtures including [LS-LS] at 77 K, with the extent of SCO increasing in the order 1 < 2 < 3. Gas phase density functional theory calculations suggest a [LS-LS] ground state for all complexes, with the [LS-HS] and [HS-HS] states successively destabilized. The relative energy separations indicate that ligand field strength increases following spiro4- < Br4spiro4- < thea4-, consistent with solid-state magnetic and EPR behavior. All three complexes show stabilization of the [LS-HS] state in relation to the midpoint energy between [LS-LS] and [HS-HS]. The relative stability of the [LS-HS] state increases with increasing ligand field strength of the bis(catecholate) bridging ligand in the order 1 < 2 < 3. The bromo substituents of Br4spiro4- increase the ligand field strength relative to spiro4-, while the stronger ligand field provided by thea4- arises from extension of the overlapping π-orbital system across the two catecholate units. This study highlights how SCO behavior in dinuclear complexes can be modulated by the bridging ligand, providing useful insights for the design of molecules that can be interconverted between more than two states.
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Valence tautomerism (VT) and spin crossover (SCO) are promising avenues for developing a range of molecular materials for sensing, memory, and optoelectronic applications. However, these phenomena arise only when specific metal-ligand combinations are employed. The underexplored combination of cobalt(II/III) paired with bis((aryl)imino)acenapthene (Ar-BIAN) ligands, which can exist as neutral Ar-BIAN0 (L0), monoanionic radical Ar-BIANâ¢- (Lâ¢-), and dianionic Ar-BIAN2- (L2-) forms, has potential to afford both VT and SCO. Aiming to develop a new family of switchable molecules, we systematically explored a dual-tuning approach by varying the redox state and aryl substituents in a series of homoleptic [Co(Ar-BIAN)3]n+ complexes (Ar = Ph, n = 2 (12+), 1 (1+), 0 (1); Ar = 3,5-CF3-Ph, n = 0 (2); Ar = 4-MeO-Ph, n = 2 (32+), 0 (3)). As a prelude to synthetic and experimental studies, density functional theory (DFT) calculations were used to explore the structure and relative energies of the different electronic forms of each complex, comprising different cobalt oxidation and spin states and different ligand oxidation states. Except for compound 3, DFT identified a HS-CoII-L0 containing ground state for all complexes, precluding thermally induced SCO or VT. For 3, calculations suggested a possible thermally accessible LS-CoIII-(Lâ¢-)3 â HS-CoII-(Lâ¢-)2(L0) VT interconversion. Experimentally, structural and magnetic data reveal a HS-CoII-L0 containing ground state for all six compounds in the solid state, including 3, discounting thermally induced VT or SCO. In solution, electrochemical and spectroscopic analysis also indicate that all compounds exist as the HS-CoII-L0-containing electromer at 298 K. Intervalence charge transfer (IVCT) bands observed for neutral 1, 2, and 3 at room temperature suggest the mixed-valence HS-CoII-(Lâ¢-)2(L0) charge distribution. However, cooling 3 to 243 K in acetonitrile uniquely affords a substantial reduction in the intensity of this IVCT band, consistent with thermally induced VT interconversion to the LS-CoIII-(Lâ¢-)3 ground state as predicted by DFT calculations. This study emphasizes the utility of computationally guided molecular design for complicated systems with redox activity at the metal and multiple ligands, thus opening new avenues for tuning electronic structure and developing new families of switchable molecules.
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The syntheses of valence tautomeric compounds with multistep transitions using new redox-active ligands are the long-term goal of the field of bistable materials. The redox-active tetraoxolene ligand, 2,7-di-tert-butylpyrene-4,5,9,10-tetraone (pyreneQ-Q), is now developed to synthesize a pair of dinuclear compounds {[CoL2]2(pyreneSq-Sq)}[Co(CO)4]2·xCH2Cl2·2C6H5CH3 (1, x = 2, L = 1,10-phenanthroline, phen; 2, x = 1.5, L = 2,2'-bipyridine, bpy). Variable-temperature magnetic susceptibilities and single-crystal X-ray diffraction measurements indicate a partial one-step valence tautomeric transition for 1 and a rare two-step valence tautomeric transition for 2, respectively. DFT calculation results are consistent with the experimental data, revealing the correlation between thermodynamic parameters and the one-step/two-step valence tautomeric behaviors.
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Polycyclic aromatic hydrocarbons are of special interest due to their promising nonlinear optical and magnetic properties. A series of acene-linked zethrenes and bisphenalenyls comprising from five to nine benzene rings in the linker group have been computationally studied by the DFT UB3LYP/6-311++G(d,p) quantum-chemical modeling of their electronic structure, possible spin states, and exchange interactions. The zethrenes with octacene and nonacene linkers as well as bisphenalenyls comprising heptacene, octacene, and nonacene linker groups have been revealed to possess tetraradicaloid nature, which makes them promising building blocks for organic optoelectronic and spintronic devices. The results obtained open a way of constructing tetraradicaloid organic molecules characterized by the presence of two types of paramagnetic centers.
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The concept of using redox-active ligands, which has become extremely widespread in organometallic chemistry, is often considered from 'their effect on the metal center properties' point of view and 'how to modify the ligands'. In this paper, we present the reverse side of this effective approach - a dramatic change of redox properties of ligands under the influence of a redox-inert metal. Germanium derivatives based on 2,3-dihydroxynaphthalene (1) and N,N'-bidentate ligands, namely 2,2'-bipyridine (2) and 1,10-phenanthroline (3), were obtained and characterized by CV, UV-vis spectroscopy, DFT calculations and in the case of 3 X-ray diffraction. It was shown that the HOMO of the complexes is almost completely located on the naphthalene fragment while the LUMO is on the N,N-ligands. At the same time, there are no boundary molecular orbitals on the germanium atom, but it forms the axial part of the molecule holding two opposite motifs together. Moreover, it sharply affects the level of HOMO and LUMO. Derivatives 2 and 3 are more easily oxidized compared to 2,3-dihydroxynaphthalene by 0.31-0.34 V (7-8 kcal mol-1) and are more easily reduced compared to N,N-donors by 1.08-1.15 V (25-26.5 kcal mol-1). All this together makes it possible to form a system with a narrow HOMO/LUMO gap (â¼2 eV). The crystal structure of 3 consists of alternating monomolecular easily oxidizing and easily reducing layers formed due to intermolecular interactions, in particular π-stacking. In addition, in contrast to 1 that starts to decompose noticeably at the temperatures from 200 °C, 2 and 3 have an extremely high thermal stability. They remain stable with no signs of decomposition and melting up to 400 °Ð¡. We believe that this approach to the formation of the supramolecular structure may present prospects for obtaining new functional materials.
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A series of neutral triangular polycyclic aromatic hydrocarbons functionalized with various radical groups (dithiadiazolyl, verdazyl, nitronylnitroxyl, tert-butyl-nitroxyl and also (2,2,6,6-tetramethylpiperidin-1-yl)oxyl) has been computationally studied by the DFT UB3LYP/6-311++G(d,p) quantum-chemical modelling of their electronic structure and magnetic properties. The dependence of the nature and strength of the exchange interactions between paramagnetic centers on the size of the triangular core, the presence of heteroatoms in the polycyclic moiety, the type of the radical substituents and their spatial arrangement has been ascertained. The molecules with the high-spin electronic ground state possessing strong ferromagnetic exchange interactions and virtually non-interacting paramagnetic centers have been revealed, which makes them promising building blocks for organic spintronics devices.
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We report the synthesis of a new bistriarylamine series having a urea bridge and investigate its mixed-valence (MV) states by electrochemical and spectroelectrochemical methods. We found that the supporting electrolytes had unusual effects on potential splitting during electrochemical behavior, in which a smaller counteranion thermodynamically stabilized a MV cation more substantially than did a bulky one. The effects contrary to those reported in conventional MV systems were explained by zwitterionization through hydrogen bonding between the urea bridge and the counteranions, increasing the electronic interactions between two triarylamino units. Furthermore, we clarified the intervalence charge transfer characteristics of the zwitterionic MV state.
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A set of Sc, Nd, Sm, Eu, Ho, Gd, Er, Yb complexes with perfluorinated 2-(benzothiazol-2-yl)phenolate ligands Ln(SONF)3(DME) were synthesized by the reactions of silylamides Ln[N(SiMe3)2]3 with phenol H(SONF). The structure of the initial phenol, Sc, and Er complexes was established using X-ray analysis, which revealed that the obtained compounds are mononuclear, in contrast to the binuclear non-fluorinated analogues [Ln(SON)3]2 synthesized earlier. All the obtained complexes, both in solid state and in tetrahydrofuran (THF) solutions, upon excitation by light with λex 395 or 405 nm show intense luminance of the ligands at 440-470 nm. The Eu complex also exhibits weak metal-centered emission in the visible region, while the derivatives of Sm luminesces both in the visible and in the infrared region, and Nd, Er, and Yb complexes emit in the near IR (NIR) region of high intensity. DFT (density functional theory) calculation revealed that energy of frontier orbitals of the fluorinated complexes is lower than that of the non-fluorinated counterparts. The level of highest occupied molecular orbital (HOMO) decreases to a greater extent than the lowest occupied molecular orbital (LUMO) level.
Assuntos
Benzotiazóis/síntese química , Complexos de Coordenação/síntese química , Metais Terras Raras/química , Benzotiazóis/química , Complexos de Coordenação/química , Teoria da Densidade Funcional , Halogenação , Ligantes , Luminescência , Estrutura Molecular , Difração de Raios XRESUMO
A series of coordination compounds of redox-active 1,10-phenanthroline-5,6-diimine with CoII bis-diketonates and FeII dihydrobis(pyrazolyl)borates has been computationally designed by means of density functional theory (DFT UB3LYP*/6-311++G(d,p)) calculations of their electronic structure, energy characteristics, and magnetic properties. Four types of complexes differing by the nature and position of the terminal metal-centered fragments have been considered. The performed systematic calculations have revealed the systems capable of undergoing thermally initiated spin-state switching rearrangements, including those governed by the synchronized mechanisms of spin crossover and valence tautomerism. The predicted magnetic characteristics allow one to consider the dinuclear cobalt complexes and heterometallic Co/Fe compounds with 1,10-phenanthroline-5,6-diimine as building blocks for molecular and quantum electronics devices. © 2019 Wiley Periodicals, Inc.
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Complexes of divalent ytterbium (1) and europium (2) with a dianionic o-amidophenolate ligand were prepared by both the direct reduction of 4,6-di-tert-butyl-N-(2,6-diisopropylphenyl)-o-iminobenzoquinone (dpp-IQ) and the salt metathesis reaction of potassium o-amidophenolate with LnI2 (Ln = Yb, Eu). Oxidation of o-amidophenolates 1, 2 with one equivalent of dpp-IQ as well as the salt metathesis reaction of potassium o-iminosemiquinolate with LnI2 afforded ligand mixed-valent o-iminosemiquinonato-amidophenolato complexes of trivalent ytterbium (3) and europium (4). All novel complexes 1-4 were fully characterized, including the solid state structures of 1 and 2 determined by single crystal X-ray diffraction. The magnetic properties of paramagnetic 2-4 were examined.
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A series of new magnetically-active coordination compounds comprising binuclear mixed-ligand complexes of cobalt bis-diketonates with acene linkers functionalized by two redox-active o-quinone moieties has been designed by means of density functional theory (DFT UB3LYP*/6-311++G(d,p)) calculations of their electronic structure, energy characteristics and magnetic properties. Two types of redox-active ligands include those with an acene linker bridging two o-benzoquinone fragments and the ligands containing an integrated π-conjugated system formed by annulation of o-quinone rings to the polycyclic core. The calculations reveal the dependence of spin density distribution in the compounds under study on the type of ligand. The considered binuclear CoII diketonate adducts manifest the capability of undergoing one- and two-step spin transitions induced by intramolecular electron transfers between the metal ions and the ligand system. An increase in the number of condensed rings of the acene linker promotes the stabilization of the biradicaloid state of the linker and enhances exchange interactions between all paramagnetic centers of the complexes giving rise to the formation of a flexible spin coupling network. The predicted unusual magnetic properties make the binuclear cobalt complexes with di-o-quinone ligand containing acene linker groups the promising building blocks for molecular electronic and spintronic devices.
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3,5-di-tert-Butylcatecholate (DTBC) germanium complexes (DTBC)2Ge[Py(CN)n]2 (n = 0 2) have been synthesized from GeO2, 3,5-di-tert-butylcatechol and cyano-substituted pyridines Py(CN)n and characterized by elemental analysis, NMR, IR and UV-VIS spectroscopy. The structure of 1 (with 4-cyanopyridine) has been determined by X-ray single crystal analysis. UV-VIS spectra have shown that these complexes are stable in CH3CN, toluene and CH2Cl2 solutions; in contrast, they are rapidly decomposed by dimethylformamide and tetrahydrofuran. Complexes 1 and 2 (with 4-cyano and 3-cyanopyridine) are electrochemically reducible in toluene/1 M Bu4NPF6 at E = -1.3 -1.7 V vs. AgCl. The quantum-chemical study of these complexes is in accordance with the unsuccessful attempts to obtain analogous derivatives with 2-cyanopyridine and 2,6-dicyanopyridine.
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We computationally proved that the planar aromatic hexagonal isomer N3P3 with the alteration of N and P is the second most stable structure for the N3P3 stoichiometry. We found that the aromatic isomer has high barriers for transition into the global minimum structure or into the three isolated NP molecules, making this structure kinetically stable. We showed that the sandwich N3P3CrN3P3 molecule corresponds to a minimum on the potential energy surface; thus, the aromatic N3P3 molecule has a potential to be a new ligand in chemistry.
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In this Review we present examples of clusters, molecules, and solid-state compounds, for which the use of σ-aromaticity and σ-antiaromaticity concepts is essential for understanding of chemical bonding. We show that the bonding patterns in these σ-aromatic and σ-antiaromatic compounds are similar to those of the corresponding π-aromatic and π-antiaromatic chemical systems, respectively. Undoubtedly, σ-aromaticity helps us understand why the high symmetry isomers are the most stable among myriads of other potential structures. We also show that besides systems exhibiting either σ- or π-aromatic features, there are species, which can possess multiple aromaticity/antiaromaticity, or conflicting aromaticity patterns. We believe that the σ-aromaticity and σ-antiaromaticity concepts will be helpful in rationalizing chemical bonding, structure, stability, and molecular properties of chemical species in both organic and inorganic chemistry. We hope that they will also be useful for other areas of science such as material science, catalysis, nanotechnology, and biochemistry.
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Theoretical investigations to evaluate the viability of extended nonmetal atom chains on the basis of molecular models with the general formula Mn F4n+2 (M=S and Se) and corresponding solid-state systems exhibiting direct SS or SeSe bonding were performed. The proposed high-symmetry molecules were found to be minima on the potential energy surface for all Sn F4n+2 systems studied (n=2-9) and for selenium analogues up to n=6. Phonon calculations of periodic structures confirmed the dynamic stability of the -(SF4 -SF4 )∞ - chain, whereas the analogous -(SeF4 -SeF4 )∞ - chain was found to have a number of imaginary phonon frequencies. Chemical bonding analysis of the dynamically stable -(SF4 -SF4 )∞ - structure revealed a multicenter character of the SS and SF bonds. A novel definition and abbreviation (ENAC) are proposed by analogy with extended metal atom chain (EMAC) complexes.
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The possibility of employing the mechanism of intramolecular electron transfer between metal and ligand centers in the valence tautomeric complexes formed as electrically neutral 2 : 1 adducts of Co(II) diketonates and redox-active tetradentate di-o-quinones, for quantum information processing, has been computationally studied using the DFT B3LYP*/6-311++G(d,p) method. It has been shown that by the proper choice of a linker group bridging the quinone rings and substituents in the diketonate fragments, complexes with the properties required in 2-qubit quantum gates (sufficiently narrow energy gaps between the spin states and weakly coupled paramagnetic centers) can be designed, in order to realize the mechanism of thermally driven migration of paramagnetic centers between the o-quinone fragments and metal atoms. These are exemplified by the adduct of bis-(hexafluoroacetylacetonate)Co(ii) with a diquinone containing dimethylene linker. Valence tautomerism is considered as a new, promising mechanistic paradigm for the molecular design of 2-qubit molecular systems.
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A new concept for the structural design of valence tautomeric (VT) metal complexes involving the formation of stable adducts of a tetracoordinate transition metal complex with a suitable bidentate redox-active ligand has been computationally studied using the DFT B3LYP*/6-311++G(d,p) method. The calculations, performed on a series of adducts of Co(II) diketonates with o-benzoquinone and its mono- and diimines, showed that the mixed-ligand complexes of bis-(hexafluoroacetylacetonate) Co(II) with o-benzoquinone, o-benzoquinone imine and o-benzoquinone diimine satisfy the whole set of necessary conditions to be met by compounds exhibiting VT behaviour (stability of the adduct with respect to dissociation into the components, energy preference of the low-spin electronic state and thermally achievable energy barrier to intramolecular electron transfer determining the intrinsic mechanism of VT rearrangements). These compounds can be regarded as a feasible synthetic target of a broad series of mixed-ligand VT complexes.