EFFECTS OF STRUCTURAL MODIFICATION ON THE GROUND STATE OF METALLABENZENES: SINGLET VERSUS TRIPLET STATE
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Extensive density functional calculations were used to explore the geometries and relative stabilities of metallabenzenes with various spin multiplicities. The structural modification effects on the energy splittings between the singlet and triplet states, including the replacement of metal, the change of ligand environment, and the substitution of hydrogen and carbon atoms in the aromatic ring, were investigated. Calculations show that the stability of the singlet and triplet metallabenzenes strongly depends on the metal center, and the first-row transition metal metallabenzenes most probably have the triplet ground state. The stability of the triplet state can be enhanced by the strong π- and weak-field ligands as well as the electron-withdrawing substituent for hydrogen at the aromatic carbon such as - PPh 3+ . Present results can help us understand the magnetic properties of metallabenzenes and construct the function-orientated metallacyclic compounds.Keywords:
Spin states
Polar effect
We investigated mer- and fac-[Fe(II)(2-pic)(3)](2+) (pic = picolylamine) and Fe(iii) analogue, mer-[Fe(III)(2-pic)(3)](3+), by the DFT method to clarify the mechanism of light-induced excited spin state trapping (LIESST). In mer-[Fe(II)(2-pic)(3)](2+), the potential energy surface (PES) of the triplet state is the least stable but it is close to the PESs of the singlet and quintet states at the equilibrium geometry of the triplet state within 5 kcal mol(-1). This indicates that intersystem crossing occurs from the triplet state to either the singlet state or the quintet state around the equilibrium geometry of the triplet state. The quintet state is as stable as the singlet state in their equilibrium geometries. All Fe-N bonds of the quintet state are longer than those of the singlet state by about 0.19 A. These are consistent with the general understanding that the Fe-ligand distances are considerably different but the relative stability is little different between the low spin and high spin states in LIESST complexes. Actually, a large activation barrier is calculated for the conversion between the singlet and quintet states, which is enough to suppress thermal spin transition and tunneling between them. The d-d transition energies are calculated with the TD-DFT method to be 2.05, 2.07, and 2.09 eV in the singlet state and 1.46 and 1.64 eV in the quintet state. Because of the significantly large difference in excitation energy between the singlet and quintet states, irradiation of visible light with different wavelengths selectively induces the excitation to the singlet excited state or the quintet one. All these results are consistent with the fact that both LIESST and reverse-LIESST are observed in mer-[Fe(II)(2-pic)(3)](2+). The fac-isomer is also useful for the LIESST/reverse-LIESST, though the mer-isomer is better. In the Fe(iii) analogue, mer-[Fe(III)(2-pic)(3)](3+), the DFT-computational results indicate small activation barriers and a large overlap of absorption spectra between the doublet and sextet states. Also, the Fe(III)-N bond distances are less different between the low spin and high spin states than the Fe(II)-N ones, leading to the narrow potential wall between the doublet and sextet states. As a result, the LIESST and reverse-LIESST cannot be observed in this Fe(iii) complex.
Intersystem crossing
Singlet fission
Spin states
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On the basis of the data obtained by X-ray diffraction, the properties of two independent crystallographic subsystems in the [Fe(tpen)](ClO4)2.2/3H2O complex are studied in detail with the density functional method B3LYP. The energies of singlet, triplet, and quintet states at different temperatures are obtained, the influences of geometry on energy changes are analyzed, the regularity of the spin-state interconversions is investigated, and the effect of the triplet and action of the anion on spin crossover are discussed. This investigation demonstrates that (1) the energy difference between the high-spin state and singlet state decreases as the Fe-N distance and geometric distortion increase, (2) the spin-equilibrium system is predominantly in low-spin form below room temperature and the proportion of high-spin state rapidly increases above room temperature, (3) one of the two cation sites has a greater presence of the high-spin content, (4) the triplet state may be responsible for the fast rate of spin-state interconversions, and (5) the B3LYP method proves to be very adequate to study the spin-state transition of this complex.
Spin states
Ethylene diamine
Spin Crossover
Perchlorate
Spin transition
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We have investigated the radicality and the vertical singlet-triplet energy gap of [n]cyclacenes (cyclic polyacenes) as a function of the system size for n even, from 6 to 22. The calculations are performed using the complete active space self-consistent field method and second-order n-electron valence perturbation theory. We present a systematic way for the selection of the active space in order to have a balanced description of the wave function as the size of the system increases. Moreover, we provide didactic insight into the failure of an approach based on a minimal active space. We find that the ground state is an open-shell singlet and its multireference character increases progressively with n. The singlet-triplet gap decreases as a function of the system size and approaches a finite positive value for the limit n → ∞. Finally, an analysis based on the one-particle reduced density matrix suggests a polyradical character for the largest cyclacenes.
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A recent computational investigation of Jahn−Teller effects in unsaturated 16-electron d4d6 [CpMLn] complexes (Abu-Hasanayn, F.; Cheong, P.; Oliff, M. Angew. Chem. 2002, 41, 2120) highlighted the typical presence of two spin-triplet and two singlet states of competing stability in these complexes and pointed out the necessity to account for more than one electronic state in studies thereof. Consequently, we have reinvestigated the addition of N2 to all the four low-energy states of CpMoCl(PH3)2, a reaction for which previously only one singlet and one triplet state have been considered (Keogh, D. W.; Poli, R. J. Am. Chem. Soc. 1997, 119, 2516). The present study was performed using density functional theory (DFT) and the thus obtained relative stabilities of the four electronic states of the educt are in good accord with those obtained using a multireference MP2 method. The spin-singlet ground state of the 18e- product of N2 addition turns out to be derived from the fourth lowest state (21A') of the 16e- educt, immediately demonstrating the importance of accounting for more than one triplet and one singlet state in such reactions. The barrier to N2 addition was found to arise from the enthalpic cost of obtaining identical geometries for this singlet state and the spin-triplet ground state of the educt (3A' ') in the minimum energy crossing point (MECP). With a spin-triplet ground-state reactant complex, a triplet−singlet MECP defining the rate-limiting step, and a singlet product, our calculated activation (14.4 kcal/mol) as well as reaction enthalpies (21.2 kcal/mol) of N2 addition to CpMoCl(PMe3)2 are found to be within the experimental error bars of those measured for Cp*MoCl(PMe3)2. For the corresponding reaction with CO, there is a delicate balance between the transition state (TS) of addition on the triplet potential energy surface (PES) and the point of crossing between the triplet and singlet PES. Our optimized TS and MECPs for this reaction suggest that the rate is controlled by the barrier defined by the spin-triplet TS, with spin inversion occurring after this point. Our calculated activation enthalpy (6.7 kcal/mol) based on the spin-triplet TS is in excellent agreement with that measured for Cp*MoCl(PMe3)2.
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The authors have previously proposed a theoretical model for exotic spin alignment in organic molecular assemblages: The alternating chain of organic biradicals in a singlet (Sb = 0) ground state and monoradicals with S = 1/2 has a ferrimagnetic ground state for the whole chain, which has been termed generalized ferrimagnetism. An important feature of the generalized ferrimagnetic spin alignment has been found in the deviation of the expectation value 〈Sb2〉 of the biradical spin from zero. Even a triplet-like spin state 〈Sb2〉 = 2 (Sb = 1) has been predicted in the theoretical calculations. In this study, we have found experimental evidence for the pseudo-triplet state appearing in the ground-state singlet biradical of a real open-shell compound. At first, we have demonstrated from theoretical calculations that the singlet biradical has 〈Sb2〉 = 2 (Sb = 1) in a molecular pair with an S = 1 metal ion as well as with the S = 1/2 monoradical. The pseudo-triplet state of the biradical affords a singlet state of the whole system of the biradical-metal ion pair, which is readily detectable in experiments for verifying the theoretical prediction. As a model compound for the biradical-metal ion pair, a transition metal complex, [(bnn)(Ni(hfac)2)1.5(H2O)] (1), has been synthesized from a nitronyl nitroxide-based ground-state singlet biradical bnn and Ni(hfac)2. From X-ray crystallographic analyses, the compound contains a molecular pair of bnn and Ni(hfac)2, which serves as a model system under the above theoretical studies. It has been found from the analysis of the temperature dependence of magnetic susceptibility that the bnn−Ni(hfac)2 pair has the singlet (S = 0) ground state. The singlet ground state of the pair results from an antiparallel coupling of the pseudo-triplet of the biradical and the S = 1 spin on the Ni ion. The pseudo-triplet state in the ground-state singlet biradical has thus been verified experimentally, which is crucially important to realize the generalized ferrimagnetic spin alignment.
Ferrimagnetism
Diradical
Spin states
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Quantum yield
Hexane
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The Equilibrium geometrical optimizations on OCS linear and nonlinear molecules in the singlet and triplet states have been made using density functional theory B3LYP method with 6-31l++G~(**)and aug-CC-pVTZ basis sets.The ground state is ~1∑with linear C_(∞v) symmetry The linear and nonlinear structures in singlet state can be stable,and there is only nonlinear stablestructure in triplet state.
Singlet fission
Basis (linear algebra)
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Extensive density functional calculations were used to explore the geometries and relative stabilities of metallabenzenes with various spin multiplicities. The structural modification effects on the energy splittings between the singlet and triplet states, including the replacement of metal, the change of ligand environment, and the substitution of hydrogen and carbon atoms in the aromatic ring, were investigated. Calculations show that the stability of the singlet and triplet metallabenzenes strongly depends on the metal center, and the first-row transition metal metallabenzenes most probably have the triplet ground state. The stability of the triplet state can be enhanced by the strong π- and weak-field ligands as well as the electron-withdrawing substituent for hydrogen at the aromatic carbon such as - PPh 3+ . Present results can help us understand the magnetic properties of metallabenzenes and construct the function-orientated metallacyclic compounds.
Spin states
Polar effect
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Potential singlet-triplet surface crossings for the ring opening of 4,6-dimethylidenebicyclo[3.1.0]hex-2-ene derivatives were explored using density functional theory (DFT) and complete active space self-consistent field (CASSCF) methods. Since these ring openings involve relatively high energy species that lead to relatively stable aromatic species, a good scenario for potential nonadiabatic events, we posited that the reaction paths of these ring openings might come close to or cross excited state surfaces. At the DFT level of theory, all reaction paths exhibited characteristics suggestive of singlet-triplet intersections along their paths. 6-Methylidenebicyclo[3.1.0]hex-3-en-2-one and a closely related derivative (4-methylidenebicyclo[3.1.0]hex-2-en-6-one) were explored at the CASSCF level of theory; CASSCF results were qualitatively similar to DFT results and yielded spin-orbit couplings of 1.1-1.4 cm(-1) at the singlet-triplet crossing points.
Ene reaction
Potential energy surface
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