Ruthenium-Grafted Vinylhelicenes: Chiroptical Properties and Redox Switching.

The properties of mono- and bis-Ru-vinyl[6]helicene complexes (2 a and 2 b, respectively), recently synthesized by using molecular engineering of helicenes based on the grafting of lateral organometallic substituents on the π-helical backbone through a vinyl bridge, are presented. These helicene derivatives are thoroughly characterized, with special attention given to their chiroptical properties and redox switching activity. The UV/Vis and electronic circular dichroism (ECD) spectra of P and M enantiopure species, both in the neutral and oxidized states ([2 a](·+), [2 b](·+), and [2 b](2+)), are analyzed with the aid of quantum-chemical calculations. The extended π-conjugation facilitated by the vinyl moiety, clearly visible in the electronic structures of 2 a,b, introduces new active bands in the ECD spectra that consequently lead to a significant increase in optical rotation of Ru-vinylhelicenes compared with the organic precursors. The vibrational circular dichroism (VCD) spectra were measured and calculated for both the organic and organometallic species and constitute the first examples of VCD for metal-based helicene derivatives. Finally, the redox-triggered chiroptical switching activity of 2 a,b is examined in detail by using ECD spectroscopy. The modifications of the ECD spectra in the UV/Vis and NIR region are well reproduced and rationalized by calculations.

enantio-Enriched CPL-active helicene-bipyridine-rhenium complexes.

The incorporation of a rhenium atom within an extended helical π-conjugated bi-pyridine system impacts the chiroptical and photophysical properties of the resulting neutral or cationic complexes, leading to the first examples of rhenium-based phosphors that exhibit circularly polarized luminescence.

Acid/base-triggered switching of circularly polarized luminescence and electronic circular dichroism in organic and organometallic helicenes.

Electronic circular dichroism and circularly polarized luminescence acid/base switching activity has been demonstrated in helicene-bipyridine proligand 1 a and in its "rollover" cycloplatinated derivative 2 a. Whereas proligand 1 a displays a strong bathochromic shift (>160 nm) of the nonpolarized and circularly polarized luminescence upon protonation, complex 2 a displays slightly stronger emission. This strikingly different behavior between singlet emission in the organic helicene and triplet emission in the organometallic derivative has been rationalized by using quantum-chemical calculations. The very large bathochromic shift of the emission observed upon protonation of azahelicene-bipyridine 1 a has been attributed to the decrease in aromaticity (promoting a charge-transfer-type transition rather than a π-π* transition) as well as an increase in the HOMO-LUMO character of the transition and stabilization of the LUMO level upon protonation.

Delocalization error and "functional tuning" in Kohn-Sham calculations of molecular properties.

Kohn-Sham theory (KST) is the "workhorse" of numerical quantum chemistry. This is particularly true for first-principles calculations of ground- and excited-state properties for larger systems, including electronic spectra, electronic dynamic and static linear and higher order response properties (including nonlinear optical (NLO) properties), conformational or dynamic averaging of spectra and response properties, or properties that are affected by the coupling of electron and nuclear motion. This Account explores the sometimes dramatic impact of the delocalization error (DE) and possible benefits from the use of long-range corrections (LC) and "tuning" of functionals in KST calculations of molecular ground-state and response properties. Tuning refers to a nonempirical molecule-specific determination of adjustable parameters in functionals to satisfy known exact conditions, for instance, that the energy of the highest occupied molecular orbital (HOMO) should be equal to the negative vertical ionization potential (IP) or that the energy as a function of fractional electron numbers should afford straight-line segments. The presentation is given from the viewpoint of a chemist interested in computations of a variety of molecular optical and spectroscopic properties and of a theoretician developing methods for computing such properties with KST. In recent years, the use of LC functionals, functional tuning, and quantifying the DE explicitly have provided valuable insight regarding the performance of KST for molecular properties. We discuss a number of different molecular properties, with examples from recent studies from our laboratory and related literature. The selected properties probe different aspects of molecular electronic structure. Electric field gradients and hyperfine coupling constants can be exquisitely sensitive to the DE because it affects the ground-state electron density and spin density distributions. For π-conjugated molecules, it is shown how the DE manifests itself either in too strong or too weak delocalization of localized molecular orbitals (LMOs). Optical rotation is an electric-magnetic linear response property that is calculated in a similar fashion as the electric polarizability, but it is more sensitive to approximations and can benefit greatly from tuning and small DE. Hyperpolarizabilities of π-conjugated "push-pull" systems are examples of NLO properties that can be greatly improved by tuning of range-separated exchange (RSE) functionals, in part due to improved charge-transfer excitation energies. On-going work on band gap predictions is also mentioned. The findings may provide clues for future improvements of KST because different molecular properties exhibit varying sensitivity to approximations in the electronic structure model. The utility of analyzing molecular properties and the impact of the DE in terms of LMOs, representing "chemist's orbitals" such as individual lone pairs and bonds, is highlighted.

Straightforward access to mono- and bis-cycloplatinated helicenes that display circularly polarized phosphorescence using crystallization resolution methods.

Enantiopure mono-cycloplatinated-[8]helicene and bis-cycloplatinated-[6]helicene derivatives were prepared through column chromatography combined with crystallization of diastereomeric complexes using a chiral ancillary sulfoxide ligand. The UV-visible spectra, circular dichroism, molar rotations, and (circularly polarized) luminescence activity of these new helical complexes have been examined in detail and analysed with the help of first-principles quantum-chemical calculations.

Unravelling the structure of Magnus' pink salt.

A combination of multinuclear ultra-wideline solid-state NMR, powder X-ray diffraction (pXRD), X-ray absorption fine structure experiments, and first principles calculations of platinum magnetic shielding tensors has been employed to reveal the previously unknown crystal structure of Magnus' pink salt (MPS), [Pt(NH3)4][PtCl4], study the isomeric Magnus' green salt (MGS), [Pt(NH3)4][PtCl4], and examine their synthetic precursors K2PtCl4 and Pt(NH3)4Cl2·H2O. A simple synthesis of MPS is detailed which produces relatively pure product in good yield. Broad (195)Pt, (14)N, and (35)Cl SSNMR powder patterns have been acquired using the WURST-CPMG and BRAIN-CP/WURST-CPMG pulse sequences. Experimentally measured and theoretically calculated platinum magnetic shielding tensors are shown to be very sensitive to the types and arrangements of coordinating ligands as well as intermolecular Pt-Pt metallophilic interactions. High-resolution (195)Pt NMR spectra of select regions of the broad (195)Pt powder patterns, in conjunction with an array of (14)N and (35)Cl spectra, reveal clear structural differences between all compounds. Rietveld refinements of synchrotron pXRD patterns, guided by first principles geometry optimization calculations, yield the space group, unit cell parameters, and atomic positions of MPS. The crystal structure has P-1 symmetry and resides in a pseudotetragonal unit cell with a distance of >5.5 Å between Pt sites in the square-planar Pt units. The long Pt-Pt distances and nonparallel orientation of Pt square planes prohibit metallophilic interactions within MPS. The combination of ultra-wideline NMR, pXRD, and computational methods offers much promise for future investigation and characterization of Pt-containing systems.

Helicene-grafted vinyl- and carbene-osmium complexes: an example of acid-base chiroptical switching.

The first helicene-based carbene-osmium complex has been prepared from a vinyl-osmium derivative and this system has been shown to behave as a potential acid-base triggered chiroptical switch.

Diastereo- and enantioselective synthesis of organometallic bis(helicene)s by a combination of C-H activation and dynamic isomerization.

Homochiral and heterochiral cis-bis-cycloplatinated-[6]helicene derivatives 1b(1,2), as representative examples of platina[6]helicenes that share a common platinum center, have been prepared. A diastereo- and enantioselective synthesis, which combines CH activation and dynamic isomerization from heterochiral structure 1b(2) into homochiral structure 1b(1), is also described. Overall, this isomerization process results in the transfer of chiral information from one helicene moiety to the other one. The chiroptical properties of homochiral (P)- and (M)-1b(1) were greatly modified upon oxidation into their corresponding (P)- and (M)-diiodo-Pt(IV) complexes (5). The changes were also analyzed by performing theoretical calculations. C-H activation in the synthesis of organometallic helicenes is further demonstrated by the preparation of cis-bis-cycloplatinated-[8]helicene 1c.

Computational analysis of (47/49)Ti NMR shifts and electric field gradient tensors of half-titanocene complexes: structure-bonding-property relationships.

Metal NMR shielding and electric-field gradient (EFG) tensors are examined by quantum-chemical calculations for a set of 14 titanium(IV) complexes. Benchmarks are performed for titanocene chlorides that have been characterized recently by solid-state NMR experiments, focusing on the dependence of Ti(IV) NMR parameters on the computational model in terms of the choice of the density functional, and considering molecular clusters versus infinite-periodic solid. Nearest-neighbor and long-range effects in the solid state are found to influence NMR parameters in systems without spatially extended ligands. Bulky ligands increase the fraction of local structure and bonding information encoded in the EFG tensors by reducing intermolecular interactions. Next, Ti shielding constants and EFG tensors for a variety of olefin (co)polymerization catalysts are analyzed in terms of contributions from localized molecular orbitals representing Lewis bonds and lone pairs. Direct links between the observed theoretical trends and the local bonding environment around the Ti metal center are found. A specific dependence of the Ti EFG tensors on the exact arrangement and type of surrounding bonds is demonstrated, providing a basis for further studies on solid-supported titanium catalytic systems.

Chiroptical properties of carbo[6]helicene derivatives bearing extended π-conjugated cyano substituents.

New carbo[6]helicene derivatives grafted with π-conjugated cyano-phenyl arms were synthesized in enantiopure forms and their π-conjugation examined by UV-vis spectroscopy. The influence of the π-conjugation on the circular dichroism spectra and molar rotations is discussed based on comparing experimental data with results from quantum-chemical calculations. The results highlight the fact that increasing the spatial extension of the π-system in a helicene molecule is an efficient way of increasing its molar rotation.

Ruthenium-vinylhelicenes: remote metal-based enhancement and redox switching of the chiroptical properties of a helicene core.

Introducing metal-vinyl ruthenium moieties onto [6]helicene results in a significant enhancement of the chiroptical properties due to strong metal-ligand electronic interactions. The electro-active Ru centers allow the achievement of the first purely helicene-based redox-triggered chiroptical switches. A combination of electrochemical, spectroscopic, and theoretical techniques reveals that the helicene moiety is a noninnocent ligand bearing a significant spin density.

Does a Molecule-Specific Density Functional Give an Accurate Electron Density? The Challenging Case of the CuCl Electric Field Gradient.

In the framework of determining system-specific long-range corrected density functionals, the question is addressed whether such functionals, tuned to satisfy the condition -ε(HOMO) = IP or other energetic criteria, provide accurate electron densities. A nonempirical physically motivated two-dimensional tuning of range-separated hybrid functionals is proposed and applied to the particularly challenging case of a molecular property that depends directly on the ground-state density: the copper electric field gradient (EFG) in CuCl. From a continuous range of functional parametrizations that closely satisfy -ε(HOMO) = IP and the correct asymptotic behavior of the potential, the one that best fulfills the straight-line behavior of E(N), the energy as a function of a fractional electron number N, was found to provide the most accurate electron density as evidenced by calculated EFGs. The functional also performs well for related Cu systems.

Tuned Range-Separated Time-Dependent Density Functional Theory Applied to Optical Rotation.

For range-separated hybrid density functionals, the consequences of using system-specific range-separation parameters (γ) in calculations of optical rotations (ORs) are investigated. Computed ORs at three wavelengths are reported for methyloxirane, norbornenone, ß-pinene, [6]helicene, [7]helicene, and two derivatives of [6]helicene. The γ parameters are adjusted such that Kohn-Sham density functional calculations satisfy the condition -ε(HOMO)(N) = IP. For ß-pinene, the behavior of the energy as a function of fractional total charge is also tested. For the test set of molecules, comparisons of ORs with available coupled-cluster and experimental data indicate that the γ "tuning" leads to improved results for ß-pinene and the helicenes and does not do too much harm in other cases.

Analysis of Optical Activity in Terms of Bonds and Lone-Pairs: The Exceptionally Large Optical Rotation of Norbornenone.

Norbornenone, which has both a C═O and a C═C chromophore in a rigid bicyclic hydrocarbon framework, exhibits optical rotation (OR) an order of magnitude larger than that of similar molecules with only one of these chromophores (e.g., α-pinene). Its OR is also very sensitive to approximations in electronic structure calculations. The present study demonstrates a novel approach to interpret optical rotation using familiar concepts of chemical bonding, aided by first-principles calculations. A theoretical procedure is developed for analyzing the OR tensor components of a molecule in terms of individual bonds and lone pairs. The link between the chemist's bond and quantum mechanics is provided by localized molecular orbitals obtained from density functional theory (DFT) calculations. Delocalization of π orbitals is shown to play a crucial role in the large OR of norbornenone, as hinted by the DFT delocalization error inherent in many standard functionals and confirmed by detailed analysis. The OR contributions generated by the double bond in α-pinene are even stronger than that of norbornenone. The isotropic average, observed in solution or in gas phase, is small as a result of cancellation of tensor components with opposite signs. The electronic coupling and delocalization of the C═C π bond and the C═O oxygen π lone pair in norbornenone selectively enhance one of the OR tensor components, resulting in the exceptionally large negative isotropic OR.

Optical rotation calculated with time-dependent density functional theory: the OR45 benchmark.

Time-dependent density functional theory (TDDFT) computations are performed for 42 organic molecules and three transition metal complexes, with experimental molar optical rotations ranging from 2 to 2 × 10(4) deg cm(2) dmol(-1). The performances of the global hybrid functionals B3LYP, PBE0, and BHLYP, and of the range-separated functionals CAM-B3LYP and LC-PBE0 (the latter being fully long-range corrected), are investigated. The performance of different basis sets is studied. When compared to liquid-phase experimental data, the range-separated functionals do, on average, not perform better than B3LYP and PBE0. Median relative deviations between calculations and experiment range from 25 to 29%. A basis set recently proposed for optical rotation calculations (LPol-ds) on average does not give improved results compared to aug-cc-pVDZ in TDDFT calculations with B3LYP. Individual cases are discussed in some detail, among them norbornenone for which the LC-PBE0 functional produced an optical rotation that is close to available data from coupled-cluster calculations, but significantly smaller in magnitude than the liquid-phase experimental value. Range-separated functionals and BHLYP perform well for helicenes and helicene derivatives. Metal complexes pose a challenge to first-principles calculations of optical rotation.

QTAIM and ETS-NOCV analyses of intramolecular CH···HC interactions in metal complexes.

The topological analysis, based on the quantum theory of atoms in molecules (QTAIM) of Bader and the ETS-NOCV charge and energy decomposition method have been used to characterize coordination bonds, chelating rings, and additional intramolecular interactions in the ZnNTA and ZnNTPA complexes in solvent. The QTAIM and ETS-NOCV studies have conclusively demonstrated that the H-clashes (they are observed only in the ZnNTPA complex and classically are interpreted as steric hindrance destabilizing a complex) are characterized by (i) the electron flow channel between the H-atoms involved, as discovered by the ETS-NOCV analysis (on average, ΔE(orb) = -1.35 kcal mol(-1)) and (ii) QTAIM-defined a bond path that indicates the presence of a preferred quantum-mechanical exchange channel, hence, they should be seen as H-H intramolecular bonding interactions. The main reason for the formation of a weaker ZnNTPA complex was attributed to the strain energy (from both QTAIM and ETS-NOCV techniques) and the larger Pauli repulsion contribution found from the ETS-NOCV analysis. An excellent agreement between physical properties controlling the stability of the two complexes was found from the two techniques, QTAIM and ETS-NOCV.

On the nature of Ni···Ni interaction in a model dimeric Ni complex.

A new dinuclear complex (NiC(5)H(4)SiMe(2)CHCH(2))(2) (2) was prepared by reacting nickelocene derivative [(C(5)H(4)SiMe(2)CH=CH(2))(2)Ni] (1) with methyllithium (MeLi). Good quality crystals were subjected to a high-resolution X-ray measurement. Subsequent multipole refinement yielded accurate description of electron density distribution. Detailed inspection of experimental electron density in Ni···Ni contact revealed that the nickel atoms are bonded and significant deformation of the metal valence shell is related to different populations of the d-orbitals. The existence of the Ni···Ni bond path explains the lack of unpaired electrons in the complex due to a possible exchange channel.

Spin ground state and magnetic properties of cobalt(II): relativistic DFT calculations guided by EPR measurements of bis(2,4-acetylacetonate)cobalt(II)-based complexes.

The spin ground state of the core ion and structure of the bis(2,4-acetylacetonate)cobalt(II) model complex and its synthetic aqua and ethanol derivatives, Co(acac)(2)L(n), (L = EtOH, H(2)O), were examined by means of density functional theory (DFT) calculations supported by electron paramagnetic resonance (EPR) measurements. Geometry optimizations were carried out for low-spin (doublet) and high-spin (quartet) states. For the Co(acac)(2) complex two possible conformations, a square-planar and a tetrahedral one, were taken into account. For all structures relative energies were calculated with both "pure" and hybrid functionals. The calculated data were complemented with the results of the EPR investigations carried out at liquid helium temperature, allowing for definite assignment of the high-spin state for the Co(acac)(2)(EtOH)(2) complex. However, because of the unresolved spectral features, only effective g-values could be assessed, whereas the zero-field splitting parameters (ZFS) were calculated by means of the spin-orbit mean field (SOMF) relativistic DFT method for which direct spin-spin (SS) and spin-orbit coupling (SOC) contributions were quantified.

Applications of the ETS-NOCV method in descriptions of chemical reactions.

The present study characterizes changes in the electronic structure of reactants during chemical reactions based on the combined charge and energy decomposition scheme, ETS-NOCV (extended transition state-natural orbitals for chemical valence). Decomposition of the activation barrier, ΔE (#), into stabilizing (orbital interaction, ΔE (orb), and electrostatic, ΔE (elstat)) and destabilizing (Pauli repulsion, ΔE (Pauli), and geometry distortion energy, ΔE (dist)) factors is discussed in detail for the following reactions: (I) hydrogen cyanide to hydrogen isocyanide, HCN → CNH isomerization; (II) Diels-Alder cycloaddition of ethene to 1,3-butadiene; and two catalytic processes, i.e., (III) insertion of ethylene into the metal-alkyl bond using half-titanocene with phenyl-phenoxy ligand catalyst; and (IV) B-H bond activation catalyzed by an Ir-containing catalyst. Various reference states for fragments were applied in ETS-NOCV analysis. We found that NOCV-based deformation densities (Δρ (i)) and the corresponding energies ΔE (orb)(i) obtained from the ETS-NOCV scheme provide a very useful picture, both qualitatively and quantitatively, of electronic density reorganization along the considered reaction pathways. Decomposition of the barrier ΔE(#) into stabilizing and destabilizing contributions allowed us to conclude that the main factor responsible for the existence of positive values of ΔE (#) for all processes (I, II, III and IV) is Pauli interaction, which is the origin of steric repulsion. In addition, in the case of reactions II, III and IV, a significant degree of structural deformation of the reactants, as measured by the geometry distortion energy, plays an important role. Depending on the reaction type, stabilization of the transition state (relatively to the reactants) originating either from the orbital interaction term or from electrostatic attraction can be of vital importance. Finally, use of the ETS-NOCV method to describe catalytic reactions allows extraction of information on the role of catalysts in determination of ΔE (#).