Helical Molecular Orbitals Research Articles

Chiral Jahn-Teller Distortion in Quasi-Planar Boron Clusters.

In this work, we have observed that some chiral boron clusters (B16-, B20-, B24-, and B28-) can simultaneously have helical molecular orbitals and helical spin densities; these seem to be the first compounds discovered to have this intriguing property. We show that chiral Jahn-Teller distortion of quasi-planar boron clusters drives the formation of the helical molecular spin densities in these clusters and show that elongation/enhancement in helical molecular orbitals can be achieved by simply adding more building blocks via a linker. Aromaticity of these boron clusters is discussed. Chiral boron clusters may find potential applications in spintronics, such as molecular magnets.

Generation of Helical States - Breaking of Symmetries, Curie's Principle, and Excited States.

Herein, we deeply detail for the very first time mathematical concepts behind the generation of helical molecular orbitals (MOs) for linear chains of atoms. We first give a definition of helical MOs and we provide an index measuring how far a given helical states is from a perfect helical distribution. Structural properties of helical distribution for twisted -cumulene and cumulene version of Möbius systems are given. We then give some simple structural assumptions as well as symmetry requirements ensuring the existence of helical MOs. Considering molecules which do not admit helical MOs, we provide a first way to induce helical states by the breaking of symmetries. We also explore an alternative way using excited conformations of given molecules as well as different electronic multiplicities.

Cooperativity and reactivity properties of medium-sized boron clusters: a combined density functional theory and information-theoretic approach study

In continuation of our previous work of small boron clusters [Phys. Chem. Chem. Phys. 23, 24118 (2021)], we systematically examined the neutral and negatively charged boron clusters B n /B − (nε{8–38}) with planar or quasi-planar conformations, whose exotic properties have aroused considerable interest in the literature. We make use of two total energy partition schemes, conceptual density functional theory, and the information-theoretic approach to appreciate the cooperativity and reactivity properties. We found that neutral boron clusters are positively cooperative, but negatively charged boron clusters are negatively cooperative. Our results show that the origin of the cooperativity effect for the negatively cooperative boron clusters is much more complicated than the neutral boron clusters. For chemical reactivity, we unveil that the reactive sites are around the cluster periphery and boron atoms can be both electrophilic and nucleophilic. Global and local aromaticity for the boron clusters can be totally different. For the first time, we have observed helical spin density distributions for negatively charged boron clusters (B16 – and B20 – ), which is reminiscent of helical molecular orbitals [Chem. Sci. 4, 4278 (2013)] in allenes, cumulenes, and oligoynes (polyalkynes). Collectively, our results should provide more insights to understand the exotic properties of boron clusters and henceforth yield novel potential applications.

Amine terminated polyynes as candidates for molecular wire applications: A DFT study

The structural and conducting properties of four amine terminated polyynes CAN[n],PHN[n],NCH3[n] and NH2[n], with n = 2,4,6,8 are studied at density functional theory (DFT) level, and compared with two non-amine terminated cases(BT[n] and PY[n]) whose high single molecule conductance was reported experimentally. Helical molecular orbitals delocalized over the whole molecule are observed for amine terminated polyynes which will improve the conductance. The amine terminated polyynes possess high HOMO energy, hence lesser transport barrier, along with reduced bond length alternation (BLA) values. The reduction in BLA of amine terminated polyynes is also confirmed by the shift of the collective CC stretching frequency to lower values. A significant reduction in BLA is noted followed by a transfer of negative charge to the molecule as shown by the BLA of the anions. Also electron reorganization energies are much reduced for CAN [2], CAN [4] and PHN [2] terminated polyynes. In this way the conducting properties of the polyynes are enhanced for amine terminated polyynes.

Highly delocalised molecular orbitals in boron-, carbon- and nitrogen-based linear chains: a DFT study

In the present work a comparison of the electronic structures of the Linear carbon chains (LCC) with Boron linear chains (BnH2 and BnH4) and boron–nitrogen linear chains (Bn/2Nn/2H2 and Bn/2Nn/2H4) is made using B97X-D/6-311++G** level of theory. BnH2 and BnH4 show comparatively more delocalised molecular orbitals and lower electron densities than CnH2 and CnH4. CnH2 and CnH4 show much more efficient charge delocalisation than the other chains. For the first time it is reported that BnH4 chains also show helical molecular orbitals for n = 2,6,10. Modification of the helical orbitals of the cumulene chains was observed upon the introduction of boron atoms.

Quantification of the Helicality of Helical Molecular Orbitals.

The frontier molecular orbital (MO) topology of linear carbon molecules, such as polyynes, can be visually identified as helices. However, there is no clear way to quantify the helical curvature of these π-MOs, and it is thus challenging to quantify correlations between the helical curvature and molecular properties. In this paper, we develop a method that enables us to compute the helical curvature of MOs based on their nodal planes. Using this method, we define a robust way of quantifying the helical nature of MOs (helicality) by their deviation from a perfect helix. We explore several limiting cases, including polyynes, metallacumulenes, cyclic allenes, and spiroconjugated systems, where the change in helical curvature is subtle yet clearly highlighted with this method. For example, we show that strain only has a minor effect on the helicality of the frontier orbitals of cycloallenes and that the MOs of spiroconjugated systems are close to perfect helices around the spiro-carbon. Our work provides a well-defined method for assessing orbital helicality beyond visual inspection of MO isosurfaces, thus paving the way for future studies of how the helicality of π-MOs affects molecular properties.

Helical Molecular Orbitals to Induce Spin-Orbit Coupling in Oligoyne-Bridged Bifluorenes.

Singlet-Triplet energy exchange is an area of active research due to its role in optoelectronic devices and photodynamic therapy. Large spin-orbit coupling (SOC) is difficult to achieve in simple hydrocarbon structures limiting the intersystem crossing (ISC) rates. A new approach to enhance the spin-orbit coupling via helical molecular orbitals is investigated in oligoyne-bridged bifluorenes. Transient absorption studies showed a singlet-to-triplet ISC rate of up to 6 ns-1 resulting in 0.84 triplet yield. Density functional calculations revealed a direct relation between high ISC and large SOC values mediated by helical molecular orbitals. Calculations and spectroscopic data also suggested that El-Sayed forbidden ISC occurs as a direct transition between 1ππ* and 3ππ*, which becomes allowed due to a symmetry-breaking interaction leading to mixing between orthogonal π-systems in the oligoyne fragment.

From Allenes to Spirobifluorenes: On the Way to Device-compatible Chiroptical Systems

The last decade has seen a huge growth in the construction of chiral systems to expand the scope of chiroptical applications. Dependence of chiroptical response on molecular conformation typically leads to low chiroptical intensities of chiral systems that feature several conformations in solution. In this respect, allenes were employed for the preparation of open and cyclic oligomers as well as molecular cages, presenting remarkable chiroptical responses in solution. Their molecular chirality was also transferred to metal surfaces, yet photoisomerization of allenes limited their further exploration. In search of a more robust chiral axis, theoretical and experimental studies confirmed that spirobifluorenes could give rise to stable systems with tailored optical and chiroptical properties. Additionally, incorporating a conformational lock into spirobifluorene cyclic architectures served as an efficient strategy towards the generation of distinct helical molecular orbitals. This review article outlines our results on developing device-compatible chiroptical systems through axially chiral allenes and spirobifluorenes. The contribution from other research groups is presented briefly.

Frontispiece: Distinct Helical Molecular Orbitals through Conformational Lock

Frontispiece: Distinct Helical Molecular Orbitals through Conformational Lock

Distinct Helical Molecular Orbitals through Conformational Lock*.

Several theoretical studies have proposed strategies to generate helical molecular orbitals (Hel-MOs) in [n]cumulenes and oligoynes. While chiral even-[n] cumulenes feature Hel-MOs, odd-[n] cumulenes may also present them if the terminal groups lie in different planes. However, the proposed systems have been either experimentally unfeasible or resulted in opposite pseudo-degenerated Hel-MOs. We hereby demonstrate the introduction of a remarkable energy difference between helical orbitals of opposite twist by fixing the torsion angle between the terminal groups in butadiyne fragments. To experimentally lock the conformation of the terminal groups, we designed and synthesized cyclic architectures by combining acetylenes with chiral spirobifluorenes. The high stability of these systems with distinct helical orbitals allowed their isolation and full characterization. In our view, these results constitute a step further in the development of real systems presenting helical molecular orbitals.

Correlation between Optical Activity and the Helical Molecular Orbitals of Allene and Cumulenes.

Helical frontier molecular orbitals (MOs) appear in disubstituted allenes and even-n cumulenes. Chiral molecules are optically active, but while these molecules are single-handed chiral, π-orbitals of both helicities are present. Here we computationally examine whether the optical activity of chiral cumulenes is controlled by the axial chirality or the helicity of the electronic structure. We exploit hyperconjugation with alkyl, silaalkyl, and germaalkyl substituents to adjust the MO helicity without altering the axial chirality. For the same axial chirality, we observe an inversion of the helical MOs contribution to the electronic transitions and a change of sign in the electronic circular dichroism and optical rotation dispersion spectra. While the magnitude of the chiroptical response also increases, it is similar to that of chiral cumulenes without helical π-orbitals. Overall, helical π-orbitals correlate with the big chiroptical response in cumulenes, but are not a prerequisite for it.

Reduced bond length alternation and helical molecular orbitals in donor and acceptor substituted linear carbon chains

Increasing chain length and end group substitution of polyynes play a crucial role in molecular electronics and nanomaterials. The studies on linear carbon chains are lesser when compared to other carbon allotropes like graphene, fullerenes, nanotube, etc. This prompted us to study the linear carbon chains of different lengths and substitutions. The electronic and optical properties of X–C[Formula: see text]–X ([Formula: see text]–15 and [Formula: see text], NH2, CN, OH) molecules have been studied by using CAM-B3LYP/6-31G* level of theory of DFT methods. Linear carbon chains with odd values of n show lower bond length alternation (BLA) values similar to that of cumulenes and may have metallic property, but the substitution of donor/acceptor molecules does not decrease the BLA significantly. Molecular orbital analysis of linear carbon chains shows that NH2 or NO2 substituted polyynes have helical molecular orbitals for smaller chain lengths which may make a good candidate for molecular wires in molecular devices. As the chain length increases, the helicity decreases and finally disappears. Also, it is seen that for smaller odd values of [Formula: see text] for donor, substituted polyynes have a singlet ground, whereas all the odd [Formula: see text] values of acceptor substitution have triplet ground state.

Helical molecular orbitals around straight-chain polyyne oligomers as models for molecular devices

Polyyne oligomers (H2CnH2), with CH2 group at each end of the oligomer, have been found to give helical molecular orbitals for the HOMO and LUMO and other molecular orbitals around the HOMO and LUMO when the two CH2 groups are tilted from their equilibrium positions. This can be explained by the changes in the symmetry of H2C2m+1H2 from D2d to D2, the former having degenerate molecular orbitals but the latter having non-degenerate orbitals. These helical molecular orbitals have been pointed out as being a kind of molecular device through which electrons pass.