In-depth theoretical analysis of the influence of an external electric field on charge transport parameters.

It is important to develop materials with environmental stability and long device shelf life for use in organic field-effect transistors (OFETs). The microscopic, molecular-level nature of the organic layer in OFETs is not yet well understood. The stability of geometric and electronic structures and the regulation of the external electric field (EEF) on the charge transport properties of four typical homogeneous organic semiconductors (OSCs) were investigated by density functional theory (DFT). The results showed that under the EEF, the structural changes in single-bond linked oligomers were more sensitive and complex than those of condensed molecules, and there were non-monotonic changes in their reorganization energy (λ) during charge transport under an EEF consisting of decreases and then increases (Series D). The change in λ under an EEF can be preliminarily and qualitatively determined by the change in the frontier molecular orbitals (FMOs) - the number of C-atoms with nonbonding characteristics. For single-bonded molecules, the transfer integral is basically unchanged under a low EEF, but it will greatly change at a high EEF. Because the structure and properties of the molecule will greatly change under different EEFs, the effect of an EEF should be fully considered when determining the intrinsic mobility of OSCs, which could cause a deviation 0.3-20 times in mobility. According to detailed calculations, one heterogeneous oligomer, TH-BTz, was designed. Its λ can be greatly reduced under an EEF, and the change in the energy level of FMOs can be adjusted to different degrees. This study provides a reasonable idea for verification of the experimental mobility value and also provides guidance for the directional design of stable high-mobility OSCs.

Theoretical insight on the charge transport properties: The formation of "head-to-tail" and "head-to-head" stacking of asymmetric aryl anthracene derivatives.

Organic semiconductors (OSCs) are widely used in flexible display, renewable energy, and biosensors, owing to their unique solid-state physical and optoelectronic properties. Among the abundant crystal library of OSCs, asymmetric aryl anthracene derivatives have irreplaceable advantages due to the interplay between their distinct π-conjugated geometry and molecular stacking as well as efficient light emission and charge transport properties that can be simultaneously utilized. However, the poor crystal stacking patterns of most asymmetric molecules limit their utility as excellent OSCs. Thus, it is crucial to clarify the structural features that enable the extremely ordered stacking and favorable electronic structure of asymmetric anthracene derivatives to become high-performance OSCs. This contribution investigates the charge transport properties of a series of asymmetric aryl anthracene derivatives to reveal the modulation factors of the molecular stacking modes and to explore the structural factors, which are beneficial to charge transport. The analysis demonstrated that the vinyl-linker facilitated the injection of hole carriers, and the alkynyl-linker effectively reduces the reorganization energy. Importantly, the linear polarizability and permanent dipole moment of a single molecule play a vital regulation to molecular stacking modes and the transfer integral of the dimer. The "head-to-head stacking" motif shows a compact stacking pattern and the maximum 2D anisotropic mobility more than 10 cm2 V-1 s-1. These findings sharpen our understanding of the charge transport properties in asymmetric organic semiconductors and are essential for developing a diverse range of high-performance OSC materials.

Theoretical Investigation of Ru(II) Complexes with Long Lifetime and a Large Two-Photon Absorption Cross-Section in Photodynamic Therapy.

Two-photon photodynamic therapy (TP-PDT), as a new method for cancer, has shown unique advantages in tumors. A low two-photon absorption cross-section (δ) in the biologic spectral window and a short triplet state lifetime are the important issues faced by the current photosensitizers (PSs) in TP-PDT. In this paper, the photophysical properties of a series of Ru(II) complexes were studied by density functional theory and time-dependent density functional theory methods. The electronic structure, one- and two-photon absorption properties, type I/II mechanisms, triplet state lifetime, and solvation free energy were calculated. The results showed that the substitution of methoxyls by pyrene groups greatly improved the lifetime of the complex. Furthermore, the addition of acetylenyl groups subtly enhanced δ. Overall, complex 3b possess a large δ(1376 GM), a long lifetime (136 µs), and better solvation free energy. It is hoped that it can provide valuable theoretical guidance for the design and synthesis of efficient two-photon PSs in the experiment.

Theoretical study of the tuning role of ß-methylthio or ß-methylselenyl on the charge-transport properties of acenedithiophenes derivatives.

To date, the manipulation of intermolecular nonconjugation interactions in organic crystals is still a great challenge due to the complexity of weak intermolecular interactions. Here we designed molecules substituted by ß-methylselenyl on naphtho[1,2-b:5,6-b']dithiophene and anthra[2,3-b:6,7-b']dithiophene, respectively (anti-ß-MS-NDT, anti-ß-MS-ADT), which together with anti-ß-MS-BDT synthesized experimentally all exhibited 2D brickwork π-stacking. Moreover, their maximum molecular carrier mobilities reached 3.30 and 16.46 cm2 V-1 s-1. These results indicated that the substitution of ß-methylselenyl could be a strategy to directionally adjust the parent herringbone stacking into 2D brickwork π-stacking. Hirshfeld surface analysis and symmetry-adapted perturbation theory (SAPT) were used to investigate the nonconjugated interactions in the pitched π-stacking formed by the ß-methylthio-substituted acenedithiophene derivatives and the 2D brickwork π-stacking of the ß-methylselenyl-substituted ones; wherein, the steric hindrance caused by the introduction of the substituents promoted Csp2-Csp2⋯π interactions to replace Csp2-H⋯π to stabilize the face-to-face stacking. Moreover, by calculating the decomposition energy of the intermediate state model of the molecular stacking mode that may exist in the replacement conversion process, it was found that the energy of this intermediate state was larger than that of the actual ones, finally confirming the inevitability of the actual existence in this stacking. In addition, because of the reduction in intensity of the special vibration modes, it could be found that the ß-methylselenyl substitution showed better phonon assistance than ß-methylthio substitution in terms of dynamic disorder. This study is a further step toward fully understanding the relationship between intermolecular interactions and regulation of the molecular stacking.

Photophysical Exploration of Zn(II) Polypyridine Photosensitizers in Two-Photon Photodynamic Therapy: Insights from Theory.

The high incidence and difficulties of treatment of cancer have always been a challenge for mankind. Two-photon photodynamic therapy (TP-PDT) as a less invasive technique provides a new perspective for tumor treatment due to its low-energy near-infrared excitation, high targeting, and minor damage. At present, the emerging metal complexes used as the photosensitizers (PSs) in TP-PDT have aroused great interest. However, most metal complexes as PSs in TP-PDT still face some problems, such as slow clearance, unsatisfactory two-photon absorption (TPA) characteristics, high price, low reactivity, and poor solubility. In this work, density functional theory and time-dependent density functional theory were used to characterize the one/two-photon response, solvation free energy, and lipophilicity of a series of novel PSs applied in TP-PDT. The results suggest that based on complex 1, replacing Ru(II) center with Zn(II) (complex 2) can effectively prolong the triplet excited state lifetime while reducing the cost and environmental pollution, and the azetidine heterospirocycles were introduced into the ligand scaffold (complex 3), which effectively reduced the vibration relaxation of the ligand group and improved the water solubility; further, the addition of acetylenyl groups subtly enhanced the light absorption and significantly improved the two-photon response (complex 4). In addition, all complexes met the requirement of a PS and could be used as potential candidates for TP-PDT. In particular, complex 4 has the advantages of high solvation free energy, a large TPA cross-section (1413 GM), a long triplet state lifetime (671 µs), good chemical reactivity, and low cost, and it is easy to be scavenged by organisms. Overall, this contribution may provide an important clue to formulate clear design principles for type I/II PSs and rational design of PSs with high intersystem crossing rates, a long lifetime, and therapeutic excitation wavelengths.

Theoretical investigations on the charge transport properties of anthracene derivatives with aryl substituents at the 2,6-position-thermally stable "herringbone" stacking motifs.

High-performance organic semiconductor materials based on the small aromatic anthracene-core and its derivatives develop comparatively slowly due to the lack of a profound understanding of the influence of chemical modifications on their charge-transfer properties. Herein, the electronic properties and the charge transport characteristics of several typical anthracene-based derivatives with aryl groups substituted at the 2,6-site are systematically investigated by multi-scale simulation methods including Molecular Dynamics (MD) simulation and the full quantum nuclear tunneling model in the framework of density functional theory (DFT). To elucidate the origin of different charge transport properties of these anthracene-based materials, analysis of the molecular stacking and noncovalent intermolecular interaction caused by different substituents was carried out. The results indicate that the electron and hole injection capabilities and the air oxidation stability of the anthracene derivatives are greatly improved when the size of the aryl substituent increases. In addition, the incorporation of 2,6-site aryl substituents can inhibit the stretching vibration of the anthracene-core during charge transport, and allow molecular packing along the long axis (a-axis of DPA and BDBFAnt, and c-axis of dNaAnt) with almost no slippage, and the main transport channels remain unchanged, exhibiting more isotropic 2D transport properties. It should be emphasized that the edge-to-face dimers with smallest dihedral angles are closest to the thermally stable dimer model, with relatively larger π-orbital distributions in transmission channels (dimer 1, 2) and the largest spatial overlap, resulting in the largest hole transfer integral in DPA (Vh1/h2 = 57 meV). Although the analysis of the thermal disorder effect shows a phonon scattering effect, the maximum hole mobility of the DPA molecule is still as high as 1.5 cm2 V-1 s-1.

Theoretical Investigations into the Electron and Ambipolar Transport Properties of Anthracene-Based Derivatives.

To obtain anthracene-based derivatives with electron transport behavior, two series of anthracene-based derivatives modified by trifluoromethyl groups (-CF3) and cyano groups (-CN) at the 9,10-positions of the anthracene core were studied. Their electronic structures and crystal packings were also analyzed and compared. The charge-carrier mobilities were evaluated by quantum nuclear tunneling theory based on the incoherent charge-hopping model. Our results suggest that introducing -CN groups at 9,10-positions of the anthracene core is more favorable than introducing -CF3 to maintain great planar rigidity of the anthracene skeleton, decreasing more lowest unoccupied molecular orbital energy levels (0.45-0.55 eV), reducing reorganization energies, and especially forming a tight packing motif. Eventually, the excellent electron transport materials could be obtained. The molecule 1-B in Series 1 containing -CF3 groups is an ambipolar organic semiconductor (OSC) material with a 2D transport network, and its value of µh-max/µe-max is 1.75/0.47 cm2 V-1 s-1 along different directions; 2-A and 2-C in Series 2 with -CN groups are excellent n-type OSC candidates with the maximum intrinsic mobilities of 3.74 and 2.69 cm2 V-1 s-1 along the π-π stacking direction, respectively. Besides, the Hirshfeld surface and quantum theory of atoms in molecules analyses were applied to reveal the relationship between noncovalent interactions and crystal stacking.