Diboron-Doped Perylene-Based Polycyclic Aromatic Hydrocarbons for Enhancing Charge Transport: A Theoretical Perspective.

The enhancement of the optoelectronic properties of organic conjugation materials through boron doping may reshape current understanding, with boron-doped polycyclic aromatic hydrocarbons (PAHs) poised to be high-performance organic optoelectronic materials. However, the impact of boron doping on charge transport remains underexplored. In this study, the effects of diboron doping, including both dense and dispersed doping, along with further π-extension on the electronic structure, stacking pattern, and charge transport of perylene-based PAHs were systematically investigated using density-functional theory.

Theoretical Investigation of Novel Nitrogen-Heterocyclic Iridium(III) Polypyridyl Complexes as Photosensitizers for Two-Photon Photodynamic Therapy.

Two-photon photodynamic therapy (TP-PDT) has become a major cancer treatment due to its larger tissue penetration depth, good spatial selectivity, and less damage to normal cells. In this contribution, a series of novel photosensitizer molecules (, ∼) have been designed based on the experimentally demonstrated photosensitizer [Ir(ppy)(osip)] (PF) by fine tuning the π-conjugated structure and introducing different nitrogen-heterocyclic substituents. The electronic structures, one- and two-photon absorption spectra, triplet excited state lifetime, solvation-free energy, and photosensitizing performance were evaluated by means of density functional theory (DFT) and time-dependent density functional theory (TDDFT).

Theoretical Investigation and Molecular Design: A Series of Tripod-Type Cu(I) Blue Light Thermally Activated Delayed Fluorescence Materials.

The photophysical properties and luminescent mechanism of a series of tripod-type Cu(I) complexes in solution and solids were comprehensively investigated through theoretical simulations. From a microscopic perspective, the experimental phenomenon is explained: (1) The intrinsic reason for the quenching of complex in solution was attributed to the significant nonradiative transition caused by structural deformation; (2) In the solid, the reduced Δ for complex effectively facilitate reverse intersystem crossing (RISC) and improves its luminescence efficiency; (3) The enhanced performance of complex in solution is attributed to that its stronger steric hindrance is advantageous to decrease not only the Δ but also the reorganization energy through intramolecular weak interactions. Based on complex , the -butyl substituted isomeric complex was designed.

Rational design of anthocyanidins-directed near-infrared two-photon fluorescent probes.

Recently, two-photon fluorescent probes based on anthocyanidin molecules have attracted extensive attention due to their outstanding photophysical properties. However, there are only a few two-photon excited fluorescent probes that really meet the requirements of relatively long emission wavelengths (>600 nm), large two-photon absorption (TPA) cross-sections (300 GM), significant Stokes shift (>80 nm), and high fluorescence intensity. Herein, the photophysical properties of a series of anthocyanidins with the same substituents but different fluorophore skeletons are investigated in detail.

Molecular Design of Highly Efficient Heavy-Atom-free NpImidazole Derivatives for Two-Photon Photodynamic Therapy and ClO Detection.

Two-photon photodynamic therapy (TP-PDT), as a treatment technology with deep penetration and less damage, provides a broad prospect for cancer treatment. Nowadays, the development of TP-PDT suffers from the low two-photon absorption (TPA) intensity and short triplet state lifetime of photosensitizers (PSs) used in TP-PDT. Herein, we propose some novel modification strategies based on the thionated NpImidazole (the combination of naphthalimide and imidazole) derivatives to make efforts on those issues and obtain corresponding fluorescent probes for detecting ClO and excellent PSs for TP-PDT.

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.

Theoretical study of the tuning role of β-methylthio or β-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 β-methylselenyl on naphtho[1,2-:5,6-']dithiophene and anthra[2,3-:6,7-']dithiophene, respectively (anti-β-MS-NDT, anti-β-MS-ADT), which together with anti-β-MS-BDT synthesized experimentally all exhibited 2D brickwork π-stacking. Moreover, their maximum molecular carrier mobilities reached 3.

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.

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.

A Theoretical Investigation into the Homo- and Hetero-leptic Cu(I) Phosphorescent Complexes Bearing 2,9-dimethyl-1,10-phenanthroline and bis [2-(diphenylphosphino)phenyl]ether Ligand.

Cu(I) complexes have received widespread attention as a promising alternative to traditional noble-metal complexes. Herein, we systematically study the properties of Cu(I) complexes from homo- to hetero-ligands, and found the following: (1) hetero-ligands are beneficial to regulate phosphorescent efficiency; (2) when the hetero-ligands in a tetracoordinated Cu(I) complex are 1:1, the ligands coordinate along the d direction of Cu(I) ion, which can observably suppress structural deformation; (3) unlike the P^P ligand, the N^N ligand can enhance the participation of Cu(I) during the transition process; (4) the addition of an appropriate amount of P^P ligand can effectively raise the energy level of HOMO (highest occupied molecular orbital), enhance the proportion of LLCT (ligand-ligand charge transfer), and thereby increase the available singlet emission transition moments which can be borrowed, thus promoting the radiative decay process. As a result, this work provides a detailed understanding of the effects of different ligands in Cu(I) complexes, and provides a valuable reference and theoretical basis for regulating and designing the phosphorescent properties of Cu(I) complexes in the future.

Persistent and Efficient Multimodal Imaging for Tyrosinase Based on Two-Photon Excited Fluorescent and Room-Temperature Phosphorescent Probes.

Tyrosinase is crucial to regulate the metabolism of phenol derivatives, playing an important role in the biosynthesis of melanin pigments, whereas an abnormal level of tyrosinase would lead to severe diseases. It is rather necessary to develop a sensitive and selective imaging tool to assess the level of tyrosinase in vivo. We thoroughly researched the luminous mechanism of the existing TPTYR probe and provided design strategies to improve its two-photon excited fluorescence properties.

Theoretical Study of a Two-Photon Fluorescent Probe Based on Nile Red Derivatives with Controllable Fluorescence Wavelength and Water Solubility.

Hypochloric acid (HOCl) plays a vital role in the natural defense system, but abnormal levels of it can cause cell damage, accelerated human aging, and various diseases. It is of great significance to develop new probes for detecting HOCl in biosystems nondestructively and noninvasively. The purpose of this work is to explore new chemical modification strategies of two-photon excitation fluorescence (TPEF) probes to improve the poor water solubility and low efficiency in imaging applications.

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.

Impact of Δ on Delayed Fluorescence Rate, Lifetime, and Intensity Ratio of Tetrahedral Cu(I) Complexes: Theoretical Simulation in Solution and Solid Phases.

Profound understanding of the luminescence mechanism and structure-property relationship is vital for Cu(I) thermally activated delayed fluorescence (TADF) emitters. Herein, we theoretically simulated luminescent behavior in both solution and solid phases for two Cu(I) complexes and found the following: (i) The strengthened spin-orbit coupling (SOC) effect by more d orbital contributions and well-restricted structural distortion via remarkable intramolecular interaction in [Cu(dmp)(POP)] enable the emission at room temperature to be a mixture of direct phosphorescence (10%) and TADF (90%). (ii) Benefiting from enhanced steric hindrance and the electron-donating ability of the paracyclophane group, the narrowed S-T energy separation (Δ) in [Cu(dmp)(phanephos)] accelerates the reverse intersystem crossing, promoting the TADF rate (1.

Theoretical design and investigation of 1,8-naphthalimide-based two-photon fluorescent probes for detecting cytochrome P450 1A with separated fluorescence signal.

As a type of enzyme with a terminal oxygen, the CYP1A subfamily possesses the ability to catalyze the reactions of many environmental toxins, endogenous substrates and clinical drugs. The development of efficient methods for the rapid and real-time detection of CYP1A enzyme activity in complex biological systems is of considerable significance for identifying potential abnormalities in these cancer-related enzymes. With this goal, we firstly provided a series of 1,8-naphthalimide-based two-photon fluorescent chromophores with large two-photon absorption (TPA) cross-sections (500-7000 GM) and remarkable changes in fluorescence spectra upon recognizing the CYP1A enzyme from its theoretical aspect.

Understanding the effects of the number of pyrazines and their positions on charge-transport properties in silylethynylated N-heteropentacenes.

The charge-transport properties of a series of silylethynylated N-heteropentacenes (TIPS-PEN-xN; x = 2, 4) were systematically investigated using Marcus electron-transfer theory coupled with kinetic Monte Carlo simulations. Electronic structure calculations showed that introducing more pyrazine rings decreases the energy levels of the lowest unoccupied molecular orbitals (LUMOs) and should aid electron transfer. The number and the positions of the pyrazine rings greatly influence the molecular packing in crystals and hence the intermolecular electronic coupling.

Computational design of two-photon fluorescent probes for intracellular free zinc ions.

Two-photon fluorescence probes used in two-photon fluorescence microscopy (TPM) can achieve intact tissue imaging without destruction. Therefore, for a long time, TPM has been an important tool in biology and medicine. In this background via a quantum chemical method, a series of zinc ion probe molecules using N,N-di(2-picolyl)ethylenediamine (DPEN) as the recognition group were studied, which are based on the photoinduced electron transfer (PET) mechanism.

Computational design of two-photon fluorescent probes for a zinc ion based on a Salen ligand.

A two-photon fluorescent probe has become a critical tool in biology and medicine owing to its capability of imaging intact tissue for a long period of time, such as in two-photon fluorescence microscopy (TPM). In this context, a series of Salen-based zinc-ion bioimaging reagents that were designed based on an intramolecular charge-transfer mechanism were studied through the quantum-chemical method. The increase of one-photon absorption and fluorescence emission wavelength and the reduction of the oscillator strength upon coordination with a zinc ion reveal that they are fluorescent bioimaging reagents used for ratiometric detection.

A theoretical investigation of two typical two-photon pH fluorescent probes.

Intracellular pH plays an important role in many cellular events, such as cell growth, endocytosis, cell adhesion and so on. Some pH fluorescent probes have been reported, but most of them are one-photon fluorescent probes, studies about two-photon fluorescent probes are very rare. In this work, the geometrical structure, electronic structure and one-photon properties of a series of two-photon pH fluorescent probes have been theoretically studied by using density functional theory (DFT) method.

Nonlinear optical properties for a class of hexa-peri-hexabenzocoronene chromophores: a computational investigation.

The systematic investigation of the linear and nonlinear optical properties on such a class of hexa-peri-hexabenzocoronene (HBC) chromophores is of significance for rationally designing two-photon absorption (TPA) materials. The results indicate that increasing the strength of electron-donating or accepting terminal groups leads to bathochromic-shift of the absorption band and enhancement of the TPA cross section (δ(max)). For the molecules with fluorinated methylene and cyano substituents, replacement of a double bond by a triple bond in the conjugated linker produces the increase of δ(max), owing to the lower bond-length alternation and better rigidity of phenylene-ethynylene.

Theoretical insight into linear optical and two-photon absorption properties for a series of N-arylpyrrole-based dyes.

N-arylpyrrole-based dyes possessing excellent opto-electronic properties are promising candidates for two-photon fluorescence labeling materials. The systematic investigation of novel N-arylpyrrole derivatives is of great importance for both fine-tuning electronic spectra and designing two-photon absorption (2PA) materials. We thoroughly studied influences of the π-conjugated center and N-substituted pyrrole moieties on the linear optical and 2PA properties.

Theoretical prediction of one- and two-photon absorption properties of N-annulated quaterrylenes as near-infrared chromophores.

Graphene nanoribbons (GNRs) have attracted increasing attention due to high potentiality in nanoelectronics. In the present study, quantum-chemical calculations of structural and nonlinear optical properties have been first carried out for the nanoelectronical materials, a new series of ladder-type N-annulated quaterrylenes and their imide chromophores. The effects of the solvent, terminal groups, the number of N-annulated bridges, and π-conjugated length are discussed in detail.

Computational study of the electronic structures, UV-Vis spectra and static second-order nonlinear optical susceptibilities of macrocyclic thiophene derivatives.

Using thiophene (which has a moderate resonance energy) as a spacer rather than benzene permits better π-electron delocalization and leads to a large nonlinear optical response. Thus, the nonlinear optical coefficients of a series of macrocyclic thiophene derivatives (C[3T_DA](n) with C(n) symmetry) were studied, and their electronic structures, UV-Vis spectra and static second-order nonlinear optical susceptibilities (β(0)) were computed. The calculated results showed that ΔE(H-L) increased and the UV-Vis spectrum redshifted as the number of C[3T_DA] units increased (one C[3T_DA] unit consists of trithiophene and diacetylene).