Neutral and Oxidized Triisopropylsilyl End‐Capped Oligothienoacenes: A Combined Electrochemical,Spectroscopic, and Theoretical Study

This work presents an analysis of the structural, electrochemical, and optical properties of a family of triisopropylsilyl end‐capped oligothienoacenes (TIPS‐ Tn ‐TIPS, n=4–8) by combining cyclic voltammetry, spectroscopic techniques, and quantum‐chemical calculations. TIPS‐ Tn ‐TIPS compounds form stable radical cations, and dications are only obtained for the longest oligomers (n=7 and 8). Oxidation leads to the quinoidization of the conjugated backbone, from which electrons are mainly extracted. The absorption and fluorescence spectra show partially resolved vibronic structures even at room temperature, due to the rigid molecular geometry. Two well‐resolved vibronic progressions are observed at low temperatures due to the vibronic coupling, with normal modes showing wavenumbers of ≈1525 and ≈480 cm^?1. Optical absorption bands display remarkable bathochromic dispersion with the oligomer length, indicative of the extent of π conjugation. The optical properties of the oxidized compounds are characterized by in situ UV/Vis/NIR spectroelectrochemistry. The radical cation species show two intense absorption bands emerging at energies lower than in the neutral compounds. The formation of the dication is only detected for the heptamer and the octamer, and shows a new band at intermediate energies. Optical data are interpreted with the help of density functional theory calculations performed at the B3LYP/6‐31G** level, both for the neutral and the oxidized compounds.     

The sensing mechanism of fluoride anion for a novel molecule D2: Desilylation and intramolecular charge transfer

In this work, the sensing mechanism of a new fluoride chemosensor 12‐([tert‐butyldiphenylsilyl]oxy)‐8a,13a‐dihydro‐7H‐benzo[de]benzo[4,5]imidazo[2,1‐a]‐isoquinolin‐7‐one (abbreviated as D2) is investigated using density functional theory (DFT) and time‐dependent DFT (TDDFT) methods. The theoretical electronic spectra (vertical excitation energies and fluorescence peak) reproduced previous experimental results (D. Li et al., Spectrochim. Acta A Mol. Biomol. Spectrosc. 2017 , 185, 173), which confirms the rationality of the theoretical level used in this work. The constructed potential energy curve of the desilylation process suggests that the low barrier could be responsible for the rapid response to fluoride anions. Analyses of the binding energies show that only fluoride anion can be detected by D2 chemosensor in dimethylsulfoxide (DMSO). In view of the excitation process, the strong intramolecular charge transfer (ICT) process of the S₀ → S₁ transition explains the red shift of the absorption peak of the D2 sensor with the addition of fluoride anions. This work not only presents a straightforward sensing mechanism of sensing of the fluoride anion by the D2 chemosensor but should also play an important role in the synthesis and design of fluorescent sensors in future.     

Intensely Fluorescent Azobenzenes: Synthesis,Crystal Structures,Effects of Substituents,and Application to Fluorescent Vital Stain

2‐[Bis(pentafluorophenyl)boryl]azobenzenes bearing hydrogen, methoxy, dimethylamino, trifluoromethyl, fluoro, n‐butyl, and tert‐butyldimethylsiloxy groups at the 4′‐position or methoxy and bromo groups at the 4‐position have been synthesized. The 4‐bromo group of the 2‐boryl‐4‐bromoazobenzene derivative was converted to phenyl and diphenylamino groups by palladium‐catalyzed reactions. The absorption and fluorescence properties have been investigated using UV/Vis and fluorescence spectroscopy. The 2‐borylazobenzenes emitted an intense green, yellow, and orange fluorescence, in marked contrast to the usual azobenzene fluorescence. The 4′‐siloxy derivative showed the highest fluorescence quantum yield (0.90) among those reported for azobenzenes to date. The correlation between the substituent and the fluorescence properties was elucidated by studying the effect of the substituent on the relaxation process and from DFT and TD‐DFT calculations. An electron‐donating group at the 4′‐position was found to be important for an intense emission. Application of fluorescent azobenzenes as a fluorescent vital stain for the visualization of living tissues was also investigated by microinjection into Xenopus embryos, suggesting these compounds are nontoxic towards embryos.     

Charge-transfer transitions in triarylamine mixed-valence systems: a joint density functional theory and vibronic coupling study

A theoretical model is developed to describe the intramolecular transfer in organic mixed-valence systems. It is applied to rationalize the intervalence charge-transfer transitions in triarylamine mixed-valence compounds. The electronic coupling parameter is evaluated at the density functional theory (DFT) and time-dependent density functional theory (TD-DFT) levels. The shapes of the charge-transfer absorption bands are analyzed in the framework of a dynamic vibronic model. The influence on the optical properties of diagonal and nondiagonal vibronic couplings is discussed. Our results are compared to recent experimental data.     

Investigation of the spectral,optical and surface morphology properties of the N,N′‐Dipentyl‐3,4,9,10‐perylenedicarboximide small molecule for optoelectronic applications

The spectral and optical properties of the solutions of the N,N′‐Dipentyl‐3,4,9,10‐perylenedicarboximide (PTCDI‐C5) small molecule for different molarities were investigated in detail. The significant spectral parameters such as molar/mass extinction coefficients, absorption coefficient, electric dipole line strength, and oscillator strength of the PTCDI‐C5 molecule were calculated. The absorption bands of PTCDI‐C5 show vibronic structures with seven peaks at 2.08, 2.35, 2.53, 2.70, 2.86, 3.32, and 3.86 eV, respectively. The electronic spectra of the PTCDI‐C5 can be characterized by two basic regions as visible and Soret band. Effects of the molarities on the significant many optical parameters were investigated in detail. The direct and indirect allowed optical band gaps of the PTCDI‐C5 decrease with increasing molarity. Then, surface morphology properties were investigated and calculated roughness parameters of the PTCDI‐C5 film. Finally, we discussed for optoelectronic applications of these parameters, and this study was compared with the similar and related studies in the literature. Copyright © 2015 John Wiley & Sons, Ltd.     

Theoretical Studies on the Electronic and Optical Properties of a New Class of Aromatic Oligomers and Polymers

The purpose of this work is to provide an in‐depth interpretation of the optical and electronic properties of a series of aromatic oligomers and polymers, including [N‐(4‐(5‐(3‐(1,3,4‐oxadiazol‐2,5‐ylene)phenyl)‐1,3,4‐oxadiazol‐2‐ylene)phenyl)‐N‐(1,4‐phenylene)amine]_n (NPPP)_n and [N‐(4‐(5‐(3‐(1,3,4‐oxadiazol‐2,5‐ylene)phenyl)‐1,3,4‐oxa‐diazol‐2‐ylene)phenyl)‐N‐(1,4‐phenylene)naphthalene‐1‐amine]_n (NPPN)_n (n=1–4). These polymers and oligomers show great potential for application to organic light‐emitting diodes (OLEDs) as efficient blue emitters due to the tuning of the optical and electronic properties. The geometric and electronic structures of the oligomers in the ground state were investigated using density functional theory (DFT) and the ab initio HF, whereas the lowest singlet excited state of NPPP₁ was optimized with ab initio configuration interaction singles (CIS). To assign the absorption and emission peaks observed in the experiment, the absorption and emission spectra of the ground and lowest singlet excited states were calculated with time‐dependent DFT (TD‐DFT) and Zerner's independent neglect of differential overlap (ZINDO). All DFT calculations were performed using the B3LYP functional and the 6‐31G basis set. The results show that the HOMO, LUMO, energy gaps, ionization potentials, and electron affinities for these polymers are affected by increasing the conjugated chain, which favors the hole and electron injection into OLED. The trend of the variation of Δ_H‐L and the lowest excitation energies with 1/n, and the electronic structure and optical properties of these polymers were extrapolated and analyzed. The absorption spectra exhibit red shifts to some extent [the absorption spectra: 359.47 (NPPP₁)<370.84 (NPPP₂)<373.84 (NPPP₃)<375.33 nm (NPPP₄); 361.14 (NPPN₁)<370.34 (NPPN₂)<373.39 (NPPN₃)<374.62 nm (NPPN₄)]. Our calculated spectra agree well with the experimental findings where available, showing small but systematic deviations.     

Synthesis,spectral, DFT calculations and antibacterial studies of Fe(III) complexes of new fluorescent Schiff bases derived from imidazo[4',5':3,4]benzo[1,2‐c]isoxazole

New fluorescent heterocyclic ligands were synthesized by the reaction of 8‐(4‐chlorophenyl)‐3‐alkyl‐3H‐imidazo[4',5':3,4]benzo [1,2‐c]isoxazol‐5‐amine with p‐hydroxybenzaldehyde and p‐chlorobenzaldehyde in good yields. The coordination ability of the ligands with Fe³⁺ ion was examined in an aqueous metanolic solution. Schiff base ligands and their metal complexes were characterized by elemental analyses, IR, UV–vis, mass, and NMR spectra. The optical properties of the compounds were investigated and the results showed that the fluorescence of all compounds is intense and their obtained emission quantum yields are around 0.15 – 0.53. Optimized geometries and assignment of the IR bands and NMR chemical shifts of the new complexes were also computed by using density functional theory (DFT) methods. The DFT‐calculated vibrational wavenumbers and NMR chemical shifts are in good agreement with the experimental values, confirming suitability of the optimized geometries for Fe(III) complexes. Also, the 3D‐distribution map for HOMO and LUMO of the compounds were obtained. The new compounds showed potent antibacterial activity and their antibacterial activity (MIC) against Gram‐positive and Gram‐negative bacterial species were also determined. Results of antibacterial test revealed that coordination of ligands to Fe(III) leads to improvement in the antibacterial activity.     

Impact of the Synergistic Collaboration of Oligothiophene Bridges and Ruthenium Complexes on the Optical Properties of Dumbbell‐Shaped Compounds

The linear and non‐linear optical properties of a family of dumbbell‐shaped dinuclear complexes, in which an oligothiophene chain with various numbers of rings (1, 3, and 6) acts as a bridge between two homoleptic tris(2,2′‐bipyridine)ruthenium(II) complexes, have been fully investigated by using a range of spectroscopic techniques (absorption and luminescence, transient absorption, Raman, and non‐linear absorption), together with density functional theory calculations. Our results shed light on the impact of the synergistic collaboration between the electronic structures of the two chemical moieties on the optical properties of these materials. Experiments on the linear optical properties of these compounds indicated that the length of the oligothiophene bridge was critical for luminescent behavior. Indeed, no emission was detected for compounds with long oligothiophene bridges (compounds 3 and 4 , with 3 and 6 thiophene rings, respectively), owing to the presence of the ³π? π* state of the conjugated bridge below the ³MLCT‐emitting states of the end‐capping Ru^II complexes. In contrast, the compound with the shortest bridge ( 2 , one thiophene ring) shows excellent photophysical features. Non‐linear optical experiments showed that the investigated compounds were strong non‐linear absorbers in wide energy ranges. Indeed, their non‐linear absorption was augmented upon increasing the length of the oligothiophene bridge. In particular, the compound with the longest oligothiophene bridge not only showed strong two‐photon absorption (TPA) but also noteworthy three‐photon‐absorption behavior, with a cross‐section value of 4×10^?78 cm⁶ s² at 1450 nm. This characteristic was complemented by the strong excited‐state absorption (ESA) that was observed for compounds 3 and 4 . As a matter of fact, the overlap between the non‐linear absorption and ESA establishes compounds 3 and 4 as good candidates for optical‐power‐limiting applications.     

A Combined Experimental and Computational Study of Linear Ruthenium(II) Coordination Oligomers with End‐Capping Organic Redox Sites: Insight into the Light Absorption and Charge Delocalization

Two series of linear ruthenium coordination oligomers, [(Ntpy)Ru_n(tppz)_n?1(tpy)]²ⁿ⁺ (mono‐Ntpy series, n=1–3) and [(Ntpy)₂Ru_n(tppz)_n?1]²ⁿ⁺ (bis‐Ntpy series, n=1–3) have been prepared, where Ntpy is the capping ligand 4′‐di‐p‐anisylamino‐2,2′:6′,2′′‐terpyridine, tppz is tetra‐2‐pyridylpyrazine, and tpy is 2,2′:6′,2′′‐terpyridine. The electrochemical measurements evidence oxidation events from both the amine segments and the metal centers and reduction waves from tppz and the capping ligands. Both series complexes display much enhanced light absorption with respect to model complexes without terminal amine units. Density functional theory (DFT) calculations have been performed on both series and time‐dependent DFT (TD‐DFT) calculations have been performed on the bis‐Ntpy‐series compounds (n=1–4) to characterize their electronic structures and excited states and predict the electronic properties of long‐chain polymers. Upon one‐electron oxidation, the mono‐Ntpy‐series monoruthenium and diruthenium complexes display N⁺‐localized transitions and metal‐to‐nitrogen charge‐transfer (MNCT) transitions in the near‐infrared (NIR) region. DFT and TD‐DFT computations on the one‐electron‐oxidized forms of the mono‐Ntpy‐series compounds (n=1–4) provide insight into the nature of the MNCT transitions and the degree of charge delocalization.     

The Quest for Photoswitches Activated by Near‐Infrared Light: A Theoretical Study of the Photochemistry of BF2‐Coordinated Azo Derivatives

Recently synthesized BF₂‐coordinated azo derivatives have been proposed as photoswitches that operate in the optical window (λ=600–1200 nm) for use in bioimaging applications. Herein, we have theoretically analyzed these compounds and modified some substituents to analyze which properties of the molecule govern its photochemistry. Our results compare rather well with the available experimental data, so our methodology, based on density functional theory (DFT) calculations for the ground electronic state and time‐dependent‐DFT for the first excited electronic state, is validated. Through systematic modification of different substituents of the parent system, we designed compounds that are predicted to operate fully within the optical window. We also analyzed several molecules for which the cis isomer is the more stable isomer, a quite unusual result for azobenzene derivatives that is a much coveted property for some applications of these photoactive molecules in pharmacology. Our results also provide insight into other properties relevant for photoswitches, such as the thermal stability of the less stable isomer and the magnitude of the gap between the wavelengths of the radiation that activates each isomerization process, which must be as large as possible to improve the yield of each photoisomerization. From a more general perspective, our results may provide a step towards the rational design of new photoswitches that fulfill a set of desired characteristics.     

Thieno[3,4‐b]pyrazine‐based low bandgap photovoltaic copolymers: Turning the properties by different aza‐heteroaromatic donors

A new series of low‐bandgap copolymers based on electron‐accepting thieno[3,4‐b]pyrazine (TPZ) and different electron‐donating aza‐heteroaromatic units, such as carbazole (CZ), dithieno[3,2‐b:2′,3′‐d]pyrrole (TPR) and dithieno[3,2‐b:2′,3′‐e]pyridine (TPY), have been synthesized by Suzuki or Stille coupling polymerization. The resulting copolymers were characterized by NMR, elemental analysis, gel permeation chromatography, thermogravimetric analysis, and differential scanning calorimetry. UV–vis absorption and cyclic voltammetry measurements show that TPZ‐based copolymer with TPR has the best absorption due to the strongest intramolecular charge transfer effect and smallest bandgap. The basic electronic structure of D‐A model compounds of these copolymers were also studied by density functional theory (DFT) calculations. The conclusion of calculation agreed also well with the experimental results. The polymer solar cells (PSCs) based on these copolymers were fabricated with a typical structure of ITO/PEDOT:PSS/copolymer:PC₇₁BM/Ca/Al under the illumination of AM 1.5G, 100 mW cm^?2. The performance results showed that TPZ‐based copolymer with TPR donor segments showed highest efficiency of 1.55% due to enhanced short‐circuit current density. The present results indicate that good electronic, optical, and photovoltaic properties of TPZ‐based copolymers can be achieved by just fine‐tuning the structures of aza‐heteroaromatic donor segments for their application in PSCs. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Luminescent compounds diphenylboron analogs of Alq3 and its methyl substituents: A theoretical investigation of their electronic and spectroscopic properties

The absorption and emission energies for diphenylboron analogs of Alq₃ (Ph₂Bq) and its methyl substituents (Ph₂Bmq) were systematically investigated at the Zerner's intermediate neglect of differential overlap (ZINDO), configuration interaction singles (CIS), and time‐dependent density functional theory (TD‐DFT) levels of theory. The lowest excited‐state geometries were optimized at the ab initio CIS level. The TD‐DFT method provides the most reliable results for the absorption and emission transition energies, compared with other methods. Moreover, the TD‐DFT calculations reliably estimate the changes of absorption and emission λ_max values upon methyl substitution, with errors of 1.2% and 1.8%, respectively. The Stokes shifts are well reproduced by TD‐DFT calculations. Various density functional theory methods have been tested and the B3LYP functional clearly seems to be the best choice for this class of compounds. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

On the Origin of the Visible‐Light Activity of Titanium Dioxide Doped with Carbonate Species

Plane‐wave‐based pseudopotential density functional theory (DFT) calculations are used to elucidate the origin of the high photocatalytic efficiency of carbonate‐doped TiO₂. Two geometrically possible doping positions are considered, including interstitial and substitutional carbon atoms on Ti sites. From the optical absorption properties calculations, we believe that the formation of carbonates after doping with interstitial carbon atoms is crucial, whereas the contribution from the cationic doping on Ti sites is negligible. The carbonate species doped TiO₂ exhibits excellent absorption in the visible‐light region of 400–800 nm, in good agreement with experimental observations. Electronic structure analysis shows that the carbonate species introduce an impurity state from Ti 3d below the conduction band. Excitations from the impurity state to the conduction band may be responsible for the high visible‐light activity of the carbon doped TiO₂ materials.     

Study of Electronic,Optical Absorption and Emission in Pure and Metal‐Decorated Graphene Nanoribbons (C29H14‐X; X=Ni,Fe, Ti,Co+, Al+, Cu+): First Principles Calculations

Density functional theory (DFT) and time‐dependent density functional theory (TDDFT) calculations were performed with the basis sets 6‐31G for DFT and 6‐31G(d), 6‐31+G(d,p) for TDDFT on pure graphene nanoribbon (GNR) C₃₀H₁₄ and metal‐decorated C₂₉H₁₄‐X (MGNRs; X=Ni, Fe, Ti, Co⁺, Al⁺, and Cu⁺). The metal/carbon ratio (X:C 3.45 %) and the doping site were fixed. Electronic properties, that is, the dipole moment, binding energy, and HOMO–LUMO gaps, were calculated. The absorption and emission properties in the visible range (λ=400–720 nm) were determined. Optical gaps, absorption and emission wavelengths, oscillator strengths, and dominant transitions were calculated. Pure graphene was found to be the most stable form. However, of the MGNRs, C₂₉H₁₄?Co⁺ and C₂₉H₁₄?Al⁺ were found to be the most and least stable, respectively. All GNRs were found to have semiconducting nature. The optical absorption of pure graphene undergoes a shift on metal doping. Emission from the pure graphene followed Kasha′s rule, unlike the metal‐doped GNRs.     

Preparation,crystal structure,spectroscopic studies,DFT calculations,antibacterial activities and molecular docking of a tridentate Schiff base ligand and its cis‐MoO2 complex

We synthesized a tridentate Schiff base ligand, 6‐(((2‐hydroxyphenyl)amino)methylene)‐2‐methoxycyclohexa‐2,4‐dienone [H₂L], as well as its Mo(VI) complex [MoO₂(L)(DMSO)], and then characterized them completely using elemental analysis, FT‐IR, UV–Vis and ¹HNMR spectroscopy techniques. X‐ray single crystal diffraction method was used for the determination of the structure of the synthesized ligand and complex. All other spectroscopic techniques performed, confirmed that [MoO₂(L)(DMSO)]had an octahedral geometry around the Mo(VI) central ion coordinated by the donor atoms of the deprotonated ligand, two oxido groups and one oxygen atom of DMSO molecule. Hybrid functional B3LYP with DGDZVP as basis set was applied for DFT calculations of the compounds in their ground state. The MEP, Mulliken, HOMO‐LUMO energy gap and thermodynamic properties of the compounds were also theoretically predicted. In‐vitro antimicrobial studies on the synthesized compounds indicated the great antibacterial activities of the Mo(VI) complex against Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa and Bacillus cereus bacteria.     

Electronic structure and spectroscopic properties of 6‐aminophenanthridine and its derivatives: Insights from density functional theory

6‐Aminophenanthridine (6AP) and its derivatives show important biological activities as antiprion compounds and inhibitors of the protein folding activity of the ribosome. Both of these activities depend on the RNA binding property of these compounds, which has been recently characterized by fluorescence spectroscopy. Hence, fundamental insights into the photophysical properties of 6AP compounds are highly important to understand their biological activities. In this work, we have calculated electronic structures and optical properties of 6AP and its three derivatives 6AP8CF₃, 6AP8Cl, and 6APi by density functional theory (DFT) and time‐dependent density functional theory (TDDFT). Our calculated spectra show a good agreement with the experimental absorption and fluorescence spectra, and thus, provide deep insights into the optical properties of the compounds. Furthermore, comparing the results obtained with four different hybrid functionals, we demonstrate that the accuracy of the functionals varies in the order B3LYP > PBE0 > M062X > M06HF. © 2015 Wiley Periodicals, Inc.     

DFT/TDDFT Studies on the Electronic Structures and Spectral Properties of Carbazole‐based Blue Light‐emitting Dendrimers

The purpose of this paper is to provide an in‐depth investigation of the electronic and optical properties of two series of carbazole‐based blue light‐emitting dendrimers, including 1 – 6 six oligomers. These materials show great potential for application in organic light‐emitting diodes as efficient blue‐light and red‐light emitting materials due to the tuning of the optical and electronic properties by the use of different electron donors (D) and electron acceptors (A). The geometric and electronic structures of these compounds in the ground state are calculated using density functional theory (DFT) and the ab initio HF, whereas the lowest singlet excited states were optimized by ab initio single excitation configuration interaction (CIS). All DFT calculations are performed using the B3LYP functional on 6‐31G* basis set. The outcomes show that the highest occupied molecular orbitals (HOMOs), lowest occupied molecular orbitals (LUMOs), energies gaps, ionization potentials, electron affinities and reorganization energies of each molecular are affected by different D and A moieties and different substitute positions.     

Theoretical insights into the absorption and emission properties of blue luminescent copper(I) complexes based on the pyrazolyl‐pyridine ligands

The ground geometrical and electronic structures, charge transfer (CT) behaviors, absorption, and emission properties of the three copper(I) complexes [Cu(pypz)(POP)]⁺ (1) , [Cu(pympz)(POP)]⁺ (2) , and [Cu(pytfmpz)(POP)]⁺ (3) (pypz=1‐(2‐pyridyl)pyrazole, pympz=3‐methyl‐1‐(2‐pyridyl)pyrazole, and pytfmpz=3‐trifluoromethyl‐1‐(2‐pyridyl)pyrazole), have been investigated using density functional theory (DFT) and time‐dependent density functional theory (TD‐DFT). The vertical absorption energies of the all copper(I) complexes are well reproduced by TD‐DFT calculations based on the CT amount calculations. The triplet emission properties of the all copper(I) complexes were correctly evaluated at BMK/LANL2DZ/6‐31G* level of theory. In addition, the thermally activated delayed fluorescence properties of 1–3 were discussed in detail based on the spatial separation of the HOMO and LUMO and vertical excited energies. These theoretical insights should be expected to provide some guides for the design and synthesis of efficient luminescent copper(I) complexes. © 2014 Wiley Periodicals, Inc.     

Chemically modified fullerene derivatives as photosensitizers in photodynamic therapy: A first‐principles study

The first‐principles density functional theory (DFT) and its time‐dependent approach (TD‐DFT) are used to characterize the electronic structures and optical spectra properties of five chemically modified fullerenes. It is revealed that the metal fullerene derivatives possess not only stronger absorption bands in visible light regions than organically modified fullerene but also the large energy gaps (ΔE_S–T > 0.98 eV) between the singlet ground state and the triplet state, which imply their significant aspect of potential candidates as a photosensitizer. We have found that a new metal‐containing bisfullerene complexes (Pt(C₆₀)₂), with the extended conjugated π‐electrons, much degenerate orbitals and a uniform electrostatic potential surface, behave more pre‐eminent photosensitizing properties than other examined fullerene derivatives. © 2012 Wiley Periodicals, Inc.