Intramolecular Charge Transfer Transition Research Articles

Design of Isoindigo-Based Small-Molecule Donors for Bulk Heterojunction Organic Solar Cell Applications in Combination with Nonfullerene Acceptors.

The development of small-molecule organic solar cells with the required efficiency depends on the information obtained from molecular-level studies. In this context, 39 small-molecule donors featuring isoindigo as an acceptor moiety have been meticulously crafted for potential applications in bulk heterojunction organic solar cells. These molecules follow the D2-A-D1-A-D2 and D2-A-π-D1-π-A-D2 framework. Similar molecules considered in the previous experimental study (molecules R1 ((3E,3″E)-6,6″-(benzo[1,2-b:4,5-b']dithiophene-2,6-diyl)bis(1,1'-dimethyl-[3,3'-biindolinylidene]-2,2'-dione)) and R2 ((3E,3″E)-6,6″-(4,8-dimethoxybenzo[1,2-b:4,5-b']dithiophene-2,6-diyl)bis(1,1'-dimethyl-[3,3'-biindolinylidene]-2,2'-dione))) have been chosen as reference molecules. Molecules with and without π-spacers have been considered to understand the impact of the length of the π-spacer on intramolecular charge-transfer transitions and absorption properties. A detailed investigation is carried out to establish the relationship between the structure and photovoltaic parameters using density functional theory and time-dependent density functional theory methods. The newly developed molecules exhibit better electronic, excited-state, and charge transport properties than the reference molecules. Additionally, model donor-acceptor interfaces are constructed by integrating the designed donor molecules with fullerene/nonfullerene acceptors. The electronic and excited-state properties of these interfaces are rigorously evaluated. Results elucidate that the donor comprising of isoindigo-bithiophene-pyrroloindacenodithiophene (IIG-T2-PIDT) emerges as a promising candidate for bulk heterojunction solar cells based on nonfullerene acceptors. This research provides systematic design strategies for the development of small-molecule donors for organic solar cells.

Selective and Effective Sensing of Cyanide Ion with no Interference in Water by Phenothiazine-indolium Fused Optical Sensor.

The sensor with electron donor phenothiazine-2-carbaldehyde and electron acceptor indolium carboxylic acid, is developed with an intramolecular charge transfer transition between them. The synthesized molecule senses cyanide ion in water. The cyanide ion reacts with the molecule via nucleophilic addition in the indolium ring with a noticeable purple to colorless change in the solution observed. Also with the cyanide ion interaction, the sensor exhibits change in UV-visible absorption and fluorescence spectra. While the other ion does not show spectral and visual changes when interacts with the sensor molecule. Also the interference study reveals that the molecule is highly selective towards cyanide ion. Different source of water samples confirms the CN- ion sensing efficiency of the molecule. 1:1 interaction between the molecule PTI and cyanide ion is confirmed from the results of Jobs plot, 1H NMR and HRMS. Paper strips were prepared and this can act as a simple tool to sense cyanide ion in various water samples.

Near-IR Capturing N-Methylbenzene Sulfonamide-Phenothiazine Incorporating Strong Electron Acceptor Push-Pull Systems: Photochemical Ultrafast Carrier Dynamics.

Unraveling the intriguing aspects of the intramolecular charge transfer (ICT) phenomenon of multi-modular donor-acceptor-based push-pull systems are of paramount importance considering their promising applications, particularly in solar energy harvesting and light-emitting devices. Herein, a series of symmetrical and unsymmetrical donor-acceptor chromophores 1-6, are designed and synthesized by the Corey-Fuchs reaction via Evano's condition followed by [2+2] cycloaddition retroelectrocyclic ring-opening reaction with strong electron acceptors TCNE and TCNQ in good yields (~60-85 %). The photophysical, electrochemical, and computational studies are investigated to explore the effect of incorporation of strong electron acceptors 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) and dicyanoquinodimethane (DCNQ) with phenothiazine (PTZ) donor. An additional low-lying broad absorption band extended towards the near-infrared (NIR) region suggests charge polarization after the introduction of the electron acceptors in both symmetrical and asymmetrical systems, leading to such strong ICT bands. The electrochemical properties reveal that reduction potentials of 3 and 6 are lower than those of 2 and 5, suggesting DCNQ imparts more on the electronic properties and hence largely contributes to the stabilization of LUMO energy levels than TCBD, in line with theoretical observations. Relative positions of the frontier orbitals on geometry-optimized structures further support accessing donor-acceptor sites responsible for the ICT transitions. Eventually, ultrafast carrier dynamics of the photoinduced species are investigated by femtosecond transient absorption studies to identify their spectral characteristics and target analysis further provides information about different excited states photophysical events including ICT and their associated time profiles. The key findings obtained here related to excited state dynamical processes of these newly synthesized systems are believed to be significant in advancing their prospect of utilization in solar energy conversion and related photonic applications.

Coumarin Linked Cyanine Dye for the Selective Detection of Cyanide Ion in Environmental Water Sample.

A benzoxazole-coumarin-based probe BOC, was synthesized and validated for its anion sensing ability and found to be effective in recognizing cyanide ions. Upon addition of cyanide, a spontaneous color change was observed that was visible to the naked eye. The sensitization process takes place with nucleophilic addition, and the cyanide ion added to the probe disrupts the intra molecular charge transfer transition (ICT) between the donor and acceptor units, causing the pink colored probe to become yellow. Ultraviolet and fluorescence methods were applied to measure the detection limits of probes with added cyanide ions, which were found to be 3.47 µM and 2.48 nM. The stoichiometry of the probe with the cyanide ion was determined by the Job's method, NMR titration, and mass spectrometry and was found to be in a 1:1 ratio. The results obtained from the visual and UV-visible spectral studies are justified by theoretical calculations. The cyanide-loaded probe induced visual changes, which enabled the development of a test strip for field application, and the prepared strip can be used to detect the ppm level of cyanide in water samples. The developed probe, BOC, can be used to detect cyanide ions in various water samples.

A ferrocene-based chemo-dosimeter for colorimetric and electrochemical detection of cyanide and its estimation in cassava flour.

A simple chemo-dosimeter VDP2 bearing a ferrocene moiety was designed, synthesized, and characterized, and exhibited both chromogenic and electrochemical responses selectively for CN- in H2O-DMSO (9 : 1, v/v) medium. The probe VDP2 showed an instantaneous color change from colorless to yellow with CN- that can readily be observed visually. The deprotonation of the benzimidazole -NH, followed by nucleophilic addition of CN- to the olefinic C-atom, as evidenced by 1H and 13C NMR titration experiments, caused the colorimetric and electrochemical responses. The mass spectral study, CV, FTIR and Mulliken charges computed well supported the proposed mechanism. The electrochemical limit of detection was calculated to be 72 nM. The results of DFT and TD-DFT calculations suggested that the colorless nature of the probe VDP2 is due to weak intramolecular charge transfer (ICT) transition and the yellow color of the VDP2+CN adduct is due to through-space ICT transition. Above all, the probe could be an ideal candidate for monitoring cyanide in water samples and cassava flour with practical significance. A simple and convenient colorimetric method was developed to determine cyanide content in cassava flour.

D−A Based 2,3‐di(pyridin‐2‐yl)pyrido[2,3‐b]pyrazine Amine derivatives as Blue‐Orange Emitting Materials: Tuning of Opto‐electrochemical and Theoretical properties

AbstractA series of six new donor‐acceptor (D−A) type 2,3‐di(pyridin‐2‐yl)pyrido[2,3‐b]pyrazine amine derivatives as blue‐orange light emitting materials were designed, synthesized, characterized and their relevant opto‐electrochemical and theoretical properties have been fully investigated. Absorption spectra of dyes 2–7 possess intramolecular charge transfer (ICT) transitions (λmax=394–449 nm) and positive solvatochromism with emission in the blue‐orange region (λemm=477–582 nm) in solution and solid state. Further, the HOMO (−5.32 to −5.86 eV) and LUMO (−3.34 to −3.40 eV) energy levels were calculated by cyclic voltammetry (CV) and correlated by DFT/TD−DFT calculations. Moreover, computed singlet (S1) and triplet (T1) excitation energy difference (ΔEST=0.27–0.68 eV) were analyzed using the DFT/TD−DFT methods. Thus, potential applications of the dyes are proposed for organic electronics.

Fabrication and comprehensive investigations on NBD-based luminescent solar concentrator

The design and development of innovative chromophoric materials for luminescent solar concentrators (LSCs) is an emerging area of research in the pursuit of low-cost photovoltaic technology. In this study, we devised and developed the optically active fluorescent dye NBDNH2 based on the skeleton of a benzoxadiazole. In NBDNH2, the electron donating amino group and the electron-withdrawing nitro group are the responsible for intramolecular charge transfer transition as well as fluorescence upon photoexcitation. The structural and photophysical properties of NBDNH2 dye have been meticulously investigated. In addition, the solvent-property relationships also investigated through time-resolved fluorescence and 1H NMR measurements. The photophysical studies reveal that the dye has a moderate Stokes shift, a long fluorescence lifetime and provides guidance for the development of LSCs. NBDNH2 was doped in polymethyl methacrylate (PMMA) to fabricate LSC devices. Due to promising optical properties, the NBDNH2 based LSC (5 × 5 × 0.3 cm3) showed the internal and external photon efficiencies as high as 29.4 % and 3.84 %, respectively. When connected with the photovoltaic cell, the champion device yielded power conversion efficiency of 1.32 % and 0.64 % with scattering and black background, respectively. Based on the findings, we unequivocally envisaged that the benzoxadiazole-based ICT probe is a prospective optical material for LSC applications.

Theoretical and experimental investigation of exciplex-forming and electroluminescent properties of 4-ethyl-3,5-bis[40-(N, N-diphenylamine)biphenyl-4-yl]-4H-1,2,4-triazole

The recently synthesized 4-ethyl-3,5-bis [40-(N, N-diphenylamine)biphenyl-4-yl]-4H-1,2,4-triazole (TPA-TZ) is in this work thoroughly studied as an efficient luminophore with an account of density functional theory. The intense fluorescence is explained as an intramolecular charge-transfer transition from the diphenylamine (donor) moiety to the central part of the dye with a characteristic electron redistribution in the triazole ring (acceptor). The photoluminescence (PL) and phosphorescence (Ph) spectra of TPA-TZ in the film and in THF solution at 77 K were studied together with the well-known 2,4,6-tris [3-(diphenylphosphinyl)phenyl]-1,3,5-triazine (PO-T2T) dye. The latter compound was used as an electron-withdrawing component of the investigated TPA-TZ: PO-T2T exciplex, which is characterized by a relatively high energy level of the excited lowest triplet state. The films of a solid-state mixture of TPA-TZ and PO-T2T showed exciplex-type emission being slightly red-shifted compared to the PL of the individual donor and acceptor compounds. Two OLED devices with emitting layers of TPA-TZ and of the exciplex-forming molecular mixture of TPA-TZ and PO-T2T were prepared. The exciplex–based OLED demonstrated 4 103 cd/m2 brightness, a current efficiency of 22 cd/A, a power efficiency of 6.77 lm/W, and an external quantum efficiency (EQE) of 7%. This confirms the possibility of triplet harvesting in the molecular mixture of TPA-TZ and PO-T2T, since the theoretical EQE limit for OLED based on the prompt fluorescence is 5%.

Synthesis of D−A based violet−red light emitting indolo[2,3-b]quinoxalin-2-yl(phenyl)methanone amine dyes: Opto-electrochemical, AIE, and theoretical properties

In this work, we have designed and synthesized seven new amine derivatives of indolo[2,3-b]quinoxalin-2-yl(phenyl)methanone through the use of palladium-catalyzed Buchwald−Hartwig (C−N) coupling amination reaction and characterized by spectroscopic methods. Molecules offers intramolecular charge transfer (ICT) transitions, which result in absorption spectra with longer wavelengths (λmax = 385−509 nm), resembling a donor−acceptor (D−A) assembly. Consequently, the dyes emit light in violet–red region (λemi = 406−637 nm) in solution and solid film. Moreover, dye 5 and 6 demonstrate aggregation–induced emission (AIE) in THF−Water system due to the formation of nanoaggregates. Electrochemical properties investigated using cyclic voltammetry. The energy levels of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) were determined within the range from −4.91 to −5.76 eV and −3.03 to −3.45 eV, respectively, and comparable with reported ambipolar materials. Theoretical studies also conducted using density functional theory (DFT) and time–dependent density functional theory (TD–DFT) calculations, which agreeing with experimental data. The small energy difference between singlet (S1) and triplet (T1) states (∆EST = 0.24−0.45 eV) suggests that these dyes possess thermally activated delayed fluorescence (TADF) emitting properties. Thus, dyes propose their potential application in optoelectronic devices.

NIR-Absorbing 1,1,4,4-Tetracyanobuta-1,3-diene- and Dicyanoquinodimethane-Functionalized Donor-Acceptor Phenothiazine Derivatives: Synthesis and Characterization.

A series of symmetrical and unsymmetrical donor-acceptor type phenothiazine derivatives 1-18 were designed and synthesized via Pd-catalyzed Sonogashira cross-coupling and [2 + 2] cycloaddition-retroelectrocyclization reactions. The incorporation of cyano-based acceptors 1,1,4,4-tetracyanobutadiene (TCBD) and dicyanoquinodimethane (DCNQ) in the phenothiazine derivatives resulted in systematic variation in the photophysical, thermal, and electrochemical properties. The electronic absorption spectra of the phenothiazine derivatives with strong acceptors 2, 3, 5, 6, 8, 9, 11, 12, 14, 15, 17, and 18 show red-shifted absorption as compared to phenothiazine derivatives 1, 4, 7, 10, 13, and 16 in the near-IR region due to a strong intramolecular charge transfer (ICT) transition. The electrochemical analysis of the phenothiazine derivatives 2, 3, 5, 6, 8, 9, 11, 12, 14, 15, 17, and 18 reveals two reduction waves at low potential due to the TCBD and DCNQ acceptors. The mono-TCBD-functionalized phenothiazine 2 shows higher thermal stability compared to other phenothiazine derivatives. The computational studies on phenothiazines 1-18 reveal the LUMO is substantially stabilized as acceptor strength increases, which lowers the HOMO-LUMO gap.

Acceptor engineering of semiconducting oligomers for improved NIR-II fluorescence imaging and therapy

Fluorescence imaging (FI) conducted over second near-infrared (NIR-II) window shows superior performance with deeper penetration, higher temporal and spatial resolution than that over the first near-infrared (NIR-I) window. Various attempts have been made to develop ideal fluorophores with high brightness, longer emission wavelength and good biocompatibility for NIR-II FI. Here, we design and synthesize three D-A-D type oligomers through acceptor engineering approach to compare their optical properties. The newly prepared oligomer (O3) based on thiadiazolobenzotriazole (TBZ) acceptor exhibits the highest NIR-II brightness compared with the counterparts because of the weakest intramolecular charge transfer transition. Water-dispersed O3 nanoparticles (NPs) are then fabricated via nanoprecipitation method, which demonstrate superior NIR-II imaging ability for in vivo vascular imaging and tumor-targeted imaging. Furthermore, O3 NPs exhibit significant photothermal performance, thus inducing obvious cancer cell elimination upon 808 nm light irradiation. Taken together, TBZ unit is a promising electron acceptor for constructing bright and functional NIR-II dyes. This acceptor engineering method has offered us a feasible strategy to develop versatile NIR-II fluorophores.

A Combination of B- and N-Doped π-Systems Enabling Systematic Tuning of Electronic Structures and Properties.

Doping heteroatoms into polycyclic aromatic hydrocarbons (PAHs) may alter their structures and thereby physical properties. This study reports the construction of B/N-codoped PAHs via combining the B- and N-doped π-systems. Two π-extended B/N-codoped PAHs were synthesized through the Mallory photoreaction. Both feature a C48 BN2 π-skeleton, which is assembled by linearly fusing three substructures including B-doped and sp2 -hybridized N-doped π-moieties and one pyrene unit. In comparison to the pristine B-doped analog, their intramolecular charge transfer (ICT) states are distinctly modulated by the fused N-doped π-system and the further incorporated cyano group, leading to their tunable optical properties, as revealed by detailed theoretical and experimental analysis. Furthermore, these three molecules have sufficient Lewis acidity and can coordinate with Lewis base to form Lewis acid-base adducts, and notably, such intermolecular complexation can further dynamically modulate their ICT transitions and thereby photophysical properties, such as producing blue, green and red fluorescence.

Tunable Yellow to Near-Infrared Fluorescent Boron-Amino-Chelating Complexes with Stokes Shifts >100 nm.

A series of diphenylboron-chelating N-substituent 8-aminoquinoline, 5-aminoquinoxaline, and 1-aminophenazine were prepared. They exhibit lowest energy absorption peaks of 444-766 nm, emission peaks of 563-820 nm, and quantum yields of up to 46.5%. Electrochemical and theoretical studies indicate that the N-substituent mainly determines the HOMO and the framework determines the LUMO, thus allowing for a wide-tuning of absorptions/emissions. Intramolecular charge transfer transition leads to large Stokes shifts of up to 166 nm. One selected compound showed satisfactory cytocompatibility and cytoplasm-targeting cell imaging ability.

2,3-Diphenylquinoxalin-6-yl based dyes: Synthesis and studies of photophysical, aggregation-induced emission enhancement and electrochemical properties

Herein, 2,3-diphenylquinoxalin-6-yl based derivatives were synthesized, characterized by various spectroscopic method and studied for photophysical, aggregation-induced emission enhancement (AIEE) and electrochemical properties. Existence of intramolecular charge transfer transition (ICT) at 372−379 nm in absorption spectra of molecules confer weak push-pull interaction within it. Broad range of emission from blue to orange with λem = 412−592 nm in dyes arose from different energy state emission viz., locally excited (LE), Twisted intramolecular charge transfer (TICT) and excimer emission. Switching in emission state of molecules from excimer to TICT emission were observed by changing the polarity of solvent due to stabilization of TICT in polar media. Dyes have good solid state emission and AIEE activity desirable for its solid/aggregate state application in OLED's. Good Stokes shift (2183−9703 cm−1), thermal stability and comparable HOMO (−5.65 to −6.02 eV) energy levels with reported hole transporting materials confer desirable role of molecules in various optoelectronic applications. Further, DFT calculation of dyes, designate comparable experimental and theoretical photophysical and electrochemical properties with respect to structure of dyes.

Structural elucidation and spectroscopic studies of acetyl substituted piperazine nucleus tethered with 4, 5-diaryl-1 H-imidazole scaffold: DNA binding, Cu2+and Sn2+ ions sensing and cytotoxicity

In this study, we report on synthesis of new imidazole based fluorescentchemosensors2-((4-(5-bromo-2-hydroxy-3-(4,5-diphenyl-1H-imidazol-2-yl)benzyl)piperazine-1-yl)methyl)-4-bromo-6-(4,5-diphenyl-1H-imidazole-2-yl)phenol(1)and2-((4-(2-hydroxy-5-methyl-3-(4,5-diphenyl-1H-imidazol-2-yl)piperazine-1-yl)methyl)-4-methyl-6-(4,5-diphenyl-1H-imidazole-2-yl)phenol(2). The synthesized chemosensors 1 and 2 were characterized by FT-IR, 1H NMR, UV–visible and fluorescence spectral studies. Further, the single crystal X-ray diffraction analysis shows that the chemosensor 1 crystallizes in triclinic system, with space group P-1.Hirshfeld surface analysis and 2D fingerprint maps revealed that 1 have remarkable H…H, C…H/H…C, and O…H/H…O Br…H/H…Br, interactions. The chemosensors have developed for selective and sensitive detection of Sn2+ and Cu2+ions in methanol among other tested cation. A bathochromic shift and color change with respect to the intra-molecular charge transfer transition in the absorption spectra was displayed after the addition of Sn2+ and Cu2+ions. The “Turn-on” fluorescence enhancement to Sn2+ ions and “turn-off” fluorescence quenching response to Cu2+ ions at λmax 450 and 448 nm, respectively, were detected in the fluorescence emission spectra of 1 and 2 upon addition of Sn2+ and Cu2+ions⁻. The receptor senses Sn2+ and Cu2+ ions via the deprotonation of the phenolic O-H unit, which was further confirmed by 1H NMR titration. Moreover, the fluorescence imaging in A549 cells suggested that chemosensors had great potential in the application of bio-imaging. The chemosensors1 and 2 with Sn2+ ions were found to be cytotoxic against A549 cells andthe IC50 of 1 and 2 have value of 107.40 μM and 8.21 μM, respectively and could be used as an anticancer agent.

Investigation into aggregation types in a benzodithiophene-isoindigo copolymer.

The type of aggregation in conjugated polymers determines their use in electronic devices. H-type aggregates are most suitable for solar cell applications, while J-type aggregates are recommended for light-emitting diodes. In this work, we used three methods to determine the type of aggregates in a benzodithiophene-isoindigo-based (PBDTI-DT) copolymer, namely, Huang-Rhys factor evolution with temperature, Franck-Condon analysis, and relative quantum yield (QY) calculation. All three methods indicate that both aggregation types are present, and the QY calculation clearly indicates that H-aggregates are more dominant. Time-dependent density functional theory was used to identify the two absorption bands of PBDTI-DT as local π - π* and intramolecular charge-transfer transitions.

Charge transfer transitions of the O2+-Ar and O2+-N2 complexes.

Electronic transitions are observed for the O2+-Ar and O2+-N2 complexes over the 225-350nm range. The transitions are not associated with recognized electronic band systems of the respective atomic and diatomic constituents (Ar+, Ar, O2+, O2, N2+, and N2) but rather are due to charge transfer transitions. Onsets of the O2+-Ar and O2+-N2 band systems occur at 3.68 and 3.62eV, respectively, corresponding to the difference in the ionization potentials of Ar and O2 (3.69eV), and N2 and of O2 (3.51eV), suggesting the band systems arise from intramolecular charge transfer transitions to states correlating with O2(X3Σg-) + Ar+ (2Pu) and O2(X3Σg-) + N2+(X2Σg+) limits, respectively. The dominant vibronic progressions have ωe values of 1565 cm-1 for O2+-Ar and 1532 cm-1 for O2+-N2, reasonably close to the value for the neutral O2 molecule in its X3Σg- state (1580 cm-1). Higher energy band systems for O2+-Ar and O2+-N2 are assigned to transitions to states correlating with the O2 (a1Δg) + Ar+ (2Pu) and O2 (a1Δg) + N2+(X2Σg+) limits, respectively.

Spectroscopic and TD-DFT studies on the chromo-fluorogenic detection of cyanide ions in organic and aquo-organic media

A new naked-eye chromogenic and fluorogenic probe KS5 has been developed for the detection of CN– ions in neat DMSO and H2O:DMSO (1:1 v/v) media. The probe KS5 exhibited selectivity towards CN– and F− ions in organic and high selectivity towards CN– ions in aquo-organic media resulting in a colour change from brown to colourless and a turn-on fluorescence response. The probe could able to detect CN– ions via a deprotonation process, which was conceived by consecutive addition of hydroxide and hydrogen ions and confirmed using 1H NMR studies. The limit of detection (LOD) of KS5 towards CN– ions were in the range of 0.07–0.62 µM in both these solvent systems. Suppression of intra-molecular charge transfer (ICT) transition and photoinduced electron transfer (PET) process of KS5 by the added CN– ions are responsible for the chromogenic and fluorogenic changes observed, respectively. Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) calculations strongly supported the proposed mechanism along with the optical properties of the probe before and after the addition of CN– ions. To prove the practical applicability, KS5 was successfully utilized to detect CN– ions in cassava powder and bitter almonds as well as to determine CN– ions in various real water samples.

Solvent Effect on the Photoinduced Intramolecular Charge-Transfer and Redox Potentials of Three Difuranones.

We report solvent-dependent excited state properties of three difuranone derivatives with a quinoidal backbone by steady-state and lifetime fluorescence measurements and theoretical calculations. Remarkable bathochromic shifts in fluorescence with diminished intensity indicate the occurrence of strong intramolecular charge-transfer transitions in high polar solvents. Cyclic voltammetric redox potentials reveal an interesting variation of biradical characters of the compounds with increasing solvent polarity. Solvent polarity also significantly modulates the energy levels of the charge-transfer (CT) states, as observed from the combined analyses of redox potentials and photophysical data via the Rehm-Weller equation. When high polar solvents favor forward CT by a more exoergic driving force and stabilize the charge-separated states, the reverse CT process diminishes. Estimated free energies of activation for CT suggest that high polar solvents lessen the activation barrier. Calculated excited state energies of the compounds at the CAM-B3LYP/6-31+G* level fulfill the primary conditions required for singlet fission, a process that can substantially increase the efficiency of solar cells, and the crystal packing for compound 1 also reveals a favorable geometry for singlet fission.

Electronic structure and spatial hindrance effects of substituents on mechanical force-induced fluorescent response of xanthone derivatives with terminal carbazole or triphenylamine groups

Two novel D-A type luminophores XAO-Cz and XAO-TPA, in which xanthone as the electron-withdrawing and carbazole or triphenylamine as the electron donating, were designed and synthesized using Suzuli-Miyaura coupling reaction. Optical research and theoretical calculation indicated that both compounds exhibited a twisted molecular conformation as well as strong intramolecular charge transfer (ICT) characteristics. Moreover, XAO-Cz and XAO-TPA also exhibited fluorescent response to mechanical force with wavelength redshifts of 14 nm and 48 nm, respectively. To the best of our knowledge, this is the first example based on xanthone derivatives exhibiting fluorescent response to mechanical force. It is worth noting that XAO-TPA showed more significant mechanochromism than those of XAO-Cz. The reason may be due to strong ICT transition, highly twisted conformation and weak intermolecular interaction. The current work provided effective strategy at the molecular level to achieve high contrast fluorescent response to mechanical force.