Boosting the Efficiency of Red Thermally Activated Delayed Fluorescence via Conjugation Enhancement in Push-Pull Naphthalimide Derivatives.

In this work, we synthesize a series of push-pull compounds bearing naphthalimide as the electron acceptor and tetraphenylethylene (TPE)/triphenylamine (TPA)/phenothiazine (PTZ) as the electron rich/electron donor units. These moieties are arranged in highly conjugated quadrupolar structures. The structure-property relationships are investigated through a joint experimental time-resolved spectroscopic and computational TD-DFT study. The femtosecond transient absorption and fluorescence up-conversion experiments reveal ultrafast photoinduced intramolecular charge transfer. This is likely the key factor leading to efficient spin-orbit CT-induced intersystem crossing for the TPA- and PTZ-derivatives as well as to small singlet-to-triplet energy gap. Consequently, evidence for a delayed fluorescence component is found together with the main prompt emission in the fluorescence kinetics both in solution and in thin film. The weight of the Thermally Activated Delayed Fluorescence (TADF) is greatly enhanced when these fluorophores are used as guests in solid-state host matrices. TADF is interestingly revealed in the orange-red region of the visible. Such long wavelength emission is here observed with surprisingly large fluorescence quantum yields, thanks to the conjugation enhancement achieved in these newly synthesized structures relative to previous studies. Our findings may be thus promising for the future development of efficient third generation TADF-based OLEDs.

Near-IR-Absorbing Bis-Donor Functionalized Aza-BODIPY Derivatives: Synthesis and Photophysical Study by Using Transient Optical Spectroscopy.

A series of near-IR absorbing 2,6-diarylated BF2-chelated aza-boron-dipyrromethenes (aza-BDPs) derivatives bearing different electron donors (benzene, naphthalene, phenanthrene, phenothiazine and carbazole) were designed and synthesized. The effect of different electron donor substitutions on the photophysical properties was studied by steady-state UV-vis absorption and fluorescence spectra, electrochemical, time-resolved nanosecond transient absorption (ns-TA) spectroscopy and theoretical computations. The UV-vis absorption spectra of AzaBDP-PTZ and AzaBDP-CAR (λabs=710 nm in toluene) showed a bathochromic absorption profile compared with the reference AzaBDP-Ph (λabs=685 nm in toluene), indicating the non-negligible electronic interaction at the ground state between donor and acceptor moieties. Moreover, the fluorescence is almost completely quenched for AzaBDP-PTZ/AzaBDP-CAR (fluorescence quantum yield, ΦF=0.2-0.7 % in toluene) as compared with the AzaBDP-Ph (ΦF=27 % in toluene). However, the apparent intersystem crossing ability of these compounds is poor, based on the singlet oxygen quantum yield (ΦΔ=0.3-1.5 %). The ns-TA spectral study showed typical Bodipy localized triplet state transient features, short-lived excited triplet state for AzaBDP-Ph (τT=53.2 µs) versus significantly long-lived triplet state for AzaBDP-CAR (τT=114 µs) was observed under deaerated experimental conditions. These triplet state lifetimes are much longer than that obtained with diiodoAzaBDP (intramolecular heavy atom effect, τT=1.5~7.2 µs). These information are useful for molecular structure design of triplet photosensitizers, for which longer triplet state lifetimes are usually desired. Theoretical computations displayed that the triplet state is mainly localized on the AzaBDP core, moreover, it was found that the HOMO/LUMO energy gap decreased after introducing donor moieties to the skeleton as compared with the reference.

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.

Novel Benzothiadiazole-based Donor-Acceptor Systems: Synthesis, Ultrafast Charge Transfer and Separation Dynamics.

Near-infrared (NIR) absorbing electron donor-acceptor (D-A) chromophores have been at the forefront of current energy research owing to their facile charge transfer (CT) characteristics, which are primitive for photovoltaic applications. Herein, we have designed and developed a new set of benzothiadiazole (BTD)-based tetracyanobutadiene (TCBD)/dicyanoquinodimethane (DCNQ)-embedded multimodular D-A systems (BTD1-BTD6) and investigated their inherent photo-electro-chemical responses for the first time having identical and mixed terminal donors of variable donor-ability. Apart from poor luminescence, the appearance of broad low-lying optical transitions extendable even in the NIR region (> 1000 nm), particularly in the presence of the auxiliary acceptors, are indicative of underlying nonradiative excited state processes leading to strong intramolecular CT and subsequent charge separation (CS) processes in these D-A constructs. The spectral and temporal responses of different photoproducts are obtained from  transient studies. All the systems are found to be susceptible to ultrafast (~ps) CT and CS before carrier recombination to the ground state, which is, however, significantly facilitated after incorporation of the secondary TCBD/DCNQ acceptors, leading to faster and thus efficient CT processes. These findings are likely to expand the horizons of BTD-based multimodular CT systems to revolutionize the realm of solar energy conversion and associated photonic applications.

Zinc Tetrapyrrole Coordinated to Imidazole Functionalized Tetracyanobutadiene or Cyclohexa-2,5-diene-1,4-diylidene-expanded-tetracyanobutadiene Conjugates: Dark vs. Light-Induced Electron Transfer.

Using the popular metal-ligand axial coordination self-assembly approach, donor-acceptor conjugates have been constructed using zinc tetrapyrroles (porphyrin (ZnP), phthalocyanine (ZnPc), and naphthalocyanine (ZnNc)) as electron donors and imidazole functionalized tetracyanobutadiene (Im-TCBD) and cyclohexa-2,5-diene-1,4-diylidene-expanded-tetracyanobutadiene (Im-DCNQ) as electron acceptors. The newly formed donor-acceptor conjugates were fully characterized by a suite of physicochemical methods, including absorption and emission, electrochemistry, and computational methods. The measured binding constants for the 1 : 1 complexes were in the order of 104 -105  M-1 in o-dichlorobenzene. Free-energy calculations and the energy level diagrams revealed the high exergonicity for the excited state electron transfer reactions. However, in the case of the ZnNc:Im-DCNQ complex, owing to the facile oxidation of ZnNc and facile reduction of Im-DCNQ, slow electron transfer was witnessed in the dark without the aid of light. Systematic transient pump-probe studies were performed to secure evidence of excited state charge separation and gather their kinetic parameters. The rate of charge separation was as high as 1011  s-1 suggesting efficient processes. These findings show that the present self-assembly approach could be utilized to build donor-acceptor constructs with powerful electron acceptors, TCBD and DCNQ, to witness ground and excited state charge transfer, fundamental events required in energy harvesting, and building optoelectronic devices.

Far-Red Excitation Induced Electron Transfer in Bis Donor-AzaBODIPY Push-Pull Systems; Role of Nitrogenous Donors in Promoting Charge Separation.

A far-red absorbing sensitizer, BF2 -chelated azadipyrromethane (azaBODIPY) has been employed as an electron acceptor to synthesize a series of push-pull systems linked with different nitrogenous electron donors, viz., N,N-dimethylaniline (NND), triphenylamine (TPA), and phenothiazine (PTZ) via an acetylene linker. The structural integrity of the newly synthesized push-pull systems was established by spectroscopic, electrochemical, spectroelectrochemical, and DFT computational methods. Cyclic and differential pulse voltammetry studies revealed different redox states and helped in the estimation of the energies of the charge-separated states. Further, spectroelectrochemical studies performed in a thin-layer optical cell revealed diagnostic peaks of azaBODIPY⋅- in the visible and near-IR regions. Free-energy calculations revealed the charge separation from one of the covalently linked donors to the 1 azaBODIPY* to yield Donor⋅+ -azaBODIPY⋅- to be energetically favorable in a polar solvent, benzonitrile, and the frontier orbitals generated on the optimized structures helped in assessing such a conclusion. Consequently, the steady-state emission studies revealed quenching of the azaBODIPY fluorescence in all of the investigated push-pull systems in benzonitrile and to a lesser extent in mildly polar dichlorobenzene, and nonpolar toluene. The femtosecond pump-probe studies revealed the occurrence of excited charge transfer (CT) in nonpolar toluene while a complete charge separation (CS) for all three push-pull systems in polar benzonitrile. The CT/CS products populated the low-lying 3 azaBODIPY* prior to returning to the ground state. Global target (GloTarAn) analysis of the transient data revealed the lifetime of the final charge-separated states (CSS) to be 195 ps for NND-derived, 50 ps for TPA-derived, and 85 ps for PTZ-derived push-pull systems in benzonitrile.

Tetracyanobutadiene Bridged Push-Pull Chromophores: Development of New Generation Optoelectronic Materials.

This review describes the design strategies used for the synthesis of various tetracyanobutadiene bridged donor-acceptor molecular architectures by a click type [2+2] cycloaddition-retroelectrocyclization (CA-RE) reaction sequence. The photophysical and electrochemical properties of the tetracyanobutadiene bridged molecular architectures based on various moieties including diketopyrrolopyrrole, isoindigo, benzothiadiazole, pyrene, pyrazabole, truxene, boron dipyrromethene (BODIPY), phenothiazine, triphenylamine, thiazole and bisthiazole are summarized. Further, we discuss some important applications of the tetracyanobutadiene bridged derivatives in dye sensitized solar cells, bulk heterojunction solar cells and photothermal cancer therapy.

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.

Near-IR absorbing 1,1,4,4-tetracyanobutadiene-functionalized phenothiazine sulfones.

Triphenylamine (TPA) substituted π-conjugated chromophores TPA1-TPA5 were designed and synthesized via Pd-catalysed Sonogashira cross-coupling followed by [2 + 2] cycloaddition-retroelectrocyclization (CA-RE) reactions. The effects of acceptor 1,1,4,4-tetracyanobutadiene (TCBD) and cyclohexa-2,5-diene-1,4-diylidene-expanded TCBD (DCNQ) units in the photophysical studies and the HOMO-LUMO energy levels of the phenothiazine sulfones TPA1-TPA5 were evaluated. The absorption spectra of chromophores TPA4 and TPA5 show a significant change due to the incorporation of DCNQ units, resulting in bathochromically shifted broad absorption in the NIR region. The photophysical studies revealed that DCNQ-based chromophores TPA4 and TPA5 have a better D-A interaction than the TCBD functionalized TPA2 and TPA3. Density functional theory calculations and electrochemical studies were performed to examine the molecular geometry and frontier energy levels of the sulfone-based chromophores. Systematic structural modification of the chromophore TPA1 modulated the electrochemical properties and successively tuned the energy gaps for TPA2-TPA5. The theoretically estimated HOMO-LUMO gaps for TPA1-TPA5 exhibit good agreement with the experimental data calculated from the electrochemical studies. The chromophore TPA1 exhibits solvatochromism and aggregation-induced emission (AIE) behavior owing to the emission in the solid state.

ß-Pyrrole Functionalized Push or Pull Porphyrins: Excited Charge Transfer Promoted Singlet Oxygen Generation.

Singlet oxygen (1O2) producing photosensitizers are highly sought for developing new photodynamic therapy agents and facilitating 1O2-involved chemical reactions. Often singlet oxygen is produced by the reaction of triplet-excited photosensitizers with dioxygen via an energy transfer mechanism. In the present study, we demonstrate a charge transfer mechanism to produce singlet oxygen involving push or pull functionalized porphyrins. For this, 20 ß-pyrrole functionalized porphyrins carrying either an electron-rich push or electron-deficient pull group have been newly synthesized. Photoexcitation of these push-pull porphyrins has been shown to produce high-energy MPδ+-Aδ- or MPδ--Dδ+ charge transfer states. Subsequent charge recombination results in populating the triplet excited states of extended lifetimes in the case of the push group containing porphyrins that eventually react with dioxygen to produce the reactive singlet oxygen of relatively higher quantum yields. The effect of the push and pull groups on the porphyrin periphery in governing initial charge transfer, the population of triplet excited states and their lifetimes, and resulting in improved singlet oxygen quantum yields are systematically probed. The improved performance of 1O2 generation by porphyrins carrying push groups is borne out from this study.

Accelerated Intramolecular Charge Transfer in Tetracyanobutadiene- and Expanded Tetracyanobutadiene-Incorporated Asymmetric Triphenylamine-Quinoxaline Push-Pull Conjugates.

The excited-state properties of an asymmetric triphenylamine-quinoxaline push-pull system wherein triphenylamine and quinoxaline take up the roles of an electron donor and acceptor, respectively, are initially investigated. Further, in order to improve the push-pull effect, powerful electron acceptors, viz., 1,1,4,4-tetracyanobutadiene (TCBD) and cyclohexa-2,5-diene-1,4-diylidene-expanded tetracyanobutadiene (also known as expanded-TCBD or exTCBD), have been introduced into the triphenylamine-quinoxaline molecular framework using a catalyst-free [2 + 2] cycloaddition-retroelectrocyclization reaction. The presence of these electron acceptors caused strong ground-state polarization extending the absorption well into the near-IR region accompanied by strong fluorescence quenching due to intramolecular charge transfer (CT). Systematic studies were performed using a suite of spectral, electrochemical, computational, and pump-probe spectroscopic techniques to unravel the intramolecular CT mechanism and to probe the role of TCBD and exTCBD in promoting excited-state CT and separation events. Faster CT in exTCBD-derived compared to that in TCBD-derived push-pull systems has been witnessed in polar benzonitrile.

Near-IR Intramolecular Charge Transfer in Strongly Interacting Diphenothiazene-TCBD and Diphenothiazene-DCNQ Push-Pull Triads.

Three types of phenothiazines dimers (PTZ-PTZ, 1-3), covalently linked with one or two acetylene linkers, were synthesized by copper-mediated Eglinton and Pd-catalyzed Sonogashira coupling reactions in excellent yields. The dimers 1-3 were further engaged in [2+2] cycloaddition-retroelectrocyclization reactions with strong electron acceptors, tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) to yield tetracyanobutadiene (TCBD, 1 a-3 a), and dicyanoquinodimethane (DCNQ, 1 b-3 b) functionalized donor-acceptor (D-A) conjugates, respectively. The conjugates were examined by a series of spectral, computational, and electrochemical studies. Strong ground state polarization leading to new optical transitions was witnessed in both series of D-A conjugates. In the case of DCNQ derived D-A system 1 b, the optical coverage extended until 1200 nm in benzonitrile, making this a rare class of D-A ICT system. Multiple redox processes were witnessed in these D-A systems, and the frontier orbitals generated on DFT optimized structures further supported the ICT phenomenon. Photochemical studies performed using femtosecond pump-probe studies confirmed solvent polarity dependent excited state charge transfer and separation in these novel multi-modular D-A conjugates. The charge-separated states lasted up to 70 ps in benzonitrile while in toluene slightly prolonged lifetime of up to 100 ps was witnessed. The significance of phenothiazine dimer in wide-band optical capture all the way into the near-IR region and promoting ultrafast photoinduced charge transfer in the D-A-D configured multi-modular systems, and the effect of donor-acceptor distance and the solvent polarity was the direct outcome of the present study.

Tuning the Fluorescence and the Intramolecular Charge Transfer of Phenothiazine Dipolar and Quadrupolar Derivatives by Oxygen Functionalization.

A series of new naphthalimide and phenothiazine-based push-pull systems (NPI-PTZ1-5), in which we structurally modulate the oxidation state of the sulfur atom in the thiazine ring, i.e., S(II), S(IV), and S(VI), was designed and synthesized by the Pd-catalyzed Sonogashira cross-coupling reaction. The effect of the sulfur oxidation state on the spectral, photophysical, and electrochemical properties was investigated. The steady-state absorption and emission results show that oxygen functionalization greatly improves the optical (absorption coefficient and fluorescence efficiency) and nonlinear optical (hyperpolarizability) features. The cyclic voltammetry experiments and the quantum mechanical calculations suggest that phenothiazine is a stronger electron donor unit relative to phenothiazine-5-oxide and phenothiazine-5,5-dioxide, while the naphthalimide is a strong electron acceptor in all cases. The advanced ultrafast spectroscopic measurements, transient absorption, and broadband fluorescence up conversion give insight into the mechanism of photoinduced intramolecular charge transfer. A planar intramolecular charge transfer (PICT) and highly fluorescent excited state are populated for the oxygen-functionalized molecules NPI-PTZ2,3 and NPI-PTZ5; on the other hand, a twisted intramolecular charge transfer (TICT) state is produced upon photoexcitation of the oxygen-free derivatives NPI-PTZ1 and NPI-PTZ4, with the fluorescence being thus significantly quenched. These results prove oxygen functionalization as a new effective synthetic strategy to tailor the photophysics of phenothiazine-based organic materials for different optoelectronic applications. While oxygen-functionalized compounds are highly fluorescent and promising active materials for current-to-light conversion in organic light-emitting diode devices, oxygen-free systems show very efficient photoinduced ICT and may be employed for light-to-current conversion in organic photovoltaics.

Charge-Transfer in Panchromatic Porphyrin-Tetracyanobuta-1,3-Diene-Donor Conjugates: Switching the Role of Porphyrin in the Charge Separation Process.

Using a combination of cycloaddition-retroelectrocyclization reaction, free-base and zinc porphyrins (H2 P and ZnP) are decorated at their ß-pyrrole positions with strong charge transfer complexes, viz., tetracyanobuta-1,3-diene (TCBD)-phenothiazine (3 and 4) or TCBD-aniline (7 and 8), novel class of push-pull systems. The physico-chemical properties of these compounds (MP-Donor and MP-TCBD-Donor) have been investigated using a range of electrochemical, spectroelectrochemical, DFT as well as steady-state and time-resolved spectroscopic techniques. Ground-state charge transfer interactions between the porphyrin and the electron-withdrawing TCBD directly attached to the porphyrin π-system extended the absorption features well into the near-infrared region. To visualize the photo-events, energy level diagrams with the help of free-energy calculations have been established. Switching the role of porphyrin from the initial electron acceptor to electron donor was possible to envision. Occurrence of photoinduced charge separation has been established by complementary transient absorption spectral studies followed by global and target data analyses. Better charge stabilization in H2 P derived over ZnP derived conjugates, and in phenothiazine derived over aniline derived conjugates has been possible to establish. These findings highlight the importance of the nature of porphyrins and second electron donor in governing the ground and excited state charge transfer events in closely positioned donor-acceptor conjugates.

Mechanochromism and Aggregation-Induced Emission in Phenanthroimidazole Derivatives: Role of Positional Change of Different Donors in a Multichromophoric Assembly.

Organic materials possessing solid-state emission responsive to external stimuli have significance in a variety of material, biomedical, and optoelectronic applications. Organic molecules having different donor-acceptor architectures integrated with aggregation-induced emission (AIE) fluorophores have been utilized in development of mechanofluorochromic (MFC) materials. In this work, we have designed and synthesized phenanthroimidazole (PI) based derivatives TPE-PI-1, TPE-PI-2, TPE-PI-3, PTZ-PI-1, PTZ-PI-2, and PTZ-PI-3 where in donors tetraphenylethylene-TPE (D) and phenothiazine-PTZ (D') of contrasting donor abilities are attached to the N and C atom positions of PI. The position and mode of attachment of the donors have been changed, and an additional PTZ spacer has been introduced which has a direct consequence on their photophysical and electronic properties. The PI derivatives manifest AIE, solvatochromic, and mechanochromic behavior. The single crystal X-ray analysis of TPE-PI-1 and PTZ-PI-2 reveals bent structures for the PTZ unit and a twisted conformation for TPE moieties. The density functional theory calculations were used to obtain optimized ground-state structures of the PI derivatives. The work shows a comprehensive comparison of the photophysical, electronic, AIE, and MFC properties of the PI derivatives as an effect of variations in the position of donor, donor-acceptor strength, and change in molecular conformation on use of spacer.

Photoinduced Charge Separation Prompted Intervalence Charge Transfer in a Bis(thienyl)diketopyrrolopyrrole Bridged Donor-TCBD Push-Pull System.

Intervalence charge transfer (IVCT), a phenomenon observed in molecular systems comprised of two redox centers differing in oxidation states by one unit, is reported in a novel, newly synthesized, multi-modular donor-acceptor system comprised of central bis(thienyl)diketopyrrolopyrrole (TDPP) hosting two phenothiazine-tetracyanobutadiene (PTZ-TCBD) entities on the opposite sides. One-electron reduction of TCBD promoted electron exchange between the two TCBD resulting in IVCT transition in the near-infrared region. The stabilization energy, -ΔGcom and comproportionation equilibrium constant, Kcom calculated from peak potentials of the split reduction waves were found to be 1.06×104  J mol-1 , and 72.3 M-1 , respectively. Further, the IVCT transition was also witnessed during the process of thermodynamically feasible electron transfer upon excitation of the TDPP entity in the system, and served as a diagnostic marker to characterize the electron transfer product. Subsequent transient absorption spectral studies and data analysis by Global and Target analyses revealed occurrence of ultrafast charge separation (kcs ≈1010  s-1 ) owing to the close proximity and good communication between the entities of the multi-modular donor-acceptor system. The role of central TDPP in promoting IVCT is borne out from the present investigation.

Excited-State Electron Transfer in 1,1,4,4-Tetracyanobuta-1,3-diene (TCBD)- and Cyclohexa-2,5-diene-1,4-diylidene-Expanded TCBD-Substituted BODIPY-Phenothiazine Donor-Acceptor Conjugates.

A new set of donor-acceptor (D-A) conjugates capable of undergoing ultrafast electron transfer were synthesized using 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY)-substituted phenothiazine, SM1-SM3, by a Pd-catalyzed Sonogashira cross-coupling reaction and a [2+2] cycloaddition-electrocyclic ring-opening reaction. The incorporation of 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) and cyclohexa-2,5-diene-1,4-diylidene-expanded TCBD (abbreviated as DCNQ=dicyanodiquinodimethane) in BODIPY-substituted phenothiazine resulted in significant perturbation of the optical and electronic properties. The absorption spectrum of both SM2 and SM3 showed red shifted absorption as compared to SM1. Additionally, both SM2 and SM3 exhibited a distinct intramolecular charge-transfer (ICT) transition in the near-IR region more so for SM3. The electrochemical study revealed multi-redox processes due to the presence of redox-active phenothiazine, BODIPY, TCBD or DCNQ entities. Using data from spectral, electrochemical and computational studies, an energy-level diagram was established to witness excited-state electron-transfer events. Finally, evidence of electron transfer and their kinetic information was secured from studies involving a femtosecond transient absorption technique. The time constants for excited-state electron-transfer events in the case of SM2 and SM3 were less than 5 ps revealing ultrafast processes.

Formation of Highly Efficient, Long-Lived Charge Separated States in Star-Shaped Ferrocene-Diketopyrrolopyrrole-Triphenylamine Donor-Acceptor-Donor Conjugates.

The significance of multiple number of donor-acceptor entities on a central electron donor in a star-shaped molecular system in improving light energy harvesting ability is reported. For this, donor-acceptor-donor type conjugates comprised up to three entities ferrocenyl (Fc)-diketopyrrolopyrrole (DPP) onto a central triphenylamine (TPA), (4-6) by the Pd-catalyzed Sonogashira cross-coupling reactions have been newly synthesized and characterized. Donor-acceptor conjugates possessing diketopyrrolopyrrole (1 to 3 entities) onto the central triphenylamine, (1-3) served as reference dyads while monomeric DPP and Fc-DPP served as control compounds. Both DPP and Fc-DPP carrying conjugates exhibited red-shifted absorption compared to their respective control compounds revealing existence of ground state interactions. Furthermore, DPP fluorescence in 4-6 was found to be quantitatively quenched while for 1-3, this property varied between 73-65 % suggesting occurrence moderate amounts of excited state events. The electrochemical investigations exhibited an additional low potential oxidation in the case of Fc-DPP-TPA based derivatives (4-6) owing to the presence of ferrocene unit(s). This was in addition to DPP and TPA redox peaks. Using spectral, electrochemical and computational studies, Gibbs free-energy calculations were performed to visualize excited state charge separation (ΔGCS ) in these donor-acceptor conjugates as a function of different number of Fc-DPP entities. Formation of Fc+ -DPP.- -TPA charge separated states (CSS) in the case of 4-6 was evident. Using spectroelectrochemical studies, spectrum of CSS was deduced. Finally, femtosecond transient absorption spectral studies were performed to gather information on excited state charge separation. Increasing the number of Fc-DPP entities in 4-6 improved charge separation rates. Surprisingly, lifetime of the charge separated state, Fc+ -DPP.- -TPA was found to persist longer with an increase in the number of Fc-DPP entities in 4-6 as compared to Fc-DPP-control and simple DPP derived donor-acceptor conjugates in literature. This unprecedented result has been attributed to subtle changes in ΔGCS and ΔGCR and the associated electron coupling between different entities.

Metal Functionalized Diketopyrrolopyrroles: A Promising Class of Materials for Optoelectronic Applications.

After first report on diketopyrrolopyrrole in 1974 by Farnum et al., a wide variety of its derivatives have been reported for material and biological applications. In this review we discuss various design strategies used for the synthesis of metal functionalized diketopyrrolopyrrole derivatives along with their photophysical and electrochemical studies with respect to material and biological applications. Some exciting applications of ferrocenyl functionalized diketopyrrolopyrrole derivatives such as non-linear optics, organic solar cells and photothermal therapy were recently reported, which are also discussed in this review.

Synthesis and Characterization of Isoindigo-Based Push-Pull Chromophores.

Symmetrical and unsymmetrical chromophores of isoindigo 3-7 were designed and synthesized, in which isoindigo was used as the central unit (electron acceptor unit A), triphenylamine as the end capping unit (electron donor group D), 1,1,4,4-tetracyanobutadiene (TCBD, A') and cyclohexa-2,5-diene-1,4-diylidene-expanded TCBD (A″) as the acceptor unit. The effects of multiacceptor units on photophysical, electrochemical, and computational studies were investigated. The photophysical properties of isoindigo 6 and 7 exhibit a strong intramolecular charge transfer (ICT) absorption band in the near IR region. The isoindigo 4-7 shows multi-redox waves with a low electrochemical band gap, which signifies the tuning of highest occupied molecular orbital-lowest unoccupied molecular orbital energy levels and enhance the π-conjugation. The computational studies demonstrate that there is a good agreement with experimental data. The molecular design and synthesis of isoindigo 4-7 gives a new avenue for the development of building blocks in organic electronics.