Cycloaddition-retroelectrocyclization Reaction Research Articles

Perspectives on push-pull chromophores derived from click-type [2 + 2] cycloaddition-retroelectrocyclization reactions of electron-rich alkynes and electron-deficient alkenes.

Various push-pull chromophores can be synthesized in a single and atom-economical step through [2 + 2] cycloaddition-retroelectrocyclization (CA-RE) reactions involving diverse electron-rich alkynes and electron-deficient alkenes. In this review, a comprehensive investigation of the recent and noteworthy advancements in the research on push-pull chromophores prepared via the [2 + 2] CA-RE reaction is conducted. In particular, an overview of the physicochemical properties of the family of these compounds that have been investigated is provided to clarify their potential for future applications.

NIR-absorbing TCBD and cyclohexa-2,5-diene-1,4-diylidene-expanded TCBD bridged derivatives of 1,1′-bis(N,N-dimethylaniline)-substituted ferrocene

Symmetrical and unsymmetrical donor-acceptor (D–A) based chromophores were designed and synthesized by the Pd–catalyzed Sonogashira cross–coupling reaction of 1,1′-diiodoferrocene with (4-N,N-dimethylaminophenyl)ethyne followed by [2+2] cycloaddition-retroelectrocyclization reaction with tetracyanoethylene (TCNE) or 7,7,8,8-tetracyanoquinodimethane (TCNQ). Ferrocene was used as a central donor unit and 4-(N,N-dimethylamino)phenyl group as the end-capping donor. Herein, we report the cycloaddition-retrocyclization reaction of TCNE/TCNQ groups on the disubstituted ferrocene containing more than one triple bond to get disubstituted tetracyanobutadiene (TCBD) and cyclohexa-2,5-diene-1,4-diylidene-expanded TCBD products. The effect of the conjugation length and different π–acceptor linkers were investigated by photophysical, redox and computational studies. The redox study reveals multiple oxidation waves corresponding to donor moieties (ferrocene and 4-(N,N-dimethylamino)phenyl group) and reduction waves corresponding to acceptor units (TCBD / cyclohexa-2,5- diene-1,4-diylidene-expanded TCBD). The thermogravimetric analysis data shows that the compounds exhibit high thermal stability. The computational studies reveal HOMO-LUMO gaps consistent with the experimentally obtained data.

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.

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.

Excitation Wavelength-Dependent Charge Stabilization in Highly Interacting Phenothiazine Sulfone-Derived Donor–Acceptor Constructs

Prolonging the lifetime of charge-separated states (CSS) is of paramount importance in artificial photosynthetic donor-acceptor (DA) constructs to build the next generation of light-energy-harvesting devices. This becomes especially important when the DA constructs are closely spaced and highly interacting. In the present study, we demonstrate extending the lifetime of the CSS in highly interacting DA constructs by making use of the triplet excited state of the electron donor and with the help of excitation wavelength selectivity. To demonstrate this, π-conjugated phenothiazine sulfone-based push-pull systems, PTS2-PTS6 have been newly designed and synthesized via the Pd-catalyzed Sonogashira cross-coupling followed by [2 + 2] cycloaddition-retroelectrocyclization reactions. Modulation of the spectral and photophysical properties of phenothiazine sulfones (PTZSO2) and terminal phenothiazines (PTZ) was possible by incorporating powerful electron acceptors, 1,1,4,4-tetracyanobutadiene (TCBD) and cyclohexa-2,5-diene-1,4-diylidene-expanded TCBD (exTCBD). The quadrupolar PTS2 displayed solvatochromism, aggregation-induced emission, and mechanochromic behaviors. From the energy calculations, excitation wavelength-dependent charge stabilization was envisioned in PTS2-PTS6, and the subsequent pump-probe spectroscopic studies revealed charge stabilization when the systems were excited at the locally excited peak positions, while such effect was minimal when the samples were excited at wavelengths corresponding to the CT transitions. This work reveals the impact of wavelength selectivity to induce charge separation from the triplet excited state in ultimately prolonging the lifetime of CCS in highly interacting push-pull systems.

Ultrafast Charge-Transfer in Panchromatic, Push-Pull Porphyrin-Tetracyanobuta-1,3-Diene-Donor Conjugates

Light-induced electron transfer is a key step in solar energy conversion, and a process with myriad relevance in the fields of artificial photosynthesis, photocatalysis, photoconductivity, and molecular photovoltaics. In a donor-acceptor, D-A system, light absorption by a chromophore results in the formation of an excited state species, followed by a charge transfer between an electron donor (D) and an electron acceptor (A) leading to a charge-separated D .+ -A .- species.The optimization of these processes and comprehending their mutual interplay to ultimately achieve charge-separated species is of paramount importance for the development of efficient systems in solar light conversion schemes. As part of our continued effort in this field of research,1-3 using a combination of cycloaddition-retroelectrocyclization reaction, free-base and zinc porphyrins (H2P and ZnP) are decorated at their b-pyrrole positions with strong charge-transfer complexes, viz., tetracyanobuta-1,3-diene (TCBD)-DONOR as a novel class of push-pull systems.4 The physicochemical properties of these compounds have been investigated using a range of electrochemical, spectroelectrochemical, DFT as well as steady-state and time-resolved spectroscopic techniques. Charge transfer interactions between the porphyrin and the electron-withdrawing TCBD directly attached to the porphyrin p-system extended the absorption well into the near-infrared region. The occurrence of photoinduced charge transfer and separation has been established by complementary transient absorption spectral studies followed by global and target data analyses. The role of central metal in the porphyrin cavity and the nature of the donor in governing these photo events will be discussed. Khan, Y. Jang, Y. Patil, R. Misra, and F. D’Souza, Photoinduced Charge Separation Prompted Intervalence Charge Transfer in a Bis(thienyl)diketopyrrolopyrrole Bridged Donor-TCBD Push-Pull System (hot article), Angew. Chem. Int. Ed. 2021, 60, 20518–20527.S. Yadav, A. Z. Alsaleh,R. Misra and F. D’Souza, ‘Excited State Charge Transfer Leading to Charge Stabilization via an Electron Exchange Mechanism in Symmetric, Central Triphenylamine Derived, Dimethylaminophenyl-Tetracyanobutadiene Donor-Acceptor Conjugates, Chem. Sci. 2021, 12, 1109-1120.Pinjari, A. Z. Alsaleh,Y. Patil, R. Misra and F. D’Souza, Interfacing High-Energy Charge Transfer States to a Near-IR Sensitizer for Efficient Electron Transfer upon Near-IR Irradiation’ Angew. Chem. Int. Ed. 2020, 59, 23697-23705.Sekaran, A. Dawson, Y. Jang, K. V. MohanSingh, R. Misra and F. D’Souza, Charge-Transfer in Panchromatic Porphyrin-Tetracyanobuta-1,3-diene-Donor Conjugates: Switching the Role of Porphyrin in the Charge Separation Process, Chem. Eur. J. 2021, 27, 14335-14344 Figure 1

2+2] Cycloaddition-retroelectrocyclization reactivity and thin film transistor performances of carbazole-based platinum polyyne polymers

Carbazole-based platinum polyyne polymers are a good platform for the postfunctional formation of donor-acceptor type narrow band gap polymers by the [2 + 2] cycloaddition-retroelectrocyclization reaction with tetracyanoethylene (TCNE). The TCNE reactivity depends on the connectivity pattern of the carbazole. The 3,6-cabazole-based polymer shows a higher reactivity than the corresponding 2,7-carbazole-based polymer due to the p-positions with respect to the sp3 nitrogen atom. The connectivity pattern leads to the regioregularity difference in the resulting polymers. When TCNE is added to one of the alkynes of the 3,6-diethynylcarbazole unit, the electron-donating nature of the carbazole is lowered and the second TCNE addition does not occur. Accordingly, the regioregular polymer is formed from the 3,6-carbazole-based polymer, which is revealed from the 1H NMR spectrum. In contrast, the TCNE addition of the 2,7-carbazole-based polymer is mainly governed by the platinum atom, which produces a regiorandom structure. Finally, the charge carrier transporting properties of the precursor polymers are evaluated in thin film transistors. The 3,6-carbazole-based polymer displays a one order higher hole mobility than the corresponding 2,7-carbazole-based polymer. This result suggests that the shallower HOMO level of the former polymer facilitates the hole injection.

1,1,4,4-Tetracyanobutadiene-Functionalized Anthracenes: Regioselectivity of Cycloadditions in the Synthesis of Small Near-IR Dyes.

Two small 1,1,4,4-tetracyanobutadiene-functionalized chromophores were obtained by careful leverage of the regioselectivity of the cycloaddition reaction of tetracyanoethylene with anthracene–ynamide derivatives, inducing either a [2 + 2] or a [4 + 2] Diels–Alder process. DFT calculations unraveled the mechanism of the [2 + 2] cycloaddition–retroelectrocyclization reaction sequence with ynamides and elucidated the differing mechanisms in the two substrates. The synthesized dyes presented panchromatic absorption extending into the near-IR and far-red/near-IR photoluminescence in the solid state up to 1550 nm.

Synthesis of 1,1,4,4‐Tetracyanobuta‐1,3‐Dienes using Tetracyanoethylene Oxide via [3+2]‐Cycloaddition‐Ring Opening Reaction

AbstractUnlike the [3+2] cycloadduct of electron‐donating group (EDG)‐free alkynes with tetracyanoethylene oxide (TCNEO), the EDG induced [3+2] cycloadduct underwent one‐pot ring‐opening and deoxygenation reactions to provide the established EDG‐substituted non‐planar 1,1,4,4‐tetracyanobuta‐1,3‐dienes (TCBDs) push‐pull chromophores. This is an alternate synthetic method that provides access to TCBDs other than the [2+2] cycloaddition–retroelectrocyclization reactions with tetracyanoethene.

Strong Ground‐ and Excited‐State Charge Transfer in C3‐Symmetric Truxene‐Derived Phenothiazine‐Tetracyanobutadine and Expanded Conjugates

AbstractThe C3‐symmetric star‐shaped phenothiazene‐substituted truxene 1 was reacted with the electron acceptors tetracyanoethylene (TCNE) and 7,7,8,8‐tetracyanoquinodimethane (TCNQ). The cycloaddition–retroelectrocyclization reaction yields the conjugates 2 and 3. A combination of spectral, electrochemical, and photophysical investigations of 2 and 3 reveals that the functionalization of the triple bond has a pronounced effect on their ground and excited‐state interactions. Specifically, the existence of strong ground‐state interactions between phenothiazine and the electron‐accepting groups results in charge‐transfer states, while subsequent ultrafast charge separation yields electron transfer products. This is unprecedented not only in phenothiazine chemistry but also in tetracyanobutadiene‐ and dicyanoquinodimethane‐derived donor–acceptor conjugates. Additionally, by manipulating spectroelectrochemical data, a spectrum of the charge‐separated species is construed for the first time, and shown to be highly useful in interpreting the rather complex transient spectra.

Strong Ground- and Excited-State Charge Transfer in C3 -Symmetric Truxene-Derived Phenothiazine-Tetracyanobutadine and Expanded Conjugates.

The C3 -symmetric star-shaped phenothiazene-substituted truxene 1 was reacted with the electron acceptors tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ). The cycloaddition-retroelectrocyclization reaction yields the conjugates 2 and 3. A combination of spectral, electrochemical, and photophysical investigations of 2 and 3 reveals that the functionalization of the triple bond has a pronounced effect on their ground and excited-state interactions. Specifically, the existence of strong ground-state interactions between phenothiazine and the electron-accepting groups results in charge-transfer states, while subsequent ultrafast charge separation yields electron transfer products. This is unprecedented not only in phenothiazine chemistry but also in tetracyanobutadiene- and dicyanoquinodimethane-derived donor-acceptor conjugates. Additionally, by manipulating spectroelectrochemical data, a spectrum of the charge-separated species is construed for the first time, and shown to be highly useful in interpreting the rather complex transient spectra.

Tetracyanobutadiene (TCBD) functionalized benzothiadiazole derivatives: effect of donor strength on the [2+2] cycloaddition–retroelectrocyclization reaction

A series of unsymmetrical and symmetrical mono/di 1,1,4,4-tetracyanobutadiene (TCBD) substituted benzothiadiazoles (BTDs) 2a–2g was synthesized by [2+2] cycloaddition–retroelectrocyclization reaction.

C3-Symmetric star shaped donor–acceptor truxenes: synthesis and photophysical, electrochemical and computational studies

This manuscript reports the design and synthesis of C3-symmetric star shaped donor and acceptor substituted truxenes 6, 7, 10 and 11 using Pd-catalyzed Sonogashira cross-coupling and [2+2] cycloaddition–retroelectrocyclization reactions.

Near-infrared absorbing tetracyanobutadiene-bridged diketopyrrolopyrroles

Herein we have synthesized near-infra red absorbing TCBD bridged diketopyrrolopyrroles by a [2+2] cycloaddition–retroelectrocyclization reaction in order to see the effects of end capping donors and electron-withdrawing TCBD on the optical and electrochemical properties.

Synthesis, Structures, and Redox Properties of Tetracyano-Bridged Diferrocene Donor–Acceptor–Donor Systems

A set of tetracyanobutadiene (TCBD)- and dicyanoquinodimethane (DCNQ)-bridged ferrocenyl dimers 5–8 were designed and synthesized by the [2 + 2] cycloaddition–retroelectrocyclization reaction of diferrocenyl complexes 3 and 4 with tetracyanoethylene (TCNE) and 7,7,8,8 tetracyanoquinodimethane (TCNQ), respectively. The effect of constitutional isomers (para vs meta) and different acceptors on their donor–acceptor interactions and photophysical and redox properties as well as electronic structures was evaluated using a variety of experimental and theoretical methods. The single-crystal X-ray structures of TCBD- and DCNQ-bridged ferrocenyl dimers 6 and 7 are reported. The DCNQ-bridged ferrocenyl dimers 7 and 8 have lower HOMO–LUMO gap values with red-shifted absorption bands in comparison to those of TCBD-bridged ferrocenyl dimers 5 and 6. Mossbauer spectra of 3–8 are suggestive of very similar isomer shifts and quadrupole splittings in all diferrocene complexes despite their different proximities to the ele...

Cs‐Symmetric Donor–Acceptor Bis(thiazole)s: Synthesis and Photophysical, Electrochemical, and Computational Studies

AbstractWe herein report the design and synthesis of Cs‐symmetric donor–acceptor (D–A) molecular systems that have electron‐donating and electron‐withdrawing groups of the type D‐π‐A‐π‐D and D‐A1‐A‐A1‐D by using a Pd‐catalyzed Sonogshira cross‐coupling and [2+2] cycloaddition–retroelectrocyclization reactions. The photophysical and electrochemical properties as well as computational studies of these systems were explored, and strong donor–acceptor interactions were found. The [2+2] cycloaddition–retroelectrocyclization reaction pathway was studied by computational calculations, which revealed that bis(thiazole)s that contain donor groups at the terminal positions were favored in the reaction with tetracyanoethene (TCNE), whereas bis(thiazole)s that contain electron‐withdrawing groups were disfavored.

Ultrafast Charge-Separation in Triphenylamine-BODIPY-Derived Triads Carrying Centrally Positioned, Highly Electron-Deficient, Dicyanoquinodimethane or Tetracyanobutadiene Electron-Acceptors.

A series of new triphenylamine (TPA)-substituted BODIPYs 1-3 have been designed and synthesized through the Pd-catalysed Sonogashira cross-coupling and [2+2] cycloaddition-retroelectrocyclization reactions in good yields. This procedure yielded highly electron-deficient tetracyanobutadiene (TCBD) or dicyanoquinodimethane (DCNQ) electron-acceptor units centrally located at the TPA-BODIPY system. As a consequence, significant perturbation of the photonic and electronic properties was observed. The triads 2 and 3 showed red-shifted absorption, in addition to a strong charge-transfer-type absorption in the case of 3. The electrochemical studies revealed multi-redox processes involving the TPA, TCBD or DCNQ and BODIPY entities. The computational studies were performed at the B3LYP/6-31G** level to elucidate the geometry and electronic structures. An energy level diagram established for triads 2 and 3 revealed that the photoinduced charge-separation from the 1 BODIPY* is thermodynamically possible. In addition, charge transfer from TPA to TCBD in 2 and DCNQ in 3 was also possible. These charge transfer mechanisms were confirmed by photochemical studies performed using time-resolved emission and femtosecond-transient-absorption studies in solvents of varying polarity. Ultrafast charge-separation has been witnessed in these closely spaced, strongly interacting triads. The charge-separated state returned to the ground state without populating the 3 BODIPY*.

Unsymmetrical and Symmetrical Push-Pull Phenothiazines.

A series of unsymmetrical and symmetrical push-pull phenothiazines (3-7) were designed and synthesized by the Pd-catalyzed Sonogashira cross-coupling reaction and subsequent [2 + 2] cycloaddition-retroelectrocyclization reaction with tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ). The effect of systematic variation of the number and nature of cyano-based acceptor TCNE and TCNQ units on the photophysical, electrochemical, and computational studies was investigated. The single-photon absorption on phenothiazines 3-7 reveals that substitution of 1,1,4,4-tetracyanobutadiene (TCBD) and a cyclohexa-2,5-diene-1,4-diylidene-expanded TCBD unit results in strong intramolecular charge transfer and lowering of the LUMO energy level. The TCBD-linked and cyclohexa-2,5-diene-1,4-diylidene-expanded TCBD-linked phenothiazines 3-7 exhibit multiredox waves. The computational studies on phenothiazines 3-7 exhibit substantial stabilization of the LUMO with the increase in acceptor strength, which results in lowering of the HOMO-LUMO gap.

Tetracyanobutadiene bridged ferrocene and triphenylamine functionalized pyrazabole dimers

Herein we have designed and synthesized tetracyanobutadiene (TCBD) bridged ferrocenyl pyrazabole dimer Fc-TCBD and triphenylamine pyrazabole dimer TPA-TCBD by [2+2] cycloaddition-retroelectrocyclization reaction of ferrocene and triphenylamine functionalized pyrazabole dimers 1 and 2, to evaluate the effect of TCBD on the photonic and electrochemical properties. The incorporation of TCBD shifts the absorption from ultraviolet region to visible region by 147 nm in TPA-TCBD. The TCBD derivatives Fc-TCBD and TPA-TCBD show red shifted broad charge-transfer (CT) bands with low HOMO – LUMO gap values compared to ethyne bridged pyrazabole dimers 1 and 2. The electrochemical study reveals that, the additional two successive one electron reduction waves at low potential in Fc-TCBD and TPA-TCBD corresponds to reduction of TCBD unit. The theoretical investigation supports the experimental observations of red shift in TCBD derivatives. The photophysical, electrochemical and computational studies show substantial donor–acceptor interaction between electron donor moiety (ferrocene and triphenylamine) and electron accepting TCBD unit.

Design and Synthesis of Low HOMO–LUMO Gap N‐Phenylcarbazole‐Substituted Diketopyrrolopyrroles

AbstractThe use of the electron‐withdrawing cyano group to lower energy levels and extend light absorption of compounds for optoelectronic applications is well known. The use of cyano group incorporation has been reported to improve the electron mobility in organic photovoltaics to increase performance. Recently, we have reported that materials based on multiple acceptors including 1,1,4,4‐tetracyanobutadiene (TCBD) and diketopyrrolopyrrole (DPP) possesses excellent photophysical characteristics such as strong light absorption, co‐planar structure and good photochemical stability, which can be utilized as non‐fullerene electron acceptors for bulk heterojunction organic solar cells. To examine the effect of TCBD on the optical properties of DPPs, we designed and synthesized ethyne‐bridged N‐phenylcarbazole‐substituted DPPs and their TCBD derivatives by Pd‐catalyzed Sonogashira cross‐coupling and [2+2] cycloaddition–retroelectrocyclization reactions, respectively. The photophysical, thermal, electrochemical and computational properties of these compounds were investigated, which show substantial donor–acceptor interactions between the N‐phenylcarbazole and DPP moieties. The N‐phenylcarbazole‐substituted DPPs exhibit excellent thermal stability. The TCBD derivatives showed redshifted, broad charge‐transfer bands in the visible region with low HOMO–LUMO gaps compared to the corresponding ethyne‐bridged N‐phenylcarbazole‐substituted compounds. The electrochemical study revealed additional reduction waves in the TCBD‐bridged compounds, which correspond to the TCBD moiety itself.