Dicyanovinyl Group Research Articles

Di- and Tricyanovinyl-Substituted Triphenylamines: Structural and Computational Studies.

We report herein on the solid-state structures of three closely related triphenylamine derivatives endowed with tricyanovinyl (TCV) and dicyanovinyl (DCV) groups. The molecules described contain structural features commonly found in the design of functional organic materials, especially donor-acceptor molecular and polymeric architectures. The common feature noticeable in these structures is the impact of these exceptionally strong electron-accepting groups in forcing partial planarity of the portion of the molecule carrying these groups and directing the molecular packing in the solid state, resulting in the formation of π-stacks of dimers within the unit cell of each. Stacks are formed between phenyl groups bearing electron-accepting groups on two adjacent molecules. Short π-π stack distances ranging from 3.283 to 3.671 Å were observed. Such motif patterns are thought to be conducive for better charge transport in organic semiconductors and enhanced device performance. Intramolecular charge transfer is evident from the shortening of the observed experimental bond lengths in all three compounds. The nitrogen atoms (of the cyano groups) have been shown to be extensively involved in short contacts in all three structures, primarily through C-H···NC interactions with distances as short as 2.462 Å. The compounds reported here are (3,3-dicyano-2-(4-(diphenylamino)phenyl)-1λ3-allylidene)amide or tricyanovinyltriphenylamine, Ph3NTCV (1); 2-(4-(diphenylamino)benzylidene)-malononitrile or dicyanovinyltriphenylamine, Ph3NDCV (2); and (3,3-dicyano-2-(4-(di-p-tolylamino)phenyl)-1λ3-allylidene)amide or dimethyltricyanovinyltriphenylamine, Me2Ph3NTCV (3). Results of density functional theory calculations using DFT-B3LYP/6-31G(d,p) indicate the lowering of LUMO levels as a result of the introduction of these groups with band gaps of 3.13, 2.61, and 2.55 eV for compounds 1-3, respectively, compared with 4.65 eV calculated for triphenylamine. This is supported by the electronic and fluorescence spectra of these molecules with absorption λmax of 483, 515, and 545 nm for compounds 1, 2, and 3, respectively.

Fluorescence emission modification of triphenylamine derivatives by aggregate formation in solution or by mechanical stress in solid state

Two derivatives of triphenylamine, 4-(diphenylamino)benzaldehyde and 2-(4- (diphenylamino)benzylidene)malononitrile, with acceptor mesomeric groups, an aldehyde moiety and a dicyanovinyl group respectively, were synthesized and found to have aggregation-induced emission (AIE) or aggregation-induced enhanced emission (AIEE) properties in several DMF/H2O mixtures. The size of the formed aggregates was studied with Dynamic Light Scattering (DLS) and a significant change of approximately 200 nm was observed according to the water fraction in DMF. Mechanoluminochromism characteristics in the solid state were also observed. A shift in the emission bands was noticed when comparing the solid before and after grinding, as well as when comparing the crystalline and amorphous form.

5‐N,N‐Diarylaminothiazoles with Electron‐Accepting Groups: Synthesis, Photophysical Properties, and Their Application for the Detection of Hydrazine Hydrate

Abstract5‐N,N‐diarylaminothiazoles containing cyano and nitro groups were synthesized using the Pd‐catalyzed Buchwald‐Hartwig amination reaction with good yields. The cyano group in the resultant thiazole was reduced to a formyl group. This was then subjected to the Knoevenagel condensation reaction, leading to the formation of thiazoles with a dicyanovinyl group. The nitro group in the thiazole was reduced to an amino group, which was subsequently reacted with triphosgene, yielding a thiazole with an isocyanate group. These thiazoles, with their electron‐accepting properties, demonstrated absorption and emission spectra at longer wavelengths. Notably, the thiazole containing the dicyanovinyl group displayed a red emission. Tests for the detection of hydrazine, a hazardous volatile organic compound, were conducted using the synthesized thiazoles. The results showed that the dicyanovinyl group effectively responded to hydrazine hydrate, evidenced by changes in the absorption and emission spectra. This change in color was also visibly detectable to the naked eye.

Panchromatic and Perturbed Absorption Spectral Features and Multiredox Properties of Dicyanovinyl- and Dicyanobutadienyl-Appended Cobalt Corroles.

Four new β-functionalized π-extended cobalt corroles with one and two dicyanovinyl (DCV) or dicyanobutadienyl (DCBD) moieties at the 3- and 3,17-positions have been synthesized and characterized by various spectroscopic techniques. Interestingly, the synthesized DCV- and DCBD-appended cobalt corroles displayed panchromatic and near-infrared absorption in the range 300-1100 nm in CH2Cl2 and pyridine solvents. (MN)2-(Cor)Co and A2MN2-(Cor)Co exhibited 8-9 times enhancement in the molar absorptivity of the Q band compared to the parent corrole ((Cor)Co). The unique absorption spectral features of these β-functionalized cobalt corroles are splitting, broadening, and red-shifting in the Soret and Q bands. One DCV unit brings a 30-46 nm red shift, whereas one DCBD unit brings a 40-75 nm red shift in the Q band compared to the corresponding precursors. This is rare that the intensity of the longest Q band is greater than or equal to the Soret-like bands. These corrole derivatives exhibit UV-vis spectral features similar to those of chlorophyll a. A 220 mV positive shift per DCV group and 160 mV positive shift per DCBD group were observed in the first oxidation potentials compared to (Cor)Co in the desired direction for the utility of these cobalt complexes in electrocatalysis. DFT studies revealed that HOMO and LUMO were stabilized after appending DCV and DCBD groups on the corrole macrocycle and exhibited a "push-pull" behavior leading to promising material applications in nonlinear optics (NLO) and catalysis.

Highly Efficient β‐Functionalized Oxidomolybdenum(V) Corroles for Catalytic Oxidative Bromination of Phenols at Room Temperature

AbstractTwo new β‐functionalized oxidomolybdenum(V) corroles, oxido[3‐formyl‐5,10,15‐triphenylcorrolato]molybdenum(V) (Mo‐1) and oxido[3‐dicyanovinyl‐5,10,15‐triphenylcorrolato]molybdenum(V) (Mo‐2) were synthesized and characterized by various spectroscopic techniques and electrochemical studies. Mo‐2 manifests splitted B bands due to x and y polarizations and highly red shifted longest B and Q bands due to the electron‐deficient nature of the dicyanovinyl group. EPR data showed that these complexes exhibit an axial compression with dxy1 configuration. DFT studies revealed that HOMO and LUMO orbitals are stabilized in Mo‐2 relative to Mo‐1. Mo‐1 exhibits two successive reversible reductions and two oxidation potentials in cyclic voltammetry. Surprisingly, Mo‐2 exhibits three successive reversible reductions and two oxidations; the one extra reduction could possibly be due to the reduction of the dicyanovinyl moiety. The catalytic activities of Mo‐1 and Mo‐2 for the oxidative bromination of various phenols using H2O2‐KBr‐HClO4 mixture in water have been explored and exhibited excellent activity at a very low catalyst loading of 0.0030 and 0.0028 mol%, respectively. Both synthesized β‐functionalized Mo(V) corroles manifest much higher conversion and TOF (59801–71174 h−1) for oxidative bromination of phenols relative to earlier reported meso‐functionalized Mo(V) corroles (20781–61646 h−1). Hence, Mo‐1 and Mo‐2 mimic vanadium bromoperoxidase (VBPO) and act as functional models for these catalytic applications. These catalysts were reused upto 3 cycles and showed conversion rate upto 82 % indicating their excellent thermal and chemical stabilities.

A reaction-based carbazole-dicyanovinyl conjugated colorimetric and ratiometric fluorescent probe for selective detection of cyanide ions

In the present work, 4-(9′-hexylcarbazol-3′-yl)benzylidenemalononitrile 5 (probe L) was tested as a colorimetric and ratiometric fluorescent probe in dimethyl sulfoxide (DMSO) medium towards anions, cations and neutral molecules. The sensing properties of probe L were investigated by using UV–Vis absorption and fluorescence spectroscopy techniques. Probe L showed selectivity and sensitivity towards cyanide ions (CN–) in the presence of analytes used. Upon the addition of CN–, intramolecular charge transfer (ICT) band at 425 nm in UV spectrum disappeared. In addition, ICT emission intensity at 593 nm decreased and ligand-centred (LC) emission intensity at 480 nm increased. These findings indicate that nucleophilic conjugate addition of CN– to the dicyanovinyl group of probe L successfully occurs, hence forming a new adduct between probe L and CN–. In this adduct, π-conjugation was partially blocked, and the ICT transfer was hindered. Adduct formation was proved by Job’s plot, 1H NMR and FT-IR analysis. Probe L showed very low limit of detection (LOD) value of 1.467 nM towards CN–. Probe L was also applied to the CN– detection in real-world water samples by the spike and recovery method. The maximum relative standard deviation (RSD) value was 4.24, indicating this method works successfully. Therefore, probe L could find a potential use in detection of CN– in liquid media.

Comparison of Reactive Sites in 2(1H)-Quinolone Derivatives for the Detection of Biologically Important Sulfur Compounds.

Novel fluorescent probes based on 2(1H)-quinolone skeleton containing a malonate group (Q1-Q3) were synthesized and proposed for biothiols detection. Their chemical reactivity toward thiols was compared to the reactivity of derivative having a dicyanovinyl group (Q4) as a reactive site. The detailed photophysical properties of these compounds were assessed through the determination of absorption and fluorescence spectra, fluorescence quantum yield, and fluorescence lifetime. In the presence of biothiols, an increase in the fluorescence intensity of compounds Q1-Q3 and a hypsochromic shift in their emission bands were observed. In contrast, the compound with the dicyanovinyl group (Q4) in the presence of biothiols and cyanide ion showed the quenching of fluorescence, while a fluorescence "turn on" effect was observed toward reactive sulfur species.

A triphenylamine-based fluorescence probe for detection of hypochlorite in mitochondria

The level of HClO/ClO− in mitochondria is essential to keep the normal function of mitochondria. Therefore, it is meaningful to accurately and quickly monitor ClO− in mitochondria. In this work, a new triphenylamine-based fluorescence probe PDTPA was designed and synthesized, in which pyridinium salt and dicyano-vinyl group were introduced as mitochondria targeting site and reaction site for ClO−. The probe showed high sensitivity and fast fluorescence response (<10 s) in the detection of ClO−. Moreover, the probe PDTPA had good linearity in a wide concentration range of ClO− and its detection limit was calculated as 10.5 μM. Confocal fluorescence images demonstrated that the probe could target mitochondria and track the fluctuations of endogenous/exogenous ClO− levels in the mitochondria of living cells.

Star-shaped benzotriindole-based donor compounds for all–small–molecule non-fullerene organic solar cells

The recent success in the development of non-fullerene acceptors (NFAs) for organic solar cells (OSCs) encourages the search for novel efficient and complementary donor materials. Moreover, the in-depth understanding of the structure–property correlations for new generations of acceptor and donor materials is of great importance for the further progress in the field of OSCs. In this work the synthesis of a series of star-shaped small molecules based on benzotriindole (BTI) electron-donating core linked through bi– or terthiophene π-spacers to either hexyl dicyanovinyl or 2-ethylhexyl cyanoacetate electron-withdrawing terminal groups (EWGs) is reported. The thermal, optical and electrochemical properties of the molecules were carefully investigated and compared. The molecules were also explored as donor materials in non-fullerene (NF) OSCs in binary blends with well-known NFAs such as IDIC or Y6. The huge impact of the donor molecular structure on the device performance (up to 6 times difference in power conversion efficiency (PCE)) was evaluated due to significant difference in the active layer morphologies, which was successfully proved via scanning near-field infrared microscopy technique. The results obtained in this work demonstrate high potential of star-shaped BTI-based molecules to be used as donor materials with a new generation of NFAs and can be used for further molecular design of the highly efficient small molecule donors for NF OSCs.

Morphology Determines an Efficient Coherent Electron Transport for Push-Pull Organic Semiconductors Based on Triphenylamine and Dicyanovinyl Groups.

The morphology of the active layer in organic solar cells is fundamental for achieving high power conversion efficiency. However, the morphological characteristics for optimal performance are still being investigated. An atomistic computational approach is required to determine the relationship between active layer morphology and performance. Since the organic solar cell has multiple phases and interfaces, the computational modeling of charge generation and transport is challenging. We then used a set of push-pull semiconductors to illustrate how the electronic transmission spectrum, derived from the Landauer-Büttiker formalism, can be used to investigate the efficiency of coherent charge transport across anisotropic organic solids. The electronic transmission spectrum was calculated from the electronic band structure obtained using the density-functional-based tight-binding method. We found that coherent charge transport was more efficient along the direction parallel with the interface between the electron-acceptor and electron-donor moieties for a herringbone morphology.

Cyanide detecting porphyrin fluorescent sensors: Effects of electron-donating/withdrawing substituents

The detection of cyanide (CN−) and other dangerous chemicals is critical in many practical scenarios. In this study, dicyanovinylporphyrins (DCVPs) 2a to 2d with electron-donating or electron-withdrawing substituents as fluorescent sensors for CN− detection were synthesized through Lindsay's condensation reaction. The 2a to 2d absorption, fluorescence, and fluorescence lifetimes of the DCVPs were investigated in THF. To probe the reactivity of DCVPs to CN−, the electron density of β-carbon in their dicyanovinyl groups was controlled by introducing electron-donating or electron-withdrawing groups. The anion (Cl−, Br−, I−, ClO4−, HSO4−, NO3−, and CN−) sensing abilities of DCVPs 2a to 2d were investigated through fluorescence spectroscopy in THF. The DCVPs exhibited selective reduction in fluorescence intensity upon the addition of CN−ions. DCVP 2d also exhibited strong detection capabilities for CN−ions. Specifically detection limit for CN− was found to be 3.14 × 10−8 M in THF.

Synthesis of Push-Pull Azulene-Based Compounds

Nowadays, non-benzenoid aromatic hydrocarbons are widely used as synthons for the production of new organic semiconductors with interesting photophysical characteristics. For instance, a non-benzoid azulene hydrocarbon with a polar structure, a narrow energy gap between the highest free and lowest occupied molecular orbital and the ability to form stable ions can be intended as a structural moiety for the synthesis of new conjugated compounds with important optical and electronic properties. The article discusses the synthesis and investigation of the optical properties of new push-pull azulene-based compounds. It shows that Friedel-Crafts acylation is used as the key reaction for the synthesis of methyl- and phenyl-dicyanovinylated azulenes. The interaction proceeds regioselectively at the C1 and C3 positions of the five-membered azulene ring. It is identified that the synthesis of push-pull dicyanovinylated azulenes by Knoevenagel condensation of azulenyl ketones with malononitrile proceeds easily in Py and DMSO. The UF-vis spectra of the obtained azulene push-pull compounds demonstrated strong electron absorption in the visible zone with λmax at 410, 430, 434 and 452 nm associated with transport of charge between the donor azulene ring and the acceptor dicyanovinyl group. The scheme of resonant structures shows the mechanism of intramolecular donoracceptor interaction. The structure of the synthesized push-pull dicyanovinylated nonazulenes was elucidated using modern physicochemical and spectroscopic research methods.

4,4-Bis(2-ethylhexyl)-6-(9-(2-ethylhexyl)-2,3,4,4a,9,9a-hexahydro-1H-carbazol-6-yl)-4H-cyclopenta[2,1-b:3,4-b′]dithiophene-2-carbaldehyde

Dyes with a donor–π–spacer–acceptor (D-π-A) structure containing a dicyanovinyl group as an acceptor have recently been of interest for the production of single-component organic solar cells. The most convenient precursors for their synthesis are the corresponding aldehydes. In this communication, 4,4-bis(2-ethylhexyl)-6-(9-(2-ethylhexyl)-2,3,4,4a,9,9a-hexahydro-1H-carbazol-6-yl)-4H-cyclopenta[2,1-b:3,4-b′]dithiophene-2-carbaldehyde was synthesized by the Suzuki cross-coupling reaction between 4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b′]dithiophene-2,6-dicarbaldehyde and 9-(2-ethylhexyl)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,3,4,4a,9,9a-hexahydro-1H-carbazole in the presence of tetrakis(triphenylphosphine)palladium(0). The structure of the newly synthesized compound was established by means of high-resolution mass spectrometry, 1H, 13C NMR, IR, and UV spectroscopy.

Real-Time Fluorescence Screening Platform for Meat Freshness

Meat's freshness is closely related to food safety and human health and has received increasing attention nowadays. To on-site visually screen meat freshness in a fast and non-destructive manner, we rationally constructed a series of fluorescent probes (JDCN, JDNS, and JDPY) with distinct electron-withdrawing substitution groups based on julolidine-fused coumarin. These probes underwent an aza-Michael addition followed by an elimination reaction with cadaverine to generate a colorimetric and ratiometric fluorescence response, and their sensing performance was rationally enhanced by improving the electron-withdrawing strength of substitution groups. Particularly, JDCN with a dicyanovinyl group as the reaction site exhibited outstanding sensing performance including rapid response (∼60 s), high selectivity, and low detection limit (14 nM). Furthermore, JDCN was fabricated into test kits to detect cadaverine vapor with a high-contrast fluorescence change from red to green. Based on two-color visualization of cadaverine vapor, on-site non-contact and non-destructive monitoring of meat freshness was successfully achieved. The good sensing performance rendered JDCN test kits a promising real-time fluorescence screening platform for rapid, non-destructive, and accurate evaluation of meat freshness.

Dual-functional turn-on fluorescent probe for discriminative sulfite and sulfide detection via organic/aqueous ratio tuning and its application in real samples

Sulfite and sulfide are substances commonly present in food, biological and industrial processes. While excess amounts of these anions can elicit physiological disorders in humans, there are only limited examples of probes capable of selectively detecting both of them. In this study, we present a sulfite/sulfide dual-functional probe 1 based on a dimethylaminonaphthalene-oxazaborine fluorophore and a dicyanovinyl reaction site. Probe 1 enabled a highly selective detection of sulfite under acetonitrile/tris buffer (85:15, v/v), discriminating sulfite from common interfering species such as sulfide, cyanide, and biothiols. The probe fully responded to sulfite within 4 min, with an 18-fold increase in the fluorescence intensity. Besides, probe 1 was also able to selectively sense sulfide in pure acetonitrile, while displaying a detection limit as low as 96 nM. Mechanistic studies revealed that a large 170 nm Stokes shift of the probe after sulfite/sulfide detection can be ascribed to the nucleophilic addition of sulfite/sulfide to the dicyanovinyl moiety, which broke the conjugation system between the fluorophore scaffold and the dicyanovinyl group, thereby triggering the intramolecular charge transfer effect. Finally, the probe displayed good capability for sensing sulfite and sulfide in real samples with good recoveries, proving its potential in the determination of sulfite and sulfide concentrations for real-life applications.

Enhancing probe's sensitivity for peroxynitrite through alkoxy modification of dicyanovinylchromene.

An intramolecular charge transfer (ICT)-based fluorescent probe P-ONOO- was synthesized to detect ONOO-. After responding to peroxynitrite, the dicyano-vinyl group of P-ONOO- generates the aldehyde group, emitting strong green fluorescence accompanied by quenching of the yellow fluorescence. According to the calculated Fukui function, the modification of the alkoxy group can enhance the f+ of P-ONOO-, which can enhance the probe's nucleophilic addition reactivity with ONOO-. It has been experimentally verified that P-ONOO- shows fast response (within 30s), excellent sensitivity (the detection limit = 10.4nM), and good selectivity towards ONOO-. Additionally, the probe P-ONOO- has high membrane permeability and good biocompatibility, which can image endogenous ONOO- and exogenous ONOO- in HeLa cells.

Isomeric Pair of E/Z Tetraphenylethene-Cored Luminogens Showing Distinguishing Mechanoresponsive Luminescence Turn-On and Two-Color Behavior

A pair of tetraphenylethylene (TPE)-based E/Z isomers (E-TPE2PD and Z-TPE2PD) using two dicyanovinyl groups as the electron-accepting moieties have been synthesized and separated successfully. Reversible E/Z isomerization for each isomer is achieved, in which the isomerization speed from E to Z is higher than that from Z to E. This pair of pure E/Z isomers exhibits obvious AIEE properties. Z-TPE2PD shows highly morphology-dependent solid-state photoluminescent properties, whose solid-state emission is red-shifted from 564 to 588 nm with an enhancement of crystalline degree together with a decrease in the emission intensity. In contrast, E-TPE2PD leads to a slightly blue-shifted emission of 5 nm dependent on its crystalline degree. To the best of our knowledge, the discrepancy in emissive color between TPE-based E and Z isomers is much larger than most of the reported ones. The absence and presence of π–π interactions between adjacent PDCV units observed in their crystal packing structures are suggested to be responsible for the distinct solid fluorescence of E and Z isomers. More interestingly, Z-TPE2PD exhibits blue-shifted mechanoresponsive luminescence (MRL) turn-on behavior when subjected to grinding, while E-TPE2PD shows a remarkable two-color photoluminescence (PL) nature. This paper offers a synthetic strategy by introducing strong polar dicyanovinyl groups into the TPE core to increase the molecular polarity difference of E and Z isomers and facilitate their separation, which makes the exploration of distinguishing morphology-dependent solid-state PL properties possible. This is the first report on an isomeric pair of E/Z tetraphenylethene-cored luminogens displaying different MRL turn-on and dichromic behavior.

Mechanofluorochromic Material toward a Recoverable Microscale Force Sensor

AbstractAmong the multiple classes of mechanofluorochromic (MFC) compounds reported in recent years, simple donor–acceptor molecules involving oligooxyethylene N‐substituted diphenylamine connected to a dicyanovinyl group by a thienyl spacer constitute a specific class of mechano‐stimulable smart materials with a unique combination of properties including turn‐on mechanofluorochromism with red‐light photoluminescence emission, turn‐off second harmonic generation, and self‐recovery in ambient conditions. While the dynamics of the MFC processes of thin films of these materials have already been investigated, the correlation of the behavior observed at the macroscale with elemental processes taking place at the micro‐ and nanoscopic scales remains largely unexplored. In this work, atomic force microscopy (AFM) coupled with wide‐field and confocal optical microscopies is used to investigate the turn‐on/recovery MFC behavior of microcrystals and nanostructures. It is shown that the red light photoluminescence of microcrystals and nano‐objects can be turned‐on by contact AFM and that the intensity of light emission is linearly correlated to the applied nominal force. Recovery is associated with a decrease in emission intensity, which can be reactivated again by subsequent contact scans. These results thus pave the way toward the development of micro‐/nanoscale recoverable force‐sensing technologies based on this particular class of smart molecular materials.

A benzothiazole-based dual reaction site fluorescent probe for the selective detection of hydrazine in water and live cells.

As hydrazine is an environmental pollutant and highly toxic to living organisms, selective and rapid detection is highly needed for the benefit of living organisms as well as the environment. Here, we first introduced a novel benzothiazole conjugated methyldicyanovinyl coumarin probe BTC, with dual recognition sites for hydrazine detection. The incorporation of the methyldicyanovinyl group into the benzocoumarin fluorophore increased the electrophilicity of the lactone ring of the probe BTC facilitating the nucleophilic attack of hydrazine and rapid (within 1 min, low detection limit = 1.7 nM) turn-on sky blue fluorescence with 700-fold fluorescence intensity enhancement was observed via hydrazine-induced lactone ring-opening followed by selective cleavage of the dicyanovinyl group. According to the literature, dicyanovinyl group assisted lactone ring opening has revealed the possibility of hydrazine recognition with a large Stokes shift (140 nm) and a high fluorescence quantum yield (0.67). Here, the DFT study and practical applications of the probe BTC in different water samples have been presented. The probe BTC was also successfully applied for the detection of hydrazine in the vapor phase using paper strips and in live MDA-MB 231 cells.

Synthesis and the spectral, electrochemical, and nonlinear optical properties of β-dicyanovinyl-appended 'push-pull' porphyrins.

A series of "push-pull" porphyrins, MTPP(MN)(TPA)2 (M = 2H, CuII, NiII, and ZnII), having triphenylamine (TPA) and dicyanovinyl (DCN) groups at antipodal positions were synthesized and characterised by UV-Vis, fluorescence and NMR spectroscopic techniques, MALDI-TOF mass spectrometry, cyclic voltammetry, DFT, and elemental analysis, which were then further utilized for third-order nonlinear optical measurements under mild conditions using femtosecond laser pulses. Remarkably, MTPP(MN)(TPA)2 (M = 2H, CuII, NiII, and ZnII) exhibited 21-48 nm and 38-80 nm bathochromic shifts in B and Qx(0,0) bands as compared to the corresponding MTPPs (M = 2H, CuII, NiII, and ZnII); the results are consistent with the effect of enhanced resonance due to TPA and -I effect of DCN moieties. In cyclic voltammetry, the push-pull porphyrins exhibited a cathodic shift (0.13-0.51 V) in their first oxidation potential as compared to the precursor owing to the presence of electron-donating TPA groups. The third-order nonlinear optical responses were recorded using a single-beam femtosecond Z-scan technique to retrieve information about the nonlinear absorption and nonlinear refraction of the samples. The two-photon absorption coefficients (β) are in the range of 0.87 × 10-13 to 4.28 × 10-13 m W-1 and the nonlinear refractive index (n2) in the range of 1.21 × 10-19 to 7.36 × 10-19 m2 W-1. The ultrafast absorption dynamics of the ground-state bleaching (GSB) and photo-induced absorption (PIA) are monitored by femtosecond broadband transient absorption studies. The strong nonlinearity of these push-pull porphyrins makes them potential candidates for nonlinear optical and photonic device applications.