Trade-off between mechanical flexibility due to amorphicity and highly facile charge transport emanating from molecular crystallinity demands the orientation of conjugated polymers (CPs) for their utilization as active semiconducting material for flexible organic electronics. We have already demonstrated that it is rather easy to orient nonregiocontrolled poly(3-hexylthiophenes) (NR-P3HT) as compared to their highly regioregular counterparts due to very high alkyl chain interdigitation. To provide an amicable solution, efforts have been directed to orient blends of two CPs such as NR-P3HT (amorphous and flexible) and poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT) (crystalline and facile charge transport) using a solution-based procedure floating film and transfer method (FTM). FTM-processed thin films of this blend system exhibited very high field effect transistor (FET) mobility reaching up to 0.1 cm2/V s, which is much higher than the corresponding individual CPs. In spite of only 10% incorporation of PBTTT in blend of NR-P3HT and PBTTT, there was a synergistically enhanced optical dichroic ratio (4.6 to 7.2) and FET mobility (8-fold) as compared to pristine NR-P3HT. At the same time, there was a 5-fold enhancement of FET mobility when 20% NR-P3HT was added in PBTTT as compared to that of PBTTT. This synergistic enhancement of charge carrier transport in the blend system has been explained by formation of oriented self-assembled fibrous domains of NR-P3HT and facile interdomain transport in crystalline PBTTT.

•A series of far-red sensitive dyes with tunable energetics were designed and developed.•6-311G/LSDA was found be optimum for reliable theoretical prediction of HOMO and λmax.•It is possible to inject electrons in TiO2 CB with minimum energy barrier of 0.16 eV.A series of far-red sensitizing squaraine dyes has been systematically designed and synthesized in order to correlate the theoretically calculated values with their corresponding experimental parameters. Efforts have been directed towards determining the minimum thermodynamic energy barrier for the electron injection in the nanoporous TiO2 by logical molecular design. Theoretical calculations using Gaussian program package were performed for ground and excited states in both of the isolated gaseous state as well as in solution including the solvent effect using a self-consistent reaction field polarizable continuum model (PCM). Implementation of the PCM model or use of LSDA functional under TD-DFT calculations gives much better results for energetics as well as absorption maximum for all of the sensitizers used in this work. Newly designed symmetrical squaraine dye SQ-5 exhibits a minimum energy barrier of 0.16 eV for electron injection and shows photon harvesting behavior in far-red region with external photoconversion efficiency of 2.02% under simulated solar irradiation.

•Carboxy functionalized unsymmetrical cyanine dyes with different substituents were successfully synthesized and characterized.•These NIR dyes were subjected to photophysical investigations in order to explore their applicability as fluorescent probes.•These dyes interact with BSA to form dye-BSA conjugates leading to enhancement in the fluorescence intensity.•Cyanine dye with mild electron withdrawing –I group (UCD-3) exhibited the highest binding affinity with BSA.Novel near infrared (NIR) sensitive unsymmetrical cyanine dyes bearing direct –COOH functionalized indole ring were synthesized, characterized and subjected to photophysical investigations. These unsymmetrical cyanine dyes were then subjected to investigate their interaction with bovine serum albumin (BSA) as a model protein in Phosphate buffer solutions. Apart from NIR absorption and emission with high molar extinction coefficients they exhibit a blue shift in PBS solution owing to their enhanced dye aggregation. Interaction of these dyes with BSA leads to not only enhanced emission intensity but also bathochromically shifted absorption maximum due to formation of dye-BSA conjugate. These dyes bind strongly with BSA having about an order of magnitude higher binding constant as compared to the typical cyanine dyes. Amongst the unsymmetrical cyanine dyes investigated in this work one bearing substituents like Iodo and carboxylic acid in the terminal Indole rings (UCD-3) exhibited highest association with the BSA having very high binding constant of 1.01 × 107 M−1.Download high-res image (158KB)Download full-size image

•Novel carboxy functionalized squaraine dye (SQ-1) have been used as NIR fluorescent probe.•One-pot dye-peptide conjugate (SQ 1 PC) was synthesized by facile synthetic route.•Efficient fluorescence quenching of SQ 1 PC (81%) assisted by dye aggregation.•Demonstration of fluorescence ON biosensing after elastase hydrolysis.Extended wavelength analyte-responsive fluorescent probes are highly desired for the imaging applications owing to their deep tissue penetration, and minimum interference from autofluorescence by biomolecules. Near infra-red (NIR) sensitive and self-quenching fluorescent probe based on the dye-peptide conjugate (SQ 1 PC) was designed and synthesized by facile and efficient one-pot synthetic route for the detection of Elastase activity. In the phosphate buffer solution, there was an efficient quenching of fluorescence of SQ 1 PC (86%) assisted by pronounced dye-dye interaction due to H-aggregate formation. Efficient and fast recovery of this quenched fluorescence of SQ 1 PC (> 50% in 30 s) was observed on hydrolysis of this peptide-dye conjugate by elastase enzyme. Presently designed NIR sensitive self-quenching substrate offers the potential application for the detection of diseases related to proteases by efficient and fast detection of their activities.Download high-res image (61KB)Download full-size image

Combined theoretical and experimental approaches were implemented to design model far-red sensitive unsymmetrical squaraine dyes in order to estimate the minimum energy barrier required for dye regeneration. Our logical molecular design indicated that it is possible to have a fine control on the energetics within 0.2 eV only by the judicious selection of substituents and alkyl chain length keeping the main π-molecular framework the same. The utilization of the LSDA functional under TD-DFT calculations offered an effective and economical computational method for the reliable prediction of the energetics as well as the absorption maximum of the sensitizers. Among the designed dyes under investigation, SQ-75 exhibited the best photovoltaic performance, having a short-circuit current density of 10.92 mA cm−2, open circuit voltage of 0.57 V and a fill factor of 0.67, leading to a photoconversion efficiency of 4.25% despite having photon harvesting mainly in the far-red region. The best photon harvesting by SQ-75, even with an energy difference of only 0.12 eV between the energy of its highest occupied molecular orbital and redox energy level I−/I3− electrolyte, corroborates the possibility for dye regeneration with such a small driving force.

Aiming toward the development of far-red sensitive organic dyes, unsymmetrical squaraine dye bearing direct cyanoacrylate functionalized indole ring has been synthesized and characterized along with its utilization as photosensitizer for dye-sensitized solar cells. Upon dye-sensitized solar cell fabrication, this sensitizer exhibits its potentiality as a good far-red sensitive dye having photoconversion efficiency of 5.03% under the simulated solar irradiation at AM 1.5 conditions. This opens up further possibility to design efficient far-red sensitive dyes by judicious implementation of suitable donor moieties with extended π-conjugation.

Symmetrical squaraine (SQ) dyes with varying alkyl chain lengths have been synthesized towards their utilization as sensitizer for enhancing the photon harvesting in far-red region of solar spectrum. It has been observed that energy level of the SQ-dyes can be systematically tuned only by alkyl chain substitution. It has also been shown that SQ-dyes behave like p-type donors forming a p–n heterojunction with soluble fullerene derivative phenyl-C61-butyric acid methyl ester (PCBM) as n-type organic electron acceptor. Thin film organic photovoltaic p–n heterojunction devices have been fabricated using soluble SQ-dyes with PCBM without using any thermal evaporation technique for the active layers. A perusal of the photo-action spectra clearly corroborates that at least 0.25 eV energy barrier is necessary for the facile electron transfer from donor moiety to the acceptor after the photo-excitation.Highlights► Squaraine dyes with systematically varying energy levels have been synthesized. ► They exhibit intense light absorption in far-red region with narrow absorption window. ► Completely solution processable organic solar cells were fabricated. ► Solar cells were made using squaraine dyes with a fullerene derivative. ► Need of about 0.25 eV energy barriers for facile electron transfer was demonstrated.

A contact free method of surface potential measurement using scanning Kelvin-probe microscopy (SKPM) was conducted to probe the nature of nanocrystalline TiO2/dye interface. In combination with electrical measurements an effort has been made to establish a correlation between the nature of sensitizing dye and observed surface potential with open circuit voltage (Voc) after dye-sensitized solar cell (DSSC) fabrication. Effect of chenodeoxycholic acid (DCA) as co-adsorbent with dyes upon the enhancement of DSSC efficiency has been probed by SKPM, which revealed a positive shift of surface potential upon treatment of thin films of TiO2 with DCA. The enhancement of DSSC performance upon DCA introduction has been explained by upward shift of TiO2 conduction band edge leading to enhanced Voc along with the prevention of π-stacked aggregation resulting in enhanced short-circuit current density.

Synthesis of novel cyan-colored sensitizing dyes bearing squaric acid core and 2,3,3-trimethyl-indole as terminal moieties has been conducted in order to fabricate dye-sensitized solar cells based on nanoporous TiO2. It has been found that position of –COOH functionality utilized for anchoring with TiO2 surface has a marked effect on solar cell performance. Carboxylic acid group directly substituted to indole ring gave about 5-fold higher conversion efficiency as compared to the dye when it was substituted in alkyl chain of the indole ring. Efficiency has been found to be hampered due to aggregation and enhancement in the efficiency was observed when dyes were used with chenodeoxycholic acid (CDCA). Using CDCA and long alkyl substituent at the N-position of indole ring to prevent aggregation and enhanced TiO2 surface passivation, respectively, has achieved a solar conversion efficiency of 3.15% with a short circuit current density of 7.26 mA/cm2, an open circuit voltage of 0.64 V and a fill factor of 0.68 for SQ-5 under standard AM 1.5 solar irradiation.

We have synthesized a series of novel blue colored symmetrical squaraine sensitizers with variable alkyl chain length for their application towards the fabrication of dye-sensitized solar cells (DSSCs). It has been found that an increase in the alkyl chain length substituted at N-position of indole ring exhibits enhanced electron diffusion length and electron life-time resulting in better passivation of nanocrystalline TiO2 surface leading to enhancement in the cell performance. Based on HOMO and LUMO energy measurement of squaraine dyes, it has been demonstrated that about 0.16 eV energy barrier is sufficient for electron injection from LUMO of dye to TiO2 conduction band and dye regeneration after photo-excitation. Performances of DSSCs using model squaraine dyes indicate that dodecyl alkyl substituent is optimum giving highest Voc and use of chenodeoxycholic acid along with the dye SQ-4 shows a photoconversion efficiency of 3.5% under AM 1.5 irradiation.

Alkyl and fluoroalkyl substituted symmetrical and unsymmetrical squaraine dyes have been synthesized for the fabrication of dye-sensitized solar cells (DSSC) based on nanoporous TiO2. Results of DSSC performance clearly indicate that introduction of molecular asymmetry and increase in the alkyl chain length of the squaraine sensitizers leads to the enhancement in the photovoltaic performance. A perusal of photo-action spectra of squaraine sensitizer corroborates that introduction of molecular asymmetry and fluoroalkyl substitution leads to hampering of blue-shifted H-aggregate formation. Estimation of energy of HOMO and LUMO for these squaraine sensitizers used in the present investigation indicates that about 0.16 eV is sufficient for electron injection from photoexcited dye to TiO2 conduction band and dye regeneration.