01326nas a2200157 4500008004100000245013300041210006900174260000800243300001600251520069100267100002100958700002000979700002400999700001701023856012801040 2011 eng d00aCompetitive binding of Ba2+and Sr2+ to 18-crown-6 in a receptor with a 1-methoxyanthraquinone analogue as the other binding site0 aCompetitive binding of Ba2and Sr2 to 18crown6 in a receptor with cOCT a4680–46903 a

Owing to their immense biological significance, development of sensors for the selective detection of alkaline earth metal ions has attracted vast research interest. In this article we have reported the synthesis, characterisation and ion binding studies of a new RuII-polypyridyl-crown-anthraquinone complex (5). Studies confirm selective binding of BaII, SrII and CaII ions, with Kmath image > Kmath image >> Kmath image, over all other metal ions, to the crown ether moiety and not to the methoxy anthraquinone component, the latter being the second binding site available and known for its affinity towards alkaline earth metal ions from one of our previous reports.

1 aBanerjee, Tanmay1 aSuresh, Moorthy1 aGhosh, Hirendra, N.1 aDas, Amitava uhttps://library.ncl.res.in/content/competitive-binding-ba2and-sr2-18-crown-6-receptor-1-methoxyanthraquinone-analogue-other02251nas a2200205 4500008004100000245015200041210006900193260000800262300001400270490000700284520148800291100001901779700002101798700001901819700001401838700001701852700002301869700002401892856012901916 2012 eng d00aPhotosensitization of nanoparticulate TiO2 using a Re(I)-polypyridyl complex: studies on interfacial electron transfer in the ultrafast time domain0 aPhotosensitization of nanoparticulate TiO2 using a ReIpolypyridy cAPR a8192-81980 v143 a

We have synthesized a new photoactive rhenium(I)-complex having a pendant catechol functionality [Re(CO)3Cl(L)] (1) (L is 4-[2-(4′-methyl-2,2′-bipyridinyl-4-yl)vinyl]benzene-1,2-diol) for studying the dynamics of the interfacial electron transfer between nanoparticulate TiO2 and the photoexcited states of this Re(I)-complex using femtosecond transient absorption spectroscopy. Our steady state absorption studies revealed that complex 1 can bind strongly to TiO2 surfaces through the catechol functionality with the formation of a charge transfer (CT) complex, which has been confirmed by the appearance of a new red-shifted CT band. The longer wavelength absorption band for 1, bound to TiO2 through the proposed catecholate functionality, could also be explained based on the DFT calculations. Dynamics of the interfacial electron transfer between 1 and TiO2 nanoparticles was investigated by studying kinetics at various wavelengths in the visible and near infrared regions. Electron injection into the conduction band of the nanoparticulate TiO2 was confirmed by detection of the conduction band electron in TiO2 (Image ID:c2cp24105f-t1.gif) and the cation radical of the adsorbed dye (1˙+) in real time as monitored by transient absorption spectroscopy. A single exponential and pulse-width limited (<100 fs) electron injection was observed. Back electron transfer dynamics was determined by monitoring the decay kinetics of 1˙+ and Image ID:c2cp24105f-t2.gif.

1 aKar, Prasenjit1 aBanerjee, Tanmay1 aVerma, Sandeep1 aSen, Anik1 aDas, Amitava1 aGanguly, Bishwajit1 aGhosh, Hirendra, N. uhttps://library.ncl.res.in/content/photosensitization-nanoparticulate-tio2-using-rei-polypyridyl-complex-studies-interfacial01847nas a2200181 4500008004100000245009700041210006900138260000800207300001600215490000600231520119900237100001901436700001901455700002101474700001701495700002401512856012901536 2012 eng d00aSequential energy and electron transfer in polynuclear complex sensitized TiO2 nanoparticles0 aSequential energy and electron transfer in polynuclear complex s cMAY a1543–15480 v33 a

Polynuclear–polypyridyl complexes exhibit a directional energy-transfer property that can improve their photosensitization activity. In the present work, the energy-transfer process is explored in a trinuclear Ru2∧Os1 complex using transient absorption spectroscopy. This study reveals an efficient excitation energy transfer from the terminal (RuII complex) to the core (OsII complex) region in the ultrafast time domain (400 fs–40 ps). The excitation energy funnel is useful in improving the functionalized core activity. This is evidenced in an interfacial electron-transfer study of Ru2∧Os1, Ru2∧Ru1, and Os1 complex sensitized TiO2 nanoparticle (TiO2 NP) systems. The intramolecular energy transfer causes sequential excitation of the core part of the Ru2∧Os1 complex, which leads to multiexponential electron injection into TiO2 NP. Besides this, the electronic coupling between the metal ion centers stabilizes the positive charge within the trinuclear complex, which results in a slow charge recombination reaction. This study shows that polynuclear complexes can be very useful for their panchromatic effects, unidirectional energy- and electron-transfer properties.

1 aVerma, Sandeep1 aKar, Prasenjit1 aBanerjee, Tanmay1 aDas, Amitava1 aGhosh, Hirendra, N. uhttps://library.ncl.res.in/content/sequential-energy-and-electron-transfer-polynuclear-complex-sensitized-tio2-nanoparticles01373nas a2200169 4500008004100000022001400041245014300055210006900198260011000267300001400377490000700391520061500398100002101013700001701034700002401051856012801075 2013 eng d a1144-054600aInterfacial charge recombination of Os(II)-polypyridyl-resorcinol complex on oleic acid capped TiO2 surface: what determines the dynamics?0 aInterfacial charge recombination of OsIIpolypyridylresorcinol co aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcJUL a3100-31080 v373 a

Femtosecond transient absorption spectroscopic studies of an osmium(II)-polypyridyl-resorcinol complex, 1, on oleic acid capped TiO2 have been carried out and the results have been compared with our previous studies on poly(vinyl) alcohol capped TiO2. While on both these surfaces the complex exhibits a single exponential <120 fs injection, the back electron transfer reaction is slower on the oleic acid capped TiO2 surface early on while it is faster on the same surface at longer times than on poly(vinyl)alcohol capped TiO2. The probable origin of these disparate observations has been analyzed.

1 aBanerjee, Tanmay1 aDas, Amitava1 aGhosh, Hirendra, N. uhttps://library.ncl.res.in/content/interfacial-charge-recombination-osii-polypyridyl-resorcinol-complex-oleic-acid-capped-001840nas a2200169 4500008004100000022001400041245012100055210006900176260007100245300001600316490000800332520113900340100001901479700001701498700002401515856013101539 2014 eng d a1932-744700aSize quantization effects on interfacial electron transfer dynamics in Ru(II)-polypyridyl complex sensitized ZnO QDs0 aSize quantization effects on interfacial electron transfer dynam a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcDEC a28898-289050 v1183 a

Quantum-size confinement in semiconductor material offers size based tunability of interband gap energy as well as intraband sublevels. In this work, size quantization of wide bandgap ZnO quantum dots has been explored in the study of interfacial charge separation reaction using a catechol functionalized Ru(II)polypyridyl complex as a photosensitizer molecule. Femtosecond time-resolved transient absorption studies have revealed multiple electron injection events based on discrete conduction band states of ZnO QDs. The electron injection rates have been rationalized for quantum confinement effects owing to different sizes of ZnO QDs. Furthermore, the size dependency of the intrinsic lifetime of electrons injected into discrete energy levels of ZnO QDs has been revealed in charge recombination reaction with the Ru(III)polypyridyl complex cation. The charge recombination dynamics reveals a competing trend of carrier confinement and carrier leak upon reducing particle size. This study shows the optimization of finite size effects in achieving better interfacial charge separation at the dye/semiconductor interface.

1 aVerma, Sandeep1 aDas, Amitava1 aGhosh, Hirendra, N. uhttps://library.ncl.res.in/content/size-quantization-effects-interfacial-electron-transfer-dynamics-ruii-polypyridyl-complex-001939nas a2200181 4500008004100000022001400041245010000055210006900155260007100224300001600295490000800311520123300319100001901552700001601571700001701587700002401604856012901628 2015 eng d a1520-610600aHydrogen bond and ligand dissociation dynamics in fluoride sensing of Re(I)-polypyridyl complex0 aHydrogen bond and ligand dissociation dynamics in fluoride sensi a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcNOV a14952-149580 v1193 a

Hydrogen bonding interaction plays an essential role in the early phases of molecular recognition and colorimetric sensing of various anions in aprotic media. In this work, the host-guest interaction between fac-[Re(CO)(3)Cl(L)] with L = 4-([2,2'-bipyridin]-4-yl)phenol and fluoride ions is investigated for the hydrogen bond dynamics and the changing local coordination environment. The stoichiometric studies using H-1 NMR and ESI-MS spectroscopies have shown that proton transfer in the H-bonded phenol-fluoride complex activates the dissociation of the CO ligand in the Re(I) center. The phenol-to-phenolate conversion during formation of HF2- ion induces nucleophilic lability of the CO ligand which is probed by intraligand charge transfer (ILCT) and ligand-to-metal charge transfer (LMCT) transitions in transient absorption spectroscopy. After photoexcitation, phenol-phenoxide conversion rapidly equilibrates in 280 fs time scale and the ensuing excited state [ReII(bpy(center dot-)-phenolate(-))(CO)(3)Cl]* undergoes CO dissociation in the ultrafast time scale of similar to 3 ps. A concerted mechanism of hydrogen cleavage and coordination change is established in anion sensing studies of the rhenium complex.

1 aVerma, Sandeep1 aAute, Sunil1 aDas, Amitava1 aGhosh, Hirendra, N. uhttps://library.ncl.res.in/content/hydrogen-bond-and-ligand-dissociation-dynamics-fluoride-sensing-rei-polypyridyl-complex-102075nas a2200193 4500008004100000022001400041245019500055210006900250260007100319300001400390490000800404520123700412100002001649700001801669700002101687700001701708700002401725856013201749 2015 eng d a1932-744700aUltrafast electron injection, hole transfer, and charge recombination dynamics in cdse QD super-sensitized Re(I)-polypyridyl complexes with catechol and resorcinol moiety: effect of coupling0 aUltrafast electron injection hole transfer and charge recombinat a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcFEB a3522-35290 v1193 a

Ultrafast charge-transfer dynamics have been demonstrated in CdSe quantum dots (QD) using two Re(I)-polypyridyl complexes having pendent catechol (Re1,2) and resorcinol (Re1,3) as the sensitizer molecules. The energy level diagram of CdSe QD and Re1,2 and Re1,3 sensitizer reveals that photoexcited hole of CdSe QD can be transferred to both Re1,2 and Re1,3 molecule, and photoexcited Re1,2 and Re1,3 can inject electron in the conduction band, which has been confirmed by steady-state and time-resolved photoluminescence studies with selective photoexcitation. Femtosecond transient absorption studies have been carried out to monitor charge-transfer dynamics in early time scale. Transient absorption spectra show formation of cation radicals for both Re1,2 and Re1,3 in the 550-650 nm region with a peak at 590 nm region and broad absorption in the 650-1000 nm region, which can be attributed to photoexcited electron in the conduction band of CdSe QD. Charge recombination was determined by monitoring the decay of cation radicals as well as decay of an electron and found to be slower in the Re1,3/CdSe system as compared to that of the Re1,2/CdSe system, which is due to weaker electronic coupling in the former system.

1 aDebnath, Tushar1 aMaity, Partha1 aBanerjee, Tanmay1 aDas, Amitava1 aGhosh, Hirendra, N. uhttps://library.ncl.res.in/content/ultrafast-electron-injection-hole-transfer-and-charge-recombination-dynamics-cdse-qd-super-002663nas a2200193 4500008004100000022001400041245013100055210006900186260007100255300001600326490000800342520188900350100001802239700002002257700002102277700001702298700002402315856013002339 2016 eng d a1932-744700aCharge delocalization in the cascade band structure CdS/CdSe and CdS/CdTe core-shell sensitized with Re(I)-polypyridyl complex0 aCharge delocalization in the cascade band structure CdSCdSe and  a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcMAY a10051-100610 v1203 a

Charge-carrier dynamics of CdS quantum dot (QD) and CdS/CdSe type-I and CdS/CdTe type-II core shell nanocrystals (NCs) sensitized with a Re(I)-polypyridyl complex have been carried with special emphasis on studies on carrier delocalization and the role of Re-complex as a hole acceptor and sensitizer molecule. Our investigation confirmed photoexcited hole transfer from CdS and CdS/CdSe to the Re-complex, while no hole transfer was observed in the CdS/CdTe Re-complex system. This was rationalized by the evaluation of the relative energy levels, which revealed that such hole migration was not energetically favorable due to low-lying highest occupied molecular orbital (HOMO) of the Re-complex as compared with the valence band (VB) of CdTe shell; however, luminescence quenching from upper excited states of Re-complex was observed in the presence of all three QD and core shell systems, which has been attributed to electron injection from hot state (energetically higher than the LUMO state) of the Re-complex to the conduction band (CB) of the QDs. Transient absorption (lambda(pump) = 400 nm, lambda(probe) = 450-750 nm) spectra recorded for Re complex-sensitized CdS and CdS/CdSe composite in the femtosecond time domain revealed a broad transient absorption band in the 580-750 nm region with a peak around 595 nm, and this was attributed to the cation radical formation for Re-complex, either by capturing photoexcited hole from the NCs or by injecting electron to the CB of the NCs. As anticipated, no such spectrum was observed for the CdS/CdTe Re-complex composite system after 400 nm excitation. Electron injection from photoexcited Re-complex to CdS QD and CdS/CdSe core shell was found to be <100 fs, while the hole transfer from photoexcited CdS QD and CdS/CdSe core shell to Re-complex took place within the time scale of 900 fs and 2.5 ps, respectively.

1 aMaity, Partha1 aDebnath, Tushar1 aBanerjee, Tanmay1 aDas, Amitava1 aGhosh, Hirendra, N. uhttps://library.ncl.res.in/content/charge-delocalization-cascade-band-structure-cdscdse-and-cdscdte-core-shell-sensitized-rei01603nas a2200169 4500008004100000245008200041210006900123260000800192300001600200490000800216520102100224100001901245700001601264700001701280700002401297856011201321 2016 eng d00aProton-coupled electron transfer in a hydrogen-bonded charge transfer complex0 aProtoncoupled electron transfer in a hydrogenbonded charge trans cOCT a10780-107850 v1203 aA proton-coupled electron transfer (PCET) reaction in a hydrogen bonded charge-transfer (CT) complex of 4-([2,2'-bipyridin]-4-yl)phenol (bpy-phenol) with a F- ion has been investigated by ultrafast time-resolved transient absorption spectroscopy. The phenolic receptor molecule, bpy-phenol, binds to the F- ion through a hydrogen bond and senses the F- ion-via the Stokes-shifted CT band. Upon photoexcitation, CT from the phenol residue to the bpy residue promotes proton transfer from the phenol radical cation (ArOH center dot+) to the fluoride ion at ultrafast time scales of <150 fs (instrument response function limited) and 3 ps, separately. The fast and slow proton-transfer times are linked to two different types of hydrogen-bonding networks between the phenol residue and fluoride ion. Crystalline water in the fluoride salt hydrates mediates the proton-transfer reaction. This work demonstrates the participation of a hydrogen-bonded water bridge within a PCET reaction in a water restricted environment.1 aVerma, Sandeep1 aAute, Sunil1 aDas, Amitava1 aGhosh, Hirendra, N. uhttps://library.ncl.res.in/content/proton-coupled-electron-transfer-hydrogen-bonded-charge-transfer-complex01821nas a2200157 4500008004100000245015300041210006900194260000800263490000700271520118300278100002401461700001701485700001601502700001801518856012701536 2017 eng d00aDemonstrating the role of anchoring functionality in interfacial electron transfer dynamics in newly synthesized BODIPY-TiO2 nanostructure composite0 aDemonstrating the role of anchoring functionality in interfacial cMAY0 v413 aNew Bodipy derivatives (Dye 1 and 2) having catechol or resorcinol functionality for anchoring to the nanostructured (NS) TiO2 surfaces have been synthesized. Extended conjugation at one of the two pyrrole rings at the C3 position has helped us in achieving the desired control in tuning the optical and redox properties of the BODIPY based dye molecules. Relative emission quantum yields (em1 = ~52 ± 2% and em2 = 54 ± 2%) are found to be much higher in polar aprotic solvent (acetonitrile), while this are found to be substantially lower for dye 1 in polar protic solvent. Steady state optical absorption studies reveal the formation of a strong charge transfer complex between dye 1 and NS-TiO2, while this interaction is much weaker for dye 2. Transient absorption studies have been carried out for 1/NS-TiO2 and 2/NS-TiO2 systems following excitation with a laser source of 400 nm for understanding the charge transfer dynamics. Results of the transient absorption spectral studies helped in elucidating role of anchoring functionality in influencing the dynamics of the interfacial electron transfer and the charge recombination process in ultrafast time scale.1 aGhosh, Hirendra, N.1 aDas, Amitava1 aAute, Sunil1 aMaity, Partha uhttps://library.ncl.res.in/content/demonstrating-role-anchoring-functionality-interfacial-electron-transfer-dynamics-newly02146nas a2200193 4500008004100000245015900041210006900200260000800269300001400277490000700291520141500298100001601713700001801729700001601747700001801763700001701781700002401798856013001822 2017 eng d00aProton-coupled electron-transfer processes in ultrafast time domain: evidence for effects of hydrogen-bond stabilization on photoinduced electron transfer0 aProtoncoupled electrontransfer processes in ultrafast time domai cMAR a3455-34650 v233 aThe proton-coupled electron-transfer (PCET) reaction is investigated for a newly synthesized imidazoleanthraquinone biomimetic model with a photoactive RuIIpolypyridyl moiety that is covalently coupled to the imidazole fragment. Intramolecular H-bonding interactions between imidazole and anthraquinone moieties favor the PCET process; this can be correlated to an appreciable positive shift in the one-electron reduction potential of the coordinated anthraquinone moiety functionalized with the imidazole fragment. This can also be attributed to the low luminescence quantum yield of the RuII-polypyridyl complex used. The dynamics of the intramolecular electron-transfer (ET) and PCET processes are studied by using femtosecond transient absorption spectroscopy. The steady- state spectroscopic studies and the results of the time- resolved absorption studies confirm that H- bonded water molecules play a major role in both ET and PCET dynamics as a proton relay in the excited state. The electron- transfer process is followed by a change in the H- bonding equilibrium between AQ and imidazole in acetonitrile solvent, and protonation of AQ(-) water leads to PCET in the presence of water. A slower forward and backward electron- transfer rate is observed in the presence of D2O compared with that in H2O. These results provide further experimental support for a detailed understanding of the PCET process.1 aDey, Ananta1 aDana, Jayanta1 aAute, Sunil1 aMaity, Partha1 aDas, Amitava1 aGhosh, Hirendra, N. uhttps://library.ncl.res.in/content/proton-coupled-electron-transfer-processes-ultrafast-time-domain-evidence-effects-hydrogen03024nas a2200193 4500008004100000022001400041245017500055210006900230260000900299300001400308490000700322520228300329100001602612700001802628700001602646700001702662700002402679856012702703 2019 eng d a1474-905X00aHydrogen bond assisted photoinduced intramolecular electron transfer and proton coupled electron transfer in an ultrafast time domain using a ruthenium-anthraquinone dyad0 aHydrogen bond assisted photoinduced intramolecular electron tran cOCT  a2430-24410 v183 a

Quinones play a significant role as primary electron acceptors in the natural photosynthetic system of photosystem II, and their reduction is known to be facilitated by hydrogen-bond donors or protonation. In this study, a ruthenium(ii) polypyridyl complex 1 coupled to an anthraquinone (AQ) functionality through a rigid imidazole (Im) spacer has been synthesized to examine the effect of H-bonding on both the thermal and photoinduced electron transfer reactions. The anthraquinone moiety of complex 1 is fused to a benzi-imidazole system bearing C & xe001;(OMIDLINE)-M-AQ HORIZONTAL ELLIPSISHNIm based H-bonding at one side of the anthraquinone moiety so that intramolecular hydrogen bonding from the imidazole group to the nearby quinone carbonyl can occur. The hydrogen bond formation involving the semiquinone radical anion produced through the photoinduced reduction process in Ru-im-AQ and the imidazole proton in complex 1 resulted in a significant positive shift of one electron reduction potential of complex 1. The kinetics for the formation of the charge-separated states was explored by using femtosecond transient absorption spectroscopy. Hydrogen bonding between water and the reduced anthraquinone accounted for thermodynamic and kinetic stabilization of these charge-separated states. An attempt has been made to assess the relative importance of the driving force and solvent polarity, in the rates of photoinduced electron transfer in complex 1. The 490 nm transient absorption band of anthraquinone radical anions (AQ(-)) and a broad absorption in the 580-750 nm region having maxima at similar to 690 nm have been observed and this is attributed to the generation of a transient Ru3+-species of the corresponding complex 1. Addition of water entails an acceleration of electron transfer rates by a factor of 3.33. The system investigated may serve as a model for the mechanistic diversity of PCET reactions in general with water as a primary proton donor. Furthermore, our studies are relevant for understanding proton-coupled electron transfer (PCET) reactivity of electronically excited states at a fundamental level because changes in hydrogen-bonding strength accompanying changes in redox states may be regarded as a variant form of PCET.

1 aDey, Ananta1 aDana, Jayanta1 aAute, Sunil1 aDas, Amitava1 aGhosh, Hirendra, N. uhttps://library.ncl.res.in/content/hydrogen-bond-assisted-photoinduced-intramolecular-electron-transfer-and-proton-coupled02376nas a2200217 4500008004100000022001400041245010500055210006900160260000900229300001400238490000700252520160400259100002901863700002001892700002601912700002001938700002201958700002401980700003002004856012402034 2023 eng d a2052-412900aDonor strapped perylene bisimide macrocycle and its lemniscate dimer with extended charge separation0 aDonor strapped perylene bisimide macrocycle and its lemniscate d cOCT  a5099-51070 v103 a

Macrocyclic structures are fascinating due to their unique design and capability to place chromophores in specific orientations, resulting in exciting optoelectronic properties. However, the synthetic challenges limit the broad exploration of such systems. Herein, we report a thiophene-diacetylene-based ring strapped perylene bisimide macrocycle and its notably different electron transfer features. Single-crystal analysis of the macrocycle pointed to the nearly orthogonal placement of donor-acceptor units, facilitating better electronic communication between them. Interestingly, introduction of an alkyl substituent on the peripheral thiophene ring opened the possibility of forming a higher oligomer macrocycle consisting of two strapped perylene bisimide units. Diffusion and two-dimensional NMR experiments provided insight into the structure of the figure-eight-shaped lemniscate dimer. Transient absorption measurements showed faster electron transfer and extended stabilization of the charge-separated state. The thiophene-diacetylene-based ring is a better donor unit to facilitate rapid electron transfer and extended charge separation in the macrocycle and its lemniscate dimer. The new macrocycle design enables the formation of higher analogs equally capable of stabilizing the charge-separated state. Donor-acceptor (D-A) macrocycle designs position the respective units to achieve ultrafast electron transfer precisely and an extended charge-separated state. Here, we report a D-A macrocycle and its lemniscate dimer molecule with exciting electron transfer features.

1 aVeer, Sairam, Dnyaneshwa1 aGoswami, Tanmay1 aRavindranathan, Sapna1 aGonnade, Rajesh1 aKharbanda, Nitika1 aGhosh, Hirendra, N.1 aBabu, Sukumaran, Santhosh uhttps://library.ncl.res.in/content/donor-strapped-perylene-bisimide-macrocycle-and-its-lemniscate-dimer-extended-charge02001nas a2200289 4500008004100000022001400041245010500055210006900160260000800229490000700237520101800244653002201262653002701284653002201311653001601333653002301349100002901372700003301401700001801434700001701452700002001469700002101489700002001510700002401530700003001554856012701584 2023 eng d a1433-785100aOligothiophene-ring-strapped perylene bisimides: functionalizable coaxial donor-acceptor macrocycles0 aOligothiopheneringstrapped perylene bisimides functionalizable c cJAN0 v623 a

Aesthetic designs from nature enable new knowledge to be gained and, at the same time, inspire scientific models. In this context, multicomponent macrocycles embody the advantage of precisely positioning the structural units to achieve efficient communication between them. However, the construction of a functionalizable macrocycle for ultrafast charge separation and stabilization has not been attempted. Herein, we report the synthesis, crystal structure, and transient absorption of a new functionalizable macrocycle consisting of an oligothiophene-ring-strapped perylene bisimide. Transient absorption results point to a sequential improvement in charge separation and stabilization from the macrocycle to the corresponding linear dimer and 2D polymer due to the unique design. Our macrocycle design with a supportive spatial arrangement of the donor and acceptor units will inspire the development of more complex synthetic systems with exciting electron-transfer and charge-separation features.

10aCharge Separation10aDonor-Acceptor Systems10aElectron Transfer10aMacrocycles10aPerylene Bisimides1 aVeer, Sairam, Dnyaneshwa1 aWakchaure, Vivek, Chandrakan1 aAsokan, Kiran1 aDixit, Ruchi1 aGoswami, Tanmay1 aSaha, Ramchandra1 aGonnade, Rajesh1 aGhosh, Hirendra, N.1 aBabu, Sukumaran, Santhosh uhttps://library.ncl.res.in/content/oligothiophene-ring-strapped-perylene-bisimides-functionalizable-coaxial-donor-acceptor