02617nas a2200253 4500008004100000022001400041245008400055210007000139260000800209490000700217520178600224653001202010653001302022653001902035653001702054653003102071100001802102700002502120700002402145700002002169700003002189700003002219856011402249 2023 eng d a1433-785100aIsomer effect on energy storage of π-extended S-shaped double[6]heterohelicene0 aIsomer effect on energy storage of πextended Sshaped double6hete cNOV0 v623 a

Recently, chiral and nonplanar cutouts of graphene have been the favorites due to their unique optical, electronic, and redox properties and high solubility compared with their planar counterparts. Despite the remarkable progress in helicenes, pi-extended heterohelicenes have not been widely explored. As an anode in a lithium-ion battery, the racemic mixture of pi-extended double heterohelical nanographene containing thienothiophene core exhibited a high lithium storage capability, attaining a specific capacity of 424 mAh g-1 at 0.1 A g-1 with excellent rate capability and superior long-term cycling performance over 6000 cycles with negligible fade. As a first report, the pi-extended helicene isomer (PP and MM), with the more interlayer distance that helps faster diffusion of ions, has exhibited a high capacity of 300 mAh g-1 at 2 A g-1 with long-term cycling performance over 1500 cycles compared to the less performing MP and PM isomer and racemic mixture (150 mAh g-1 at 2 A g-1). As supported by single-crystal X-ray analysis, a unique molecular design of nanographenes with a fixed (helical) molecular geometry, avoiding restacking of the layers, renders better performance as an anode in lithium-ion batteries. Interestingly, the recycled nanographene anode material displayed comparable performance. A pi-extended double heterohelical nanographene of thienothiophene core fused with two hexabenzocoronene units exhibits excellent performance as an anode in a lithium-ion battery. The isomer (PP and MM) with more interlayer distance exhibited a high lithium storage capability compared to the other isomer and racemic mixture. Helical nanographene anodes display excellent rate capability, superior long-term cycling performance, and recyclability.image

10aBattery10agraphene10aLi-ion battery10ananographene10aOrganic Electrode Material1 aKumar, Viksit1 aBharathkumar, H., J.1 aDongre, Sangram, D.1 aGonnade, Rajesh1 aKrishnamoorthy, Kothandam1 aBabu, Sukumaran, Santhosh uhttp://library.ncl.res.in/content/isomer-effect-energy-storage-%CF%80-extended-s-shaped-double6heterohelicene02426nas a2200277 4500008004100000022001400041245012800055210007000183260000900253490000700262520147600269653003801745653001001783653001801793653001701811653000901828100002201837700001801859700003001877700002401907700002001931700002001951700001801971700003001989856012902019 2024 eng d a0947-653900aBoron- and oxygen-doped π-extended helical nanographene with circularly polarised thermally activated delayed fluorescence0 aBoron and oxygendoped πextended helical nanographene with circul cAPR 0 v303 a

Helical nanographenes have garnered substantial attention owing to their finely adjustable optical and semiconducting properties. The strategic integration of both helicity and heteroatoms into the nanographene structure, facilitated by a boron-oxygen-based multiple resonance (MR) thermally activated delayed fluorescence (TADF), elevates its photophysical and chiroptical features. This signifies the introduction of an elegant category of helical nanographene that combines optical (TADF) and chiroptical (CPL) features. In this direction, we report the synthesis, optical, and chiroptical properties of boron, oxygen-doped pi-extended helical nanographene. The pi-extension induces distortion in the DOBNA-incorporated nanographene, endowing a pair of helicenes, (P)-B2NG, and (M)-B2NG exhibiting circularly polarized luminescence with glum of -2.3x10-3 and +2.5x10-3, respectively. B2NG exhibited MR-TADF with a lifetime below 5 mu s, and a reasonably high fluorescence quantum yield (50 %). Our molecular design enriches the optical and chiroptical properties of nanographenes and opens up new opportunities in multidisciplinary fields. B, O-doped pi-extended helical nanographene has been explored for its optical and chiroptical properties. The presence of helical and nanographene segments stabilize the helicity and imparts tunable optical properties. Helical nanographene display circularly polarized thermally activated delayed fluorescence. image

10acircularly polarized luminescence10aDOBNA10adual emission10ananographene10aTADF1 aVenugopal, Geethu1 aKumar, Viksit1 aJadhav, Ashok, Badrinaray1 aDongre, Sangram, D.1 aKhan, Abujunaid1 aGonnade, Rajesh1 aKumar, Jatish1 aBabu, Sukumaran, Santhosh uhttp://library.ncl.res.in/content/boron-and-oxygen-doped-%CF%80-extended-helical-nanographene-circularly-polarised-thermally02167nas a2200253 4500008004100000245009100041210006900132260000900201300001500210490000700225520131300232653003801545653002301583653001301606653001701619653001801636100002401654700002201678700001801700700003001718700001801748700003001766856011701796 2025 eng d00aChiroptical amplification of [7]-helicene nanographene by additional helical chirality0 aChiroptical amplification of 7helicene nanographene by additiona cFEB  ae2024207670 v643 a

Nanographenes have captivated scientific interest since the pioneering discovery of graphene. Recently, attention has shifted towards exploring chiral and nonplanar nanographenes, for their distinct optical, chiroptical, and electronic properties. Despite the growing acceptance of helicenes, the research on inducing helical chirality on pi-extended derivatives to boost chiroptical properties remains unattended. In our study, we introduce a new pi-extended [7]-helicene resulting from the condensation of diamines with 3,6-dibromophenanthrene-9,10-dione, complemented by two hexabenzocoronene arms in the periphery. Notably, the nanographene containing binaphtho-[1,4]diazocine, compared to the corresponding phenazine, exhibits a remarkable average 2.5, 5, and 10-fold enhancements in quantum yield, dissymmetry factor, and brightness, respectively, when measured in five different solvents. These improvements underscore the significance of the induced helical chirality by the antiaromatic binaphtho-[1,4]diazocine in influencing the chiroptical properties of the helical nanographene. Our research represents a significant stride toward unlocking the potential of pi-extended helicenes and lays the groundwork for further exploration in designing and synthesizing new chiral nanomaterials.

10acircularly polarised luminescence10adissymmetry factor10ahelicene10ananographene10aquantum yield1 aDongre, Sangram, D.1 aVenugopal, Geethu1 aKumar, Viksit1 aJadhav, Ashok, Badrinaray1 aKumar, Jatish1 aBabu, Sukumaran, Santhosh uhttp://library.ncl.res.in/content/chiroptical-amplification-7-helicene-nanographene-additional-helical-chirality02406nas a2200313 4500008004100000245008500041210007000126260000800196300001500204490000700219520144500226653001401671653000801685653001401693653001701707653002001724653000901744100001801753700002201771700003001793700002401823700002001847700001801867700001901885700001901904700002101923700003001944856011801974 2025 eng d00aRegioisomeric π-extended nanographene with long-lived phosphorescence afterglow0 aRegioisomeric πextended nanographene with longlived phosphoresce cFEB ae2024221250 v643 a

The cutouts of graphene sheets, particularly those with a nonplanar topology, present vast opportunities for advancement. Even a slight deviation from the planar structure can lead to intriguing (chiro)optical features for helically twisted nanographenes. In this context, we introduce two regioisomeric pi-extended nanographenes that exhibit distinct excited-state characteristics. The helicene structure and the photophysical features can be easily tuned by changing the connecting position of the nanographene to the carbazole core (2,7- and 3,6-). Single-crystal X-ray diffraction analysis confirmed the formation of nanographenes with bent and helical conformations. Both derivatives exhibited thermally activated delayed fluorescence at room temperature and phosphorescence at low temperatures. Notably, the nanographene with the bent structure displayed an impressive red afterglow lasting over 30seconds, in contrast to the very weak afterglow observed in the helical structure. DFT calculations revealed the existence of an isoenergetic higher triplet state (T-8) and comparatively weak spin-orbit coupling (T-1-S-0), thereby enabling the bent nanographene to exhibit a long-lived component and strong afterglow. Our findings highlight the significance of regioisomeric nanographenes with exceptional optical properties and offer a deeper understanding of the structure-property relationship in nonplanar nanographenes.

10aAfterglow10aCPL10aHelicenes10ananographene10aPhosphorescence10aTADF1 aKumar, Viksit1 aVenugopal, Geethu1 aJadhav, Ashok, Badrinaray1 aDongre, Sangram, D.1 aGonnade, Rajesh1 aKumar, Jatish1 aRuer, Paul, C.1 aHupp, Benjamin1 aSteffen, Andreas1 aBabu, Sukumaran, Santhosh uhttp://library.ncl.res.in/content/regioisomeric-%CF%80-extended-nanographene-long-lived-phosphorescence-afterglow