Isomeric Fluorene-based Heteroundecenes with Different Side Chains Anchoring Positions for Small Molecule Acceptors

Two isomeric fluorene-based heteroundecenes of bis(thienocyclopenthieno[3,2-b]thieno)fluorene(BT2T-F)and bis(dithieno[3,2-b:2’,3’-d]thiophene)cyclopentafluorene(B3T-F)have been designed and synthesized.The side chains of 4-hexylphenyl anchor on the 5th and 8th positions in B3T-F while on the 4th and 9th positions in BT2T-F,in which the former is closer to the center of the fused ring.The corresponding acceptor-donor-acceptor(A-D-A)type small molecule acceptors(SMAs)of BT2T-FIC and B3T-FIC were prepared by linking BT2T-F and B3T-F as fused ring donor units with the acceptor unit of 2-(5,6-difluoro-3-oxo-2,3-dihydroinden-1-ylidene)malononitrile(IC-2F),respectively.B3T-FIC presents a superior crystallinity with intense face-on π-π stacking in its neat film while BT2T-FIC is more disordered.When blended with PBDB-T-2Cl as a polymer donor,the optimized PBDB-T-2Cl:BT2T-FIC device exhibits an averaged power conversion efficiency(PCE)of 10.56%while only 7.53%in the PBDB-T-2Cl:B3T-FIC device.The improved short-circuit current(J_(sc))and fill factor(FF)of the PBDB-T-2Cl:BT2T-FIC device are the main contribution of its higher performance,which is attributed to its more efficient and balanced charge transport and better carrier recombination suppression.Given that BT2T-FIC blend and B3T-FIC blend films both take a preferential face-on orientatedπ-πstacking with comparable distances,the suitable SMA domain size obtained in the BT2T-FIC blend could account for its more efficient photovoltaic performance.These results highlight the importance of side-chain strategy in developing efficient SMAs with huge fused ring cores.

Optimizing side chains on different nitrogen aromatic rings achieving 17% efficiency for organic photovoltaics

Balancing charge generation and low energy loss(E_(loss)), especially in the wide spectral absorption region is critical to obtain high-performance organic photovoltaics(OPVs). Therefore, Y11-M and Y11-EB are designed and synthesized through modifying alkyl chains on different nitrogen aromatic rings of the reported non-fullerene acceptor Y11. Although all the molecules have almost similar low band-gap(around 1.30 e V), Y11-M and Y11-EB exhibit wider absorption in 410–870 nm region. Eventually, the conventional devices based on Y11-M and Y11-EB possess more efficient charge generation with low Eloss(around 0.44 e V). In addition, outstanding efficiencies of 16.64% and 17.15% with the fill factor of 76.15% and 74.73% are obtained in PM6:Y11-M and PM6:Y11-EB-based devices, both higher than Y11:PM6. The results highlight the importance of rational alkyl chains optimization, and a good structureproperty relationship is established as well.

18.55% Efficiency Polymer Solar Cells Based on a Small Molecule Acceptor with Alkylthienyl Outer Side Chains and a Low-Cost Polymer Donor PTQ10

The development of A-DA′D-A type small molecule acceptors(SMAs)has promoted the rapid progress of polymer solar cells(PSCs)in recent years.The outer side chains on the terminal thiophene ring and inner side chains on nitrogen atoms of the pyrrole ring of the DA′D fused ring play important roles in the photovoltaic performance of the SMAs.Here,we synthesized two new SMAs,2,2′-((2Z,2′Z)-((12,13-bis(2-ethylhexyl)-3,9-bis(4-(2-ethylhexyl)thiophen-2-yl)-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3″:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2-g]thieno[2′,3′:4,5]thieno[3,2-b]indole-2,10-diyl)bis(methaneylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(T2EH)and 2,2′-((2Z,2′Z)-((12,13-bis(2-ethylhexyl)-3,9-bis(3-(2-ethylhexyl)phenyl)-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3″:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2-g]thieno[2′,3′:4,5]thieno[3,2-b]indole-2,10-diyl)bis(methaneylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene)(P2EH),with 2-ethylhexylβ-substituted thienyl or phenyl as the outer side chains,respectively,to improve the photovoltaic properties of the SMAs.Compared with P2EH,T2EH exhibits closerπ−πstacking,slightly red-shifted absorption,and higher electron mobility.Moreover,the active layer of T2EH blended with the low-cost polymer donor poly[(thiophene)-alt-(6,7-difluoro-2-(2-hexyldecyloxy)quinoxaline)](PTQ10)possesses higher mobilities,a longer lifetime,and less recombination of the charge carriers in comparison with that of the PTQ10:P2EH active layer.Eventually,the PTQ10:T2EH-based PSCs showed an outstanding power conversion efficiency(PCE)of 18.55%,while the PSC based on PTQ10:P2EH displayed a PCE of 17.50%.Importantly,18.55%is the highest PCE in the PTQ10-based binary PSCs so far.The results indicate that T2EH is one of the best SMAs for the PTQ10-based PSCs and is a promising SMA for the application of PSCs.

Fine-tuning of Polymer Photovoltaic Properties by the Length of Alkyl Side Chains

This paper reports the synthesis and characteristics of a series of alkyl-substituted planar polymers. The physical properties are carefully tuned to optimize their photovoltaic performance. Depending on the length of soluble alkyl side chains which modify the structural order and orientation substantially in polymer backbones, the device performance can be improved significantly. The tuning of HOMO energy levels optimized polymers＇ spectral coverage of absorption and their hole mobility, as well as miscibility with fullerene; all these efforts enhanced polymer solar cell performances. The short- circuit current, Jsc for polymer solar cells was increased by adjusting polymer chain packing ability. It was found that films with well distributed polymer/fullerene interpenetrating network exhibit improved solar cell conversion efficiency. Enhanced efficiency up to 5.8% has been demonstrated. The results provide important insights about the roles of flexile chains in structure-property relationship for the design of new polymers to be used in high efficient solar cells.

Influence of bifurcation position and length of side chains on the structure of isoindigo-based conjugated polymer thin films

We chose a series of isoindigo-based conjugated polymer（ⅡDDT,ⅡDDT-C3 and ⅡDDT-C4） with different length of side chains and bifurcation positions to investigate the relationship between the degree of alignment and the length of side chains and bifurcation positions.We found that the dichroic ratio was increased from 2.37 to 5.23 when the side chain was longer and the bifurcation position was away from the backbone.The π-π stacking distance was decreased from 3.67 A to 3.61 A when the bifurcation position was away from the backbone because of its smaller hindrance and the d-spacing of the（100）was increased from 20.06 A to 25.21 A when the side chain was longer.All the polymers were adopted an edge-on orientation with the backbone paralleled with the long axis of fibers.The weak interaction of side-chain in ⅡDDT-C4 was beneficial for the molecules being rearranged in parallel during the contact line receding and the strong n-n interaction could accelerate the interchain assembly of the parallel molecules through π-π interaction to form aligned fibers.

Enhancing the Intermolecular Interactions of Ladder-Type Heteroheptacene-Based Nonfullerene Acceptors for Efficient Polymer Solar Cells by Incorporating Asymmetric Side Chains

Asymmetric nonfullerene acceptors(NFAs)possess larger dipole moments and stronger intermolecular bonding energy than their symmetric counterparts thereby making them promising candidates for high-performance polymer solar cells(PSCs).Herein,we report twoefficient acceptor–donor–acceptor(A–D–A)type NFAs(M14 and M18)with asymmetric side chains that show enhanced intermolecular interactions compared with their corresponding counterparts(M17 and M19)based on symmetric side chains.Furthermore,M14 and M18 exhibit elevated lowest unoccupiedmolecular orbitals and smallerπ–πstacking distances in comparison with M17 and M19,respectively.In combination with the benchmark polymer donor of PM6,the PM6:M14 blend affords superior charge transport properties,and more importantly,an increased power conversion efficiency(PCE)of 15.49%in comparison with the M17-based counterpart(13.01%PCE).Similarly,the asymmetric M18-based blend also shows a higher PCE of 13.00%than the M19-based blend(11.55%).Through further interface engineering,the bestperforming M14-based device delivers an enhanced PCE of 16.46%,which represents a record value among all asymmetric A–D–A type NFAs.Our results provide new insights into the design of asymmetric NFAs with enhanced intermolecular interactions for highperformance PSCs.

Novel Waterborne Fluorinated Polyurethane Containing Fluoroalkyl Side Chain:Synthesis,Characterization and Application on Cotton Fabric

A polyether diol poly[3-bromomethyl-3-tridecafluorooctyloxymethyloxetane]glycol(PFBOX 3) was prepared in 91% yield from ring opening polymerization of 3-bromomethyl-3-tridecafluorooctyloxymethyloxetane 2 which was derived from 3,3-dibromomethyloxetane 1 and 1H,1H,2H,2H-perfluorooctanol.The waterborne fluorinated polyurethane FPU was thus obtained by condensed polymerization of PFBOX 3 with isophoronediisocyanate(IPDI).The structure of FPU was characterized by Fourier transform infrared spectrometer(FTIR).FPU showed good thermal stability under 300℃.The surface properties of FPU were studied by applied on cotton fabric.The treated fabric surface showed excellent water repellent property as the contact angle reached 147°.On the other hand,the surface showed slightly oil repellent property as the contact angle for nujol droplet was 126°.

Side chain engineering investigation of non-fullerene acceptors for photovoltaic device with efficiency over 15%

Side chain engineering plays a substantial role for high-performance organic solar cells (OSCs).Herein,a series of non-fullerene acceptor (NFA) molecules with A-D-A structures,TTCn-4F,with gradient substituent lengths of terminal side chains (T-SCs) on the molecular backbones have been designed and synthesized.The effects of T-SCs length,ranging from hydrogen atom to n-dodecyl,their optoelectronic properties,thin film molecular packing,blend film morphology,and overall photovoltaic performance have been systematically studied.The results show that among this series of molecules,TTC8-4F with n-octyl substituent,showed the best photovoltaic performance when applied with PM6 as the donor due to its favorable morphology,balanced charge mobility,effective exciton dissociation and less charge recombination.Based on this,its ternary device with F-Br as the secondary acceptor achieved a high PCE of 15.34%with the simultaneously enhanced Voc of 0.938 V,Jscof 22.66 mA cm^-2,and FF of 72.15%.These results indicate that the engineering of T-SCs is an effective strategy for designing high-performance NFAs.

Synergetic Alkoxy Side-Chain and Chlorine-Contained End Group Strategy toward High Performance Ultra-Narrow Bandgap Small Molecule Acceptors

Ultra-narrow bandgap(ultra-NBG)small molecule acceptors(SMAs)show great potential in organic solar cells(OSCs)due to the extended near-infrared(NIR)absorption.In this work,a synergetic alkoxy side-chain and chlorine-contained end group strategy is employed to achieve A-DA'D-A type ultra-NBG SMAs by introducing alkoxy chains with oxygen atom at the second position into the thiopheneβposition as well as replacing the F atoms with Cl atoms in the end group.As a result,the heptacyclic BZO-4F shows a redshifted absorption onset(960 nm)compared with Y11(932 nm)without oxygen atoms in the side chains.Then,the fluorinated end groups are substituted with the chlorinated ones to synthesize BZO-4Cl.The absorption onset of BZO-4Cl is further redshifted to 990 nm,corresponding to an optical ultra-NBG of 1.25 eV.When blending with the polymer donor PBDB-T,the binary devices based on PBDB-T:BZO-4F and PBDB-T:BZO-4Cl deliver power conversion efficiencies(PCEs)over 12%.Furthermore,ternary devices with the addition of BZ4F-O-1 into PBDB-T:BZO-4Cl system achieve the optimal PCE of 15.51%.This work proposes a synergetic alkoxy side-chain and chlorine-contained end group strategy to achieve A-DA'D-A type ultra-NBG SMAs,which is important for future molecular design.

Synthesis and antibacterial activity of pleuromutilin derivatives with novel C(14) side chain

In order to find novel antibacterial agents with superior antibacterial activity and overcoming multidrug resistance,a series of pleuromutilin derivatives with novel C（14） side chain were synthesized and evaluated for their in vitro antibacterial activities.The results of antibacterial acticities indicated that most of the derivatives showed potent activities against Gram-positive organisms.In particular,compound lOd exhibited the most potent inhibitory activity compared with pleuromutilin and linezoid,emerged as potential molecule for further investigation.

A-DA’D-A Type Pentacyclic Small Molecule Acceptors to Exceed 16.5%Efficiency by Heteroatom Effect at the Outer Side Chain

Comprehensive Summary In this work,we adopt a“heteroatom side-chains”modification strategy to modify the thiophene units in A-DA'D-A(acceptor-donor-acceptor’-donor-acceptor)type pentacyclic SMAs(small molecule acceptors),that is,introducing branched alkyl chain at theβ-position of thiophene instead of straight alkyl chain,and then introducing oxygen atom at the third-position on the basis of branched chain.Two new pentacyclic SMAs(BZ4F-EH and BZ4F-OEH)were synthesized,and the influence of the heteroatom side-chains on photoelectric properties of A-DA'D-A type pentacyclic SMAs was systematically studied.Compared with our previously reported BZ4F(Y26),BZ4F-EH shows slightly blue-shifted absorption,while BZ4F-OEH has obvious red-shifted absorption.As a result,BZ4F-OEH-based binary device achieved a high power conversion efficiency(PCE)of 16.56%with a fill factor(FF)of 79.3%,which is the highest efficiency of pentacyclic SMAs to date.

Alkyl side chain engineering enables high performance as-cast organic solar cells of over 17%efficiency

Achieving high-performance as-cast OSCs is crucial for industrialization in the future,owing to the advantages of better stability,environmental-friendly,and decreasing production cost.In this regard,we synthesized an ADA′D-A type acceptor,Y6-eC6-BO,by shortening the straight alkyl side-chains on the thiophene position from C_(11) to C_(6) as well as lengthening the branched alkyl side-chains on the pyrrole position of Y6 to achieve a stronger crystallization and better miscibility than Y6.As a result,the corresponding chloroform-processed as-cast PM6:Y6-eC6-BO OSC showed a high PCE of 17.33%,which was one of the highest efficiencies of as-cast OSCs.And the as-cast PM6:Y6-eC6-BO OSCs processed from o-xylene displayed a PCE of 16.38%,as far as we know,this is among the highest efficiencies of non-halogenated-solvent processed as-cast OSCs.These results demonstrated tailoring the alkyl side-chain of NFAs is a feasible and simple approach to achieve high performance as-cast OSCs and provides guideline in molecular design in the future.