Recent trends in molecular aggregates:An exploration of biomedicine

Molecular aggregates are receiving tremendous attention,demonstrating immense potential for biomedical applications in vitro and in vivo.For instance,the molecular aggregates of conventional fluorophores influence the electronic excitation states of the aggregates,causing characteristic photophysical property changes.A fundamental understanding of this classical relationship between molecular aggregate structures and photophysics has allowed for innovative biological applications.The chemical characteristics of drug molecules generally trigger the formation of colloidal aggregates,and this is considered detrimental to the drug discovery process.Furthermore,nano-sized supramolecular aggregates have been used in biomedical imaging and therapy owing to their optimal properties for in vivo utility,including enhanced cell permeability,passive tumor targeting,and convenient surface engineering.Herein,we provide an overview of the recent trends in molecular aggregates for biomedical applications.The changes in photophysical properties of conventional fluorophores and their biological applications are discussed,followed by the effects of conventional drug molecule-aggregates on drug discovery and therapeutics development.Recent trends in the investigation of biologically important analytes with aggregation-induced emission are discussed for conventional and unconventional fluorophores.Lastly,we discuss nano-sized supramolecular aggregates used in imaging and therapeutic purposes,with a focus on in vivo utilization.

Intermolecular charge-transfer aggregates enable high-efficiency near-infrared emissions by nonadiabatic coupling suppression

Pursuing purely organic materials with high-efficiency near-infrared(NIR) emissions is fundamentally limited by the large nonradiative decay rates(k_(nr)) governed by the energy gap law. To date, reported endeavors to decelerate k_(nr) are mainly focused on reducing the electron-vibration coupling with the electronic nonadiabatic coupling assumed as a constant. Here, we demonstrated a feasible and innovative strategy by employing intermolecular charge-transfer(CT) aggregates(CTA) to realize high-efficiency NIR emissions via nonadiabatic coupling suppression. The formation of CTA engenders intermolecular CT in the excited states;thereby, not only reducing the electronic nonadiabatic coupling and contributing to small k_(nr) for high-efficiency NIR photoluminescence, but also stabilizing excited-state energies and achieving thermally activated delayed fluorescence for highefficiency NIR electroluminescence. This work provides new insights into aggregates and opens a new avenue for organic materials to overcome the energy gap law and achieve high-efficiency NIR emissions.

Poly(3-hexylthio) thiophene Field-effect Transistor Device Performance: Impact of the Content of Hexylthio Side Chain on Backbone

Regioregular poly(3-hexylthio)thiopene(P3HTT) has emerged tremendous potential in organic electronic applications due to the strong noncovalent interactions from the sulfur atom linked to thiophene. However, P3HTT generally exhibits low charge mobility mostly due to poor solution processability attributed to dense arrangement of hexylthio side chain in polymer, which led to strong noncovalent interactions among sulfur atoms. To balance the nonvalent interaction and aggregation for P3HTT, herein, we systematically study the effect of hexylthio side chain content in polymer backbone on the structure and properties. A series of regioregular P3HTT-based homopolymers(P3HTT, P3HTT-50,P3HTT-33 and P3HTT-25) were prepared via Kumada catalyst transfer polycondensation method from a set of mono-, bi-, ter-and quarterthiophenes containing different contents of hexylthio side chain. The DFT calculation shows the planarity of polymers backbone could be improved through reducing the density of hexylthio side chain in polymer mainchain. And significant changes in their crystallinity, aggregation and optical properties were observed with the content of hexylthio side chain reducing. The P3HTT-33 displayed the highest field-effect transistor hole mobility of 2.83×10^(-2) cm^(2)·V^(-1)·s^(-1) resulting from a balance between the crystallinity and planarity. This study demonstrates modulating the content of hexylthio side chain in P3HTT is an effective strategy to optimize the opto-electronic properties of polymer obtaining excellent semiconductor device performance.

Spectroscopic identification towards tunable mesoscale aggregates of zinc tetraphenylporphyrin for materials

We present a study of spectroscopic identification towards the molecular aggregates of zinc tetraphenylporphyrin （ZnTPP） illustrating how the energy states and intermolecular interactions determine the tunable properties of functional materials in condensation processes. Distinguishable fingerprints of ZnTPP nanorods and nanosheets are addressed utilizing X-ray diffraction （XRD）, Raman and UV-vis absorption spectroscopies. Although these ZnTPPs are assigned to J-aggregation at different extent, the spectral analysis reveals a significant role of the intermolecular interactions associated with varying mesoscale architectures. Energy decomposition analysis （EDA） revealed that the varied ZnTPP aggregates are stabilized by altered dispersion interactions due to the dominant ~r...zr stacking between the monomers.

Highly Efficient Random Terpolymers for Photovoltaic Applications with Enhanced Absorption and Molecular Aggregation

A series of copolymers, based on benzo[1,2-b：4,5-b＇]dithiophene （BDT） as the electron donor and 2,1,3- benzothiadiazole （BT）/diketopyrrolo[3,4-c]pyrrole （DPP） as the electron acceptors, were synthesized for highly efficient polymer solar cells. By changing the BT/DPP ratio in the conjugated backbone, the absorption, energy levels, molecular aggregation and carrier mobility could be finely tuned. With increased DPP content, the absorption range was extended to the longer wavelength region with narrower bandgaps. The highest occupied molecular orbital （HOMO） levels were also raised up and the molecular aggregation was enhanced. The balance of these factors would afford a remarkable device performance enhancement. Polymer P3 with BT：DPP = 0.7：0.3 （molar ratio） exhibited the highest power conversion efficiency （PCE） of 9.01%, with open circuit voltage （Voc） = 0.73 V, short current density （Jsc） = 18.45 mA.cm-2, and fill factor （FF） - 66.9%. The PCE value was improved by 48.7% compared to P1 and by 117.6% compared to P7, respectively, indicating a great potential in photovoltaic application.

Influence of thermal annealing-induced molecular aggregation on film properties and photovoltaic performance of bulk heterojunction solar cells based on a squaraine dye

Squaraine （SQ） dyes have been considered as efficient photoactive materials for organic solar cells. In this work, we purposely controlled the molecular aggregation of an SQ dye, 2,4-bis[4-（N,N-dibutylamino）-2-dihydroxyphenyl] SQ （DBSQ- （OH）2） in the DBSQ（OH）2：[6,6]-phenyl-Cel-butyric acid methyl ester （PCBM） blend film by using the thermal annealing method, to study the influence of the molecular aggregation on film properties as well as the photovoltaic performance of DBSQ（OH）2：PCBM-based bulk heterojunction （BHJ） solar cells. Our results demonstrate that thermal annealing may change the aggregation behavior of DBSQ（OH）2 in the DBSQ（OH）2：PCBM film, and thus significantly influence the surface morphology, optical and electrical properties of the blend film, as well as the photovoltaic performance of DBSQ（OH）2：PCBM BHJ cells.

Comparative studies on molecular induced aggregation of hepta-imidazoliumyl-β-cyclodextrin towards anionic surfactants

A β cyclodextrin derivative bearing seven cationic arms and its singly charged analogue, i.e., per-6- deoxy-f-（1-methylimidazol-3-ium-3-yl）-β-cyclodextrin （3） and mono-fi-deoxy-6-（1-methylimidazol- 3-ium-3-yl）-β-cyclodextrin （4） were synthesized and fully characterized. Their induced aggregation behaviours towards two anionic surfactant, that is, sodium dodecyl sulfonate （SDS） and dioctyl sodium sulfosuccinate （Aerosol OT, AOT）, were investigated by UV-vis, NMR, Zeta-potential, dynamic light scattering （DLS）, and transmission electron microscopy. The results revealed that host 3 can induce the molecular aggregation of anionic surfactant at concentration far lower than its original CAC, leading to the larger diameter, the narrower size distribution and the higher thermal stability of the induced aggregate towards the anionic surfactant possessing more hydrophobic tails.

Controlling molecular weight of naphthalenediimide-based polymer acceptor P(NDI2OD-T2)for high performance all-polymer solar cells

A widely-used naphthalenediimide （NDI） based electron acceptor P（NDI2OD-T2） with different number- average molecular weight （Mn） of 38 （N2200L）, 56 （N2200M）, 102 （N2200H） kDa were successfully prepared. The effect of molecular-weight on the performance of all-polymer solar cells based on Poly（5-（5-（4,8- bis（ 5-decylthiophen-2-yl ）-6-methylbenzo[1,2-b： 4,5-b＇]dithophen-2-yl ）thiophen-2-yl ）-6,7-difluoro-8- （5-methylthiophen-2-yl）-2,S-bis（3-（octyloxy）phenyl）quinoxaline） （P2F-DE）：N2200 was systematically investigated. The results reveal that N2200 with increased M. show enhanced intermolecular interac- tions, resulting in improved light absorption and electron mobility. However, the strong aggregation trend of N2200H can cause unfavorable morphology for exciton dissociation and carrier transport. The blend film using N2200 with moderate M. actually develops more ideal phase segregation for efficient charge separation and transport, leading to balanced electron/hole mobility and less carrier recombi- nation. Consequently, all-polymer solar cells employing P2F-DE as the electron donor and N2200M as the electron acceptor show the highest efficiency of 4.81%, outperforming those using N2200L （3,07~;） and N2200H （S,92%）. Thus, the Mn of the polymer acceptor plays an important role in all-polymer solar ceils, which allows it to be an effective parameter for the adjustment of the device morphology and efficiency.