Congratulations to Dr. Yuan Fang on receiving the Royal Society of Canada's Alice Wilson Award at the Royal Society of Canada's celebration of Excellence and Engagement (COEE, formerly Annual General Meeting)! Awarded to women of outstanding academic qualifications who are entering a career in scholarship or research at the postdoctoral level.
Congratulations to Ehsan Hamzehpoor in our group for the new paper titled 'Crystal Engineering of Room Temperature Phosphorescence in Organic Solids' on Angew. Chem. Int. Ed.!
We report a series of highly emissive azatriangulenetrione(TANGO) solids in which the luminescent properties are controlled by engineering the molecular packing by adjusting the steric size of substituents. The co-alignment of ‘phosphorogenic’ carbonyl groups within the pi-stacks results in an almost pure triplet emission in HTANGO, TCTANGO, TBTANGO and TITANGO, while their rotation by ~60 degrees in the sterically hindered tBuTANGO leads to an almost pure singlet emission. Despite strong pi-interactions, aggregation-induced quenching and triplet-triplet annihilation are avoided in HTANGO and TCTANGO which display efficient phosphorescence in the solid state. To our knowledge, HTANGO with the solid-state phosphorescence quantum yield of 42% at room temperature is the most efficient phosphor composed of the 1st/2nd raw elements only.
The group went apple picking at Mont St. Bruno, and then we had BBQ at Dima's place! Great weather, great apples, great food! Twitter link with photos is coming up!
Congrats to Dr. Yuan Fang and co-workers in our group for the new paper titled 'Covalent organic frameworks from a monomer with reduced symmetry: polymorphism and Sierpinski triangles' ; on Chem. Commun.!
We report on the synthesis of a covalent organic framework based on the low-symmetry 1,3-benzenediboronic acid precursor. Control over polymorph formation, either honeycomb network or Sierpinski triangles, was achieved by varying the precursor concentration for on-surface synthesis as elucidated by scanning tunneling microscopy.
Tags: COF, STM
Congrats to Ehsan Hamzehpoor and co-workers in our group and Prof. Federico Rosei's group for the new paper titled 'Temperature-induced molecular reorganization on Au(111) driven by oligomeric defects'; on Nanoscale!
The formation of ordered molecular structures on surfaces is determined by the balance between molecule–molecule and molecule–substrate interactions. Whether the aggregation process is guided by non-covalent forces or on-surface reactions, a deeper understanding of these interactions is pivotal to formulating a priori predictions of the final structural features and the development of bottom-up fabrication protocols. Theoretical models of molecular systems corroborate the information gathered through experimental observations and help explain the thermodynamic factors that underpin on-surface phase transitions. Here, we report a scanning tunneling microscopy investigation of a tribromo-substituted heterotriangulene on the Au(111) surface, which initially forms an extended close-packed ordered structure stabilized by Br⋯Br halogen bonds when deposited at room temperature. X-ray photoelectron spectroscopy reveals that annealing the self-assembled layer induces a fraction of the molecular precursors to partially dehalogenate that in turn leads to the formation of a less stable Br⋯O non-covalent network which coexists with the short oligomers. Density functional theory (DFT) and Monte Carlo (MC) simulations illustrate how dimer moieties act as defects whose steric hindrance prevents the retention of the more stable configuration. A small number of dimers is sufficient to drive the molecular reorganization into a lower cohesive energy phase. Our study shows the importance of a combined DFT – MC approach to understand the evolution of molecular systems on substrates.
Congrats to Dr. Chaoying Fu and co-workers in our group for the new paper titled 'Dynamic covalent conjugated polymer epitaxy on graphene'; on J. Mater. Chem. C!
Hybrid heterostructures formed from ordered molecular layers on two-dimensional materials can have unique properties differing from those of their bulk phases. By employing principles of dynamic covalent chemistry, we have synthesized a series of novel conjugated polyimines that form epitaxial ordered monolayers on graphene. The interplay between molecular physisorption and dynamic polymerization at the solid–liquid interface drives the formation of longer chains at the surface with dramatically higher rates than in solution. The physico-chemical properties of such assemblies at different length scales on graphene were investigated by a combination of experimental techniques. ‘Covalent dynamic epitaxy’ was also found to modulate the properties of both substrate and dynamers such as doping and photoluminescence, respectively.
Tags: Polymers, STM
Congrats to Cheng-Hao Liu & Dr. M. Rizwan Niazi in our group for the new paper titled 'Remarkable Enhancement of of pi-Electron Donor/Acceptor Ability by DD/AA Complementary Hydrogen Bonding' on Angew. Chem. Int. Ed.!
Supramolecular control is critical for devices of organic pi-conjugated materials, but it often lack directionality and neglect changes in electronic structures. In their Research Article, C.-H. Liu, M.R. Niazi, D.F. Perepichka present a DD/AA complementary hydrogen bonding method to directionally assemble a family of weak donor/acceptor molecules that then act as strong D/A assemblies. The dramatically altered electronic structures manifest in low bandgaps, close π-π distances, emergence of radicals, and tunable semiconducting behaviours (p-type, ambipolar, intrinsic; gate- or light-controlled).
Tags: Crystal enginnering, Charge-transfer, (Photo)transistors
Congrats to Dr. Thaksen Jadhav and co-workers for the new paper titled '2D Poly(arylene vinylene) Covalent Organic Frameworks via Aldol Condensation of Trimethyltriazine' on Angew. Chem. Int. Ed.!
Here we report a series of 2D vinylene-linked covalent organic frameworks via aldol condensation of trimethyltriazine. The crystalline, porous, pi-conjugated COFs display numerous interesting properties such as swellability (i.e. dynamic behaviour) and tunable emission (up to 50% quantum yield).
Tags: 2D sp2 COF, Luminescence, Dynamic
Congrats to Dr. Fang Yuan and Dr. M. Rizwan Niazi in our group and Prof. Ori Gidron's group for the new paper titled 'A macrocyclic oligofuran: synthesis, solid state structure and electronic properties' on Chem. Sci!
We report the first π-conjugated macrocyclic system with an oligofuran backbone. The calculated HOMO–LUMO gap is similar to that of the corresponding linear polymer, indicating a remarkable electron delocalization. The X-ray structure reveals a planar conformation, in contrast to the twisted conformation of macrocyclic oligothiophenes. The intermolecular π–π stacking distance is extremely small (3.17 Å), indicating very strong interactions. The macrocycle forms large π-aggregates in solution and shows a tendency toward highly ordered multilayer adsorption at the solid–liquid interface. The face-on orientation of molecules explains the higher hole mobility observed in the out-of-plane direction.
Tags: Small pi-conjugated molecule, SCLC
Congrats to Yuxuan Che, Cheng-Hao Liu and co-workers for the new paper titled 'Understanding the Photovoltaic Behavior of A–D–A Molecular Semiconductors through a Permutation of End Groups' on J. Org. Chem.!
We report the facile synthesis of a series of benzodithiophene (BDT)- and indacenodithiophene (IDT)-based A–D–A oligomers with different end groups, where their properties are studied by optical spectroscopy, electrochemistry, and density functional theory calculations. The permutation of central and terminal units tunes the optoelectronic properties and photovoltaic device characteristics in a predictable way, aiding in the rational design of small molecule semiconducting materials. Among the three rhodanine-derived terminal groups, N-alkylthiazolonethione revealed the strongest electron-withdrawing character, resulting in the lowest band gap, the highest stability, and the best photovoltaic device performance. The crystallographic analysis of two IDT derivatives yielded a highly unusual three-dimensional packing of the conjugated backbone, which is likely responsible for the remarkable photovoltaic performance of such A–D–A semiconductors.
Tags: Small pi-conjugated molecule, Photovoltaics
Congratulations to Cheng-Hao Liu and Ehsan Hamzehpoor for winning the first place in the ChemiSTEAM contest at the 102nd Canadian Chemistry Conference and Exhibition! The image will be the regular issue cover for Can. J. Chem. in 2020! A few group members including Cheng-Hao and Ehsan presented oral presentations at the conference.
The group went hiking to Parc National du Mont Tremblant (then to the resort!) as a pre-farewell trip for Thaksen's departure. The group later gathered for brunch in Montreal on the day of Thaksen's flight and gave him a gift. Best of luck to Dr. Thaksen Jadhav!