Self-assembly Protocol Research Articles

Alkoxy-Bridged Dicopper(II) Cores Meet Tetracyanonickelate Linkers: Structural, Magnetic, and Theoretical Investigation of Cu/Ni Coordination Polymers.

Two heterometallic Cu(II)/Ni(II) coordination polymers, [Cu2(Hbdea)2Ni(CN)4]n (1) and [Cu2(dmea)2Ni(CN)4]n·nH2O (2), were successfully self-assembled in water by reacting Cu(II) nitrate with H2bdea (N-butyldiethanolamine) and Hdmea (N,N-dimethylethanolamine) in the presence of sodium hydroxide and [Ni(CN)4]2-. These new coordination polymers were investigated by single-crystal and powder X-ray diffraction and fully characterized by FT-IR spectroscopy, thermogravimetry, elemental analysis, variable-temperature magnetic susceptibility measurements, and theoretical DFT and CASSCF calculations. Despite differences in crystal systems, in both compounds, each dinuclear building block [Cu2(μ-aminopolyalcoholate)2]2+ is bridged by diamagnetic [Ni(CN)4]2- linkers, resulting in 1D (1) or 2D (2) metal-organic architectures. Experimental magnetic studies show that both compounds display strong antiferromagnetic coupling (J = -602.1 cm-1 for 1 and -151 cm-1 for 2) between Cu(II) ions within the dimers mediated by the μ-O-alkoxo bridges. These results are corroborated by the broken symmetry DFT studies, which also provide further insight into the electronic structures of copper dimeric units. By reporting a facile self-assembly synthetic protocol, this study can be a model to widen a still limited family of heterometallic Cu/Ni coordination polymer materials with different functional properties.

Modulated Self-Assembly of Catalytically Active Metal-Organic Nanosheets Containing Zr6 Clusters and Dicarboxylate Ligands.

Two-dimensional metal-organic nanosheets (MONs) have emerged as attractive alternatives to their three-dimensional metal-organic framework (MOF) counterparts for heterogeneous catalysis due to their greater external surface areas and higher accessibility of catalytically active sites. Zr MONs are particularly prized because of their chemical stability and high Lewis and Brønsted acidities of the Zr clusters. Herein, we show that careful control over modulated self-assembly and exfoliation conditions allows the isolation of the first example of a two-dimensional nanosheet wherein Zr6 clusters are linked by dicarboxylate ligands. The hxl topology MOF, termed GUF-14 (GUF = Glasgow University Framework), can be exfoliated into monolayer thickness hns topology MONs, and acid-induced removal of capping modulator units yields MONs with enhanced catalytic activity toward the formation of imines and the hydrolysis of an organophosphate nerve agent mimic. The discovery of GUF-14 serves as a valuable example of the undiscovered MOF/MON structural diversity extant in established metal-ligand systems that can be accessed by harnessing the power of modulated self-assembly protocols.

2D capsid formation within an oscillatory energy landscape: orderly self-assembly depends on the interplay between a dynamic potential and intrinsic relaxation times.

Multiple dissipative self-assembly protocols designed to create novel structures or to reduce kinetic traps have recently emerged. Specifically, temporal oscillations of particle interactions have been shown effective at both aims, but investigations thus far have focused on systems of simple colloids or their binary mixtures. In this work, we expand our understanding of the effect of temporally oscillating interactions to a two-dimensional coarse-grained viral capsid-like model that undergoes a self-limited assembly. This model includes multiple intrinsic relaxation times due to the internal structure of the capsid subunits and, under certain interaction regimes, proceeds via a two-step nucleation mechanism. We find that oscillations much faster than the local intrinsic relaxation times can be described via a time averaged inter-particle potential across a wide range of interaction strengths, while oscillations much slower than these relaxation times result in structures that adapt to the attraction strength of the current half-cycle. Interestingly, oscillation periods similar to these relaxation times shift the interaction window over which orderly assembly occurs by enabling error correction during the half-cycles with weaker attractions. Our results provide fundamental insights to non-equilibrium self-assembly on temporally variant energy landscapes.

Defect-Induced Secondary Crystals Drive Two-Dimensional to Three-Dimensional Morphological Evolution in the Co-Self-Assembly of Polyferrocenylsilane Block Copolymer and Homopolymer.

Bottom-up fabrication protocols for uniform 3D hierarchical structures in solution are rare. We report two different approaches to fabricate uniform 3D spherulites and their precursors using mixtures of poly(ferrocenyldimethylsilane) (PFS) block copolymer (BCP) and PFS homopolymer (HP). Both protocols are designed to promote defects in 2D assemblies that serve as intermediate structures. In a multistep seeded growth protocol, we add the BCP/HP mixture to (1D) rod-like PFS micelles in a selective solvent as first-generation seeds. This leads to 2D platelet structures. If this step is conducted at a high supersaturation, secondary crystals form on the basal surface of these platelets. Co-crystallization and rapid crystallization of BCP/HP promote the formation of defects that act as nucleation sites for secondary crystals, resulting in multilayer platelets. This is the key step. The multilayer platelets serve as second-generation seeds upon subsequent addition of BCP/HP blends and, with increasing supersaturation, lead to the sequential formation of uniform (3D) hedrites, sheaves, and spherulites. Similar structures can also be obtained by a simple one-pot direct self-assembly (heating-cooling-aging) protocol of PFS BCP/HP blends. In this case, for a carefully chosen but narrow temperature range, PFS HPs nucleate formation of uniform structures, and the annealing temperature regulates the supersaturation level. In both protocols, the competitive crystallization kinetics of HP/BCP affects the morphology. Both protocols exhibit broad generality. We believe the morphological transformation from 2D to 3D structures, regulated by defect formation, co-crystallization, and supersaturation levels, could apply to various semicrystalline polymers. Moreover, the 3D structures are sufficiently robust to serve as recoverable carriers for nanoparticle catalysts, exhibiting valuable catalytic activity and opening new possibilities for applications requiring exquisite 3D structures.

Theoretical Investigation on the Metamaterials Based on the Magnetic Template-Assisted Self-Assembly of Magnetic-Plasmonic Nanoparticles for Adjustable Photonic Responses.

The assembly of artificial nano- or microstructured materials with tunable functionalities and structures, mimicking nature's complexity, holds great potential for numerous novel applications. Despite remarkable progress in synthesizing colloidal molecules with diverse functionalities, most current methods, such as the capillarity-assisted particle assembly method, the ionic assembly method based on ionic interactions, or the field-directed assembly strategy based on dipole-dipole interactions, are confined to focusing on achieving symmetrical molecules. But there have been few examples of fabricating asymmetrical colloidal molecules that could exhibit unprecedented optical properties. Here, we introduce a microfluidic and magnetic template-assisted self-assembly protocol that relies mainly on the magnetic dipole-dipole interactions between magnetized magnetic-plasmonic nanoparticles and the mechanical constraints resulting from the specially designed traps. This novel strategy not only requires no specific chemistry but also enables magnetophoretic control of magnetic-plasmonic nanoparticles during the assembly process. Moreover, the assembled asymmetrical colloidal molecules also exhibit interesting hybridized plasmon modes and produce exotic optical properties due to the strong coupling of the individual nanoparticle. The ability to fabricate asymmetrical colloidal molecules based on the bottom-up method opens up a new direction for the fabrication of novel microscale structures for biosensing, patterning, and delivery applications.

Interfacial properties and strengthening mechanisms of few-layered MXene reinforced Mg-based composites

In the present study, MXene-reinforced Mg matrix composites were manufactured via the electrostatic self-assembly protocol and spark plasma sintering (SPS) process to develop lightweight materials with high mechanical performance. Uniform dispersion of MXene sheets was achieved in MXene/AZ91 composites. A unique interfacial structure was confirmed in these composites, which exhibited an ultrafine MgO interlayer (grain size of ∼10 nm) coherently incorporated or intercalated into MXene layers. The unique interfacial structure contributed to robust interfacial bonding between MXene sheets and Mg matrix, resulting in a substantial mechanical performance enhancement. The yield strength of 325.3 ± 7.9 MPa and elongation of 8.8 ± 0.2% were achieved in 0.3vol% MXene/AZ91 composites, showing a significantly high strengthening efficiency of 159.1 without sacrificing ductility. Quantitatively investigation of strengthening behavior manifested that the load-transfer effect was the primary strengthening mechanism in MXene/AZ91 composites, and the simulated strength was well-matched with experimental results due to the special interfacial structure and excellent dispersion properties. This study could offer significant guidance for developing novel lightweight materials with high mechanical performance for structural applications.

Self-assembled colloidal gold nanoparticles as substrates for plasmon enhanced fluorescence

Decades of intense research in the field of nanoscience have led to the ability to produce nanoparticles (NPs) with controlled composition, shape, and size. One of the next key challenges is the self-assembly of appropriate NP building blocks into larger systems to obtain micro- or macroscale materials. To achieve this, self-assembly protocols must not only produce high-quality structures, but also deliver the assemblies of interest to desired locations on a substrate. In this review, we discuss different self-assembly strategies, focusing on colloidal gold NPs and applications as plasmon-enhanced fluorescence (PEF) platforms. These plasmonic substrates have been used for biosensing and cell imaging, based on the enhancement of fluorescent emitters, and applied to improve the emission efficiency of luminescent NPs. It is important to note that higher fluorescence enhancement relies on precise control of the location of gold NPs and fluorescent emitters on the plasmonic substrate. Despite the diversity of available self-assembly strategies, many of them provide similar levels of structural control over the placement of gold NPs on the substrate. To highlight this, we have organized the discussion according to strategies that result in similar degrees of structural control over the placement of gold NPs and its associated PEF effect.

Active phase morphology engineering of NiMo/Al2O3 through La introduction for boosting hydrodesulfurization of 4,6-DMDBT

Herein, we designed and constructed a mesoporous LaAlOx via a solvent evaporation induced self-assembly protocol. The structure and physicochemical property of the corresponding NiMo supported catalyst was analyzed by a set of characterizations, and its catalytic activity was investigated for hydrodesulfurization (HDS) of 4,6-dimethyldibenzothiophene. It has confirmed that the incorporation of La profoundly facilitate the generation of “Type II” NiMoS phase by weakening the interaction of Mo–O–Al leakage and promoting the sulfidation of both Ni and Mo oxides as well as changing the morphology of Ni promoted MoS2 slabs, thereafter boosting the HDS performance substantially. The finding here may contribute to the fundamental understanding of structure-activity in ultra-deep desulfurization and inspire the advancement of highly-efficient HDS catalyst in future.

Mesoscopic 2D molecular self-assembly on an insulator

Two-dimensional (2D) nanostructures and nanomaterials offer potential for a wide range of technological applications in electronics, optoelectronics, data storage, sensing and catalysis. On-surface molecular self-assembly—where organic molecules act as building blocks and where surfaces play the role of supporting templates—allows for the bottom-up synthesis of such 2D systems with tuneable atomically precise morphologies and tailored electronic properties. These self-assembly protocols are well established on metal surfaces, but remain limited on electronically gapped substrates (insulators, semiconductors). The latter are useful for preventing electronic coupling (that is, hybridization between molecular assembly and underlying surface) and for avoiding quenching of optical processes, necessary for prospective electronic and optoelectronic applications. In particular, molecular self-assembly on surfaces other than weakly interacting metals can be challenging due to substrate reactivity, defects and inhomogeneities, resulting in intricate energy landscapes that limit the growth kinetically and hampers the synthesis of large-area defect-free 2D systems. Here, we demonstrate the self-assembly of a 2D, atomically thin organic molecular film on a model wide bandgap 2D insulator, single-layer hexagonal boron nitride (hBN) on Cu(111). The molecular film consists of flat, aromatic 9,10-di-cyano-anthracene (DCA) molecules. Our low-temperature scanning tunnelling microscopy and spectroscopy measurements revealed mesoscopic (>100 × 100 nm2), topographically homogeneous crystalline molecular domains resulting from flat molecular adsorption and noncovalent in-plane cyano-ring bonding, with electronically decoupled molecular orbitals (MOs) lying within the hBN electronic gap. These MOs exhibit an energy level spatial modulation (∼300 meV) that follows the moiré work function variation of hBN on Cu(111). These findings pave the way for large-area, atomically precise, highly crystalline 2D organic (and metal-organic) nanomaterials on electronically functional wide bandgap insulators.

Stimuli-Responsive Triblock Terpolymer Conversion into Multi-Stimuli-Responsive Micelles with Dynamic Covalent Bonds for Drug Delivery through a Quick and Controllable Post-Polymerization Reaction

Stimuli-responsive copolymers are of great interest for targeted drug delivery. This study reports on a controllable post-polymerization quaternization with 2-bromomethyl-4-fluorophenylboronic acid of the poly(4-vinyl pyridine) (P4VP) block of a common poly(styrene)-b-poly(4-vinyl pyridine)-b-poly(ethylene oxide) (SVE) triblock terpolymer in order to achieve a selective responsivity to various diols. For this purpose, a reproducible method was established for P4VP block quaternization at a defined ratio, confirming the reaction yield by 11B, 1H NMR. Then, a reproducible self-assembly protocol is designed for preparing stable micelles from functionalized stimuli-responsive triblock terpolymers, which are characterized by light scattering and by cryogenic transmission electron microscopy. In addition, UV-Vis spectroscopy is used to monitor the boron-ester bonding and hydrolysis with alizarin as a model drug and to study encapsulation and release of this drug, induced by sensing with three geminal diols: fructose, galactose and ascorbic acid. The obtained results show that only the latter, with the vicinal diol group on sp2-hybridized carbons, was efficient for alizarin release. Therefore, the post-polymerization method for triblock terpolymer functionalization presented in this study allows for preparation of specific stimuli-responsive systems with a high potential for targeted drug delivery, especially for cancer treatment.

Polyferrocenylsilane Block Copolymer Spherulites in Dilute Solution

Self-assembly of block copolymers (BCP) into uniform 3D structures in solution is an extremely rare phenomenon. Furthermore, the investigation of general prerequisites for fabricating a specific uniform 3D structure remains unknown and challenging. Here, through a simple one-pot direct self-assembly (heating and cooling) protocol, we show that uniform spherulite-like structures and their precursors can be prepared with various poly(ferrocenyldimethylsilane) (PFS) BCPs in a variety of polar and non-polar solvents. These structures all evolve from elongated lamellae into hedrites, sheaf-like micelles, and finally spherulites as the annealing temperature and supersaturation degree are increased. The key feature leading to this growth trajectory is the formation of secondary crystals by self-nucleation on the surface of early-elongated lamellae. We identified general prerequisites for fabricating PFS BCP spherulites in solution. These include corona/PFS core block ratios in the range of 1-5.5 that favor the formation of 2D structures as well as the development of secondary crystals on the basal faces of platelets at early stages of the self-assembly. The one-pot direct self-assembly provides a general protocol to form uniform spherulites and their precursors consisting of PFS BCPs that match these prerequisites. In addition, we show that manipulation of various steps in the direct self-assembly protocol can regulate the size and shape of the structures formed. These general concepts show promise for the fabrication and optimization of spherulites and their precursors from semicrystalline BCPs with interesting optical, electronic, or biomedical properties using the one-pot direct self-assembly protocol.

Engineering quantum states and electronic landscapes through surface molecular nanoarchitectures

Surfaces are at the frontier of every known solid. They provide versatile supports for functional nanostructures and mediate essential physicochemical processes. Being intimately related with 2D materials, interfaces and atomically thin films often feature distinct electronic states with respect to the bulk, which are key for many relevant properties, such as catalytic activity, interfacial charge-transfer, or crystal growth mechanisms. Of particular interest is reducing the surface electrons' dimensionality and spread with atomic precision, to induce novel quantum properties via lateral scattering and confinement. Both atomic manipulation and supramolecular principles provide access to custom-designed molecular superlattices, which tailor the surface electronic landscape and influence fundamental chemical and physical properties at the nanoscale. Herein, we review the confinement of surface state electrons focusing on their interaction with molecule-based scaffolds created by molecular manipulation and self-assembly protocols under ultrahigh vacuum conditions. Starting from the quasi-free 2D electron gas present at the (111)-terminated surface planes of noble metals, we illustrate the enhanced molecule-based structural complexity and versatility compared to simple atoms. We survey low-dimensional confining structures in the form of artificial lattices, molecular nanogratings or quantum dot arrays, which are constructed upon appropriate choice of their building constituents. Whenever the realized (metal-)organic networks exhibit long-range order, modified surface band structures with characteristic features emerge, revealing intriguing physical properties, such as discretization, quantum coupling or energy and effective mass renormalization. Such collective electronic states can be additionally modified by positioning guest species at the voids of open nanoarchitectures [...].

Optimization of non-equilibrium self-assembly protocols using Markov state models.

The promise of self-assembly to enable the bottom-up formation of materials with prescribed architectures and functions has driven intensive efforts to uncover rational design principles for maximizing the yield of a target structure. Yet, despite many successful examples of self-assembly, ensuring kinetic accessibility of the target structure remains an unsolved problem in many systems. In particular, long-lived kinetic traps can result in assembly times that vastly exceed experimentally accessible timescales. One proposed solution is to design non-equilibrium assembly protocols in which system parameters change over time to avoid such kinetic traps. Here, we develop a framework to combine Markov state model (MSM) analysis with optimal control theory to compute a time-dependent protocol that maximizes the yield of the target structure at a finite time. We present an adjoint-based gradient descent method that, in conjunction with MSMs for a system as a function of its control parameters, enables efficiently optimizing the assembly protocol. We also describe an interpolation approach to significantly reduce the number of simulations required to construct the MSMs. We demonstrate our approach with two examples; a simple semi-analytic model for the folding of a polymer of colloidal particles, and a more complex model for capsid assembly. Our results show that optimizing time-dependent protocols can achieve significant improvements in the yields of selected structures, including equilibrium free energy minima, long-lived metastable structures, and transient states.

Low-dissipation self-assembly protocols of active sticky particles

We use neuroevolutionary learning to identify time-dependent protocols for low-dissipation self-assembly in a model of generic active particles with interactions. When the time allotted for assembly is sufficiently long, low-dissipation protocols use only interparticle attractions, producing an amount of entropy that scales as the number of particles. When time is too short to allow assembly to proceed via diffusive motion, low-dissipation assembly protocols instead require particle self-propulsion, producing an amount of entropy that scales with the number of particles and the swim length required to cause assembly. Self-propulsion therefore provides an expensive but necessary mechanism for inducing assembly when time is of the essence.

Bioactive Fibronectin-III10-DNA Origami Nanofibers Promote Cell Adhesion and Spreading.

The integration of proteins with DNA nanotechnology would enable materials with diverse applications in biology, medicine, and engineering. Here, we describe a method for the incorporation of bioactive fibronectin domain proteins with DNA nanostructures using two orthogonal coiled-coil peptides. One peptide from each coiled-coil pair is attached to a DNA origami cuboid in a multivalent fashion by attaching the peptides to DNA handles. These structures can then be assembled into one-dimensional arrays through the addition of a fibronectin domain linker genetically fused with the complementary peptides to those on the origami. We validate array formation using two different self-assembly protocols and characterize the fibers by atomic force and electron microscopy. Finally, we demonstrate that surfaces coated with the protein-DNA nanofibers can serve as biomaterial substrates for fibroblast adhesion and spreading with the nanofibers showing enhanced bioactivity compared to that of the monomeric protein.

Interface Engineering of a Bifunctional Cu-SSZ-13@CZO Core–Shell Catalyst for Boosting Potassium Ion and SO2 Tolerance

The poisoning of sulfur oxides and alkali metals emitted from diesel exhaust to active sites of copper ion-exchanged chabazite (Cu-CHA) catalysts is still present and remains a formidable challenge in practical application. Herein, a bifunctional core–shell structural Cu-SSZ-13@Ce0.75Zr0.25O2 (Cu-SSZ-13@CZO) catalyst was designed and fabricated via a hydrothermally induced self-assembly protocol, and the catalytic activity of Cu-SSZ-13@CZO for selective catalytic reduction (SCR) of nitrogen oxides (NOx) with ammonia was systematically investigated. It unveils that Cu-SSZ-13@CZO features Cu-SSZ-13 as the core and dispersed CZO as the shell and that the CZO shell could not only serve as a sacrificial site protecting the Cu-SSZ-13 active core from SO2 poisoning by the formation of Ce2(SO4)3, which could further act as adsorption sites capturing the K+ through the strong interaction between K+ and cerium sulfate, but also render additional Brønsted acid sites functioning as sacrificial sites to trap K+, thereafter inhibiting the adsorption of K+ directly on active Cu species in the Cu-SSZ-13 core. As a result, the as-constructed Cu-SSZ-13@CZO catalyst, therefore, exhibits perceptibly enhanced coresistance to sulfur and potassium ion poisoning with almost 100% NOx conversion in the temperature window of 275–475 °C as compared to 350–450 °C on pristine Cu-SSZ-13. The finding here may contribute to the fundamental understanding of the coresistance to sulfur oxides and alkali metal poison and thereafter inspire the advancement of a highly efficient NH3-SCR catalyst in the future.

Neuroevolutionary Learning of Particles and Protocols for Self-Assembly

Within simulations of molecules deposited on a surface we show that neuroevolutionary learning can design particles and time-dependent protocols to promote self-assembly, without input from physical concepts such as thermal equilibrium or mechanical stability and without prior knowledge of candidate or competing structures. The learning algorithm is capable of both directed and exploratory design: it can assemble a material with a user-defined property, or search for novelty in the space of specified order parameters. In the latter mode it explores the space of what can be made, rather than the space of structures that are low in energy but not necessarily kinetically accessible.

Theoretical investigation of the microfluidic and magnetic field-assisted self-assembly of colloidal magnetic-plasmonic nanoparticles

Patterning a wide range of colloidal plasmonic nanoparticles into prescribed spatial arrangements, analogous to the formation of natural materials, enables the fabrication of functionalized structures with novel optical properties, such as Fano resonance, magneto-optical Kerr effect, negative refraction, etc. Currently, capillarity-assisted particle assembly is always utilized to place colloidal particles at predetermined positions by exploiting the capillary forces resulting from the motion of an evaporating droplet. However, this technique requires specialized equipment and the assembly process is always carried out in an open system, thereby introducing the risk of contamination and limiting its applications. Here, we present a microfluidic and magnetic field-assisted self-assembly of colloidal magnetic-plasmonic nanoparticles by utilizing magnetic dipole–dipole interactions resulting from the localized magnetic gradient field produced by an array of soft-magnetic elements and external magnetic bias field. The magnetized magnetic-plasmonic nanoparticles are controlled to deposit at the predesigned traps microfabricated onto the soft-magnetic elements. After deposition, the inlet velocity of the microchannel is improved to clear away the particles out of the traps, forming arrays of patterns with consistent structures. Furthermore, a Lagrangian–Eulerian model is introduced for the first time to predict the processing of the microfluidic and magnetic field-assisted self-assembly of colloidal magnetic-plasmonic nanoparticles by taking the magnetic and hydrodynamic forces and particle–fluid interaction into account. Our analysis demonstrates that the particle–fluid interaction not only plays a significant role in determining the final self-assembled nanostructures, but provides an opportunity to improve the consistency of the assembled nanostructures. The microfluidic and magnetic field-assisted self-assembly protocol proposed here enables the patterning of colloidal magnetic-plasmonic nanoparticles to be carried out in a controlled environment and also opens up a new direction for assembling complex structures.

Sustainable synthesis of five-membered heterocycles using carbon dioxide and Fe-iminopyridine catalysts

Sustainable Fe-iminopyridine catalysts were investigated for the formation of five-membered heterocycles, cyclic carbonates and oxazolidinones from carbon dioxide and epoxides, aziridines and propargyl amines respectively. The homoleptic and heteroleptic Fe catalysts were prepared by a convenient self-assembly protocol. The optimal catalyst contained a hydrogen bond donor to activate substrate ring opening and a nucleophilic imidazole group to activate the CO2 electrophile. This approach represents a green CO2 recycling method to afford value-added chemicals with potential industrial applications.

Wafer-Scale and Full-Coverage Two-Dimensional Molecular Monolayers Strained by Solvent Surface Tension Balance.

Inspired by the outstanding properties discovered in two-dimensional materials, the bottom-up generation of molecular monolayers is becoming again extremely popular as a route to develop novel functional materials and devices with tailored characteristics and minimal materials consumption. However, achieving a full-coverage over a large-area still represents a grand challenge. Here we report a molecular self-assembly protocol at the water surface in which the monolayers are strained by a novel solvent surface tension balance (SSTB) instead of a physical film balance as in the conventional Langmuir-Blodgett (LB) method. The obtained molecular monolayers can be transferred onto any arbitrary substrate including rigid inorganic oxides and metals, as well as flexible polymeric dielectrics. As a proof-of-concept, their application as ideal modification layers of a dielectric support for high-performance organic field-effect transistors (OFETs) has been demonstrated. The field-effect mobilities of both p- and n-type semiconductors displayed dramatic improvements of 1-3 orders of magnitude on SSTB-derived molecular monolayer, reaching values as high as 6.16 cm2 V-1 s-1 and 0.68 cm2 V-1 s-1 for pentacene and PTCDI-C8, respectively. This methodology for the fabrication of wafer-scale and defect-free molecular monolayers holds potential toward the emergence of a new generation of high-performance electronics based on two-dimensional materials.